1

Part I

Introduction
Masamichi Fujihira Tokyo Institute of Technology, Yokohama, Japan

Researches on chemically modified electrodes was initiated about three decades ago by Hubbard [1, 2], Murray [3], and Millar [4] and their coworkers. The field of the chemically modified electrodes diverged sharply from the traditional field of adsorption on electrode surfaces [5] in a sense that one deliberately seeks to immobilize a chemical on an electrode surface so that the electrode displays the chemical, electrochemical, optical, and other properties of the immobilized molecule(s). After this first review, researches in the field in 1986 [6] is summarized and the concept of the chemically modified electrodes is extended from the viewpoint of the broadened definition of an electrode (system). In the broad sense, an ionically conductive phase being in contact with an electronically conductive phase can be regarded as the electrode (system). Then, a side view of an electrode (system) consists of (1) an electrode phase (the electronically conductive phase), (2) a transfer layer, (3) a diffused double layer, (4) a diffusion layer, and (5) a bulk solution. The region covering (2) and (3) is called an electrical double layer, and the region (2) ∼ (5) together corresponds to the ionically conductive phase. By broadening the

definition of the electrode surface (or interface) including the region (2) ∼ (5) into the bulk of solution, variation of possible ways to deliberately design the functional electrode surfaces has been expanded. For example, electrochemistry in micelles, microemulsions, and related microheterogeneous fluids has been studied [7]. Not only the functional variations but also the chemical variations of the chemically modified electrodes have been broadened. Atomically modified electrode surfaces [7] have become popular with the developments in electrochemistry on surfaces of single crystals [8, 9] as well as the study of underpotential depositions (UPD) [10]. Introduction of functions into the region (2)–(4) has been attained by using polymers [11, 12]. After a pioneering electrochemical study by Taniguchi et al. [13], self-assembled monolayers (SAMs) of disulfides and thiols on gold electrodes [14, 15] have been studied extensively. This Volume describes, how to prepare monolayer modified electrodes on metals, carbons, silicon, conducting metal oxides, and chalcogenides; how to prepare film modified electrodes including polymer

Encyclopedia of Electrochemistry. Edited by A.J. Bard and M. Stratmann Vol. 10 Modified Electrodes. Edited by M.Fujihira, I.Rubinstein, and J.F.Rusling Copyright  2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. ISBN: 978-3-527-30402-8

2

Part I Introduction

modified electrodes; how to characterize ex situ or in situ the modified electrodes, and, finally, functions and applications of modified electrodes.
References
1. R. F. Lane, A. T. Hubbard, J. Phys. Chem. 1973, 77, 1401–1410. 2. R. F. Lane, A. T. Hubbard, J. Phys. Chem. 1973, 77, 1411–1421. 3. P. R. Moses, L. Wier, R. W. Murry, Anal. Chem. 1975, 47, 1882–1886. 4. B. F. Watkins, J. R. Behling, E. Kariv et al., J. Am. Chem. Soc. 1975, 97, 3549–3550. 5. R. W. Murray, in Electroanalytical Chemistry (Ed.: A. J. Bard), Marcel Dekker, New York, 1984, pp. 191–368, Vol. 13. 6. M. Fujihira, in Topics in Organic Electrochemistry (Eds.: A. J. Fry, W. E. Britton), Plenum, New York, 1986, pp. 255–294. 7. J. F. Rusling, in Electroanalytical Chemistry (Ed.: A. J. Bard), Marcel Dekker, New York, 1994, pp. 1–88, Vol. 18.

8. J. Clavilier, J. Electroanal. Chem. 1980, 107, 205–209. 9. A. Hamelin, in Modern Aspect of Electrochemistry (Eds.: B. E. Conway, R. H. White, J. O. M. Bockris), Plenum, New York, 1985, pp. 1–101, Vol. 16. 10. D. M. Kolb, in Advances in Electrochemistry and Electrochemical Engineering (Eds.: H. Gerischer, C. W. Tobias), John Wiley & Sons, New York, 1978, pp. 125–271, Vol. 11. 11. R. Murray (Ed.), Molecular Design of Electrode Surfaces, in Techniques of Chemistry (Eds.: A. Weissberger, W. H. Saunders Jr.), John Wiley & Sons, New York, 1992, Vol. 22. 12. G. Inzelt, in Electroanalytical Chemistry (Ed.: A. J. Bard), Marcel Dekker, New York, 1994, pp. 89–241, Vol. 18. 13. I. Taniguchi, K. Toyosawa, H. Yamaguchi et al., J. Chem. Soc., Chem. Commun. 1982, 1032–1033. 14. R. G. Nuzzo, D. L. Allara, J. Am. Chem. Soc. 1983, 105, 4481–4483. 15. L. H. Dubois, R. G. Nuzzo, Annu. Rev. Phys. Chem. 1992, 43, 437–463.

15

1.1

Modification of Transparent Conducting Oxide (TCO) Electrodes through Silanization and Chemisorption of Small Molecules Michael Brumbach and Neal R. Armstrong University of Arizona, Tucson, Arizona
1.1.1

Introduction The Metal Oxide Electrode and Modification Schemes Surface modification of transparent conducting oxide (TCO) thin film electrodes (indium–tin oxide (ITO), SnO2 , TiO2 , ZnO, etc.) has traditionally been directed toward enhancement of heterogeneous electron transfer rates of solution species for which the electron transfer process is thermodynamically favored but kinetically inhibited. The surface-confined molecule is intended to exhibit rapid and reversible electron transfer at the oxide surface to provide rapid mediation of electron transfer to a solution species [1]. Surface-confined molecules are typically not directly ‘‘wired’’ into the conduction or valence band of the oxide, but electron transfer rates are often reasonably fast for these species simply because they have been brought into close
1.1.1.1

proximity to the electronically active sites of the metal oxide. Chemical modification of the TCO surface can be accomplished through covalent bond formation (silanization) or through chemisorption of molecules containing functional groups such as carboxylic acids, phosphonic acids, alkanethiols, and amines. Initial modification strategies were employed for oxidation of biomolecules, such as ascorbic acid, neurotransmitters, heme proteins, and so forth using various surface-confined molecules or thin films of conducting polymers. Modification schemes have also been used to attach photoactive dye molecules, such as phthalocyanines, porphyrins, and a variety of organometallic complexes, to oxide surfaces to enhance redox processes between solution species and semiconducting electrodes [2–6]. Chemical modification of conducting oxide surfaces has also been used to enhance charge injection rates into condensed phase organic thin film devices (for example, in organic light emitting diodes (OLEDs) and organic photovoltaics (OPVs)). There is still some debate as to whether the enhancement in device performance is due to enhancements in wettability of the oxide surface toward the nonpolar molecules used in these devices, to changes in work function of the oxide surface, and/or to enhancements in

Encyclopedia of Electrochemistry. Edited by A.J. Bard and M. Stratmann Vol. 10 Modified Electrodes. Edited by M.Fujihira, I.Rubinstein, and J.F.Rusling Copyright  2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. ISBN: 978-3-527-30402-8

16

1 Preparation of Monolayer Modified Electrodes

intrinsic rates of charge injection [7–13]. Many of the same strategies initially used to enhance solution electron transfer rates on these oxide surfaces appear to positively impact device efficiencies in simple OLEDs and OPVs [9, 14–18].
Commonly Encountered TCO Electrodes The most commonly encountered TCO electrodes, typically studied as thin films, are antimony-doped tin oxide (ATO) or fluorine-doped tin oxide (FTO), ITO, titanium oxide (anatase or rutile, TiO2 ), and zinc oxide (ZnO) [19]. There are also some recently reported trinary and ternary oxides based on modifications of ITO, zincindium tin oxide, ZITO or IZTO, for example, which may become more popular with time as electrodes for solution-based redox chemistry and as anodes in devices such as OLEDs and OPVs [7]. These new tailored composition oxides may exhibit higher stability, higher work functions, and/or a greater variety of surface sites with more possibilities for chemical modification. An idealized metal oxide surface is shown in Fig. 1, where the metal atoms are in tetrahedral coordination with four oxygen atoms. This metal oxide, empirical formula MOx , is stoichiometric, having no defects or surface hydrolysis products, and can be considered as a typical platform for understanding the modification of most TCO thin film materials of electrochemical interest. TCO films are typically deposited by sputtering, chemical vapor deposition, or pulsed laser deposition, and tend to be ‘‘microcrystalline’’ whose dominant exposed faces tend to be either 111 or 100
1.1.1.2
O M O O O M O O M O O M O O M O O M O O

lattice terminations [19–23]. The structure and electronic properties of several TCO films can be summarized as follows: Indium–Tin Oxide (ITO): ITO has the complex unit cell of indium oxide (bixbyite lattice) consisting of more than 80 atoms. Indium oxide has two distinct indium sites in the lattice and as many as four oxygen species, considering surface hydrolysis products and oxygen vacancies [24]. Oxygen vacancies and electron-rich interstitial tin dopant sites lie close in energy to the conduction band edge so that promotion of electrons into the conduction band, at room temperature, is facile [25]. Figure 2 shows the proposed band diagram for ITO exhibiting the common features that dictate the electrical properties of many TCO materials. The upper portion of the valence band arises from filled O(2p) orbitals, while the lower part of the conduction band arises from unfilled metal orbitals (In(5s) orbitals in the case of ITO). Oxygen defects are induced into the TCO material during its formation, usually by depositing or annealing the thin film in an oxygen-deficient atmosphere, thus creating electron-rich sites within a few kT of the conduction band edge. An interstitial dopant, tin, is often introduced into these In2 O3 lattices at concentrations up to 10% (atomic), producing additional electron-rich sites within a few kT of the conduction band edge. In ITO, the donor density can be as high as 1020 cm−3 with a sheet resistance as low as 10 sq−1 . The introduction of oxygen defect sites and other dopants, however, may also increase the chemical reactivity of these oxide surfaces toward hydrolysis
O M
Fig. 1 Schematic view of an O ideal metal oxide surface.

1.1 Modification of TCO Electrodes through Silanization and Chemisorption of Small Molecules
Fig. 2 Schematic view of the energy levels in ITO showing the components of the valence band and conduction band regions of the oxide, the presence of oxygen defect sites and interstitial tin dopant sites that contribute to electron density near the conduction band edge, rendering the oxide conductive at room temperature (after Ref. 25).

17

In: 5p

In: 5s Energy

0.03 eV EF

and other components of the vacuum deposition system. The reactivity of the oxide surface has important consequences for their further modification and enhancement of electron transfer rates, which have been extensively studied as functions of surface pretreatment [8, 24, 26, 27]. Tin Oxide (SnO2 ): Tin oxide has a tetragonal rutile structure with a unit cell of six atoms. The electrical conductivity of n-doped SnO2 is due to the presence of oxygen vacancies, interstitial tin (in excess), or added dopants such as fluorine, chlorine, or antimony. Carrier concentrations can be increased to approximately 1020 cm−3 through doping from the intrinsic concentration of approximately 1018 cm−3 for SnO2 [19]. Titanium Oxide (TiO2 ): Titanium oxide exists in three different crystallographic structures, rutile, anatase, and brookite. The most commonly studied material is rutile, being the most stable phase, although many studies have been conducted on the anatase phase as well [28]. Stoichiometric rutile contains Ti4+ in six-fold coordination with oxygen staggered by Ti4+ in five-fold coordination. Oxygen atoms at the surface are often bridging and only two-fold coordinated [23]. The band gap of rutile is 3.0 eV, and 3.2 eV for anatase, making titanium oxide a useful material for photocatalysis [29–31]. Photoelectrochemical cells based on sintered nanoparticulate arrays of anatase or

V o: s 2

Sn3+: 5s1

O2−: 2p6 In: 3d10

thin film TiO2 electrodes have been quite successful [32, 33]. Both anatase and rutile forms of TiO2 are readily n-doped by creation of oxygen vacancies leaving electron-rich Ti3+ and Ti2+ states in the band gap, with electron energies sufficiently close to the conduction band edge so as to provide for reasonable room temperature conductivity.
Variability in TCO Electrodes TCO thin films can exhibit tremendous variability in transparency, microstructure (and surface roughness), surface composition, conductivity, chemical stability at high current densities (in OLEDs, OPVs, and chemical sensors), and in their chemical compatibility with contacting organic layers. Variability is often noticeable from production batch to production batch and within batches of the same metal oxide material [34]. Surface pretreatment conditions have also been shown to dramatically impact the electrochemical, physical, and photophysical properties of metal oxide films [8, 9, 24, 26, 27, 35]. Modification
1.1.1.3

18

1 Preparation of Monolayer Modified Electrodes

of these surfaces through silanization and chemisorption would appear to be a means for improving the stability of these oxide surfaces, enhancing their compatibility with nonpolar solvents and condensed phase materials, and optimizing rates of interfacial electron transfer.
1.1.2

Factors that Control the Surface Composition of the TCO Electrode

The structure shown in Fig. 1, representing an ideal metal oxide surface, provides a useful platform for understanding metal oxide surfaces. A further, and more realistic, modification to the model would account for the presence of surface hydrolysis products as shown in Fig. 3. Surface hydrolysis critically affects the chemical modification of the TCO surface. Moderate hydrolysis may only break bridging oxygen-metal bonds leaving surface hydroxyl groups. More extensive hydrolysis can lead to fully hydroxylated metal species that may remain physisorbed. The presence of dopants and/or oxygen vacancies, as shown in Fig. 4, can also affect the metal oxide surface by creating sites that can react with adventitious impurities present during, or after, deposition. Varying degrees of hydroxylation and defect density, as well as the preferential migration of dopants to the near surface region, contribute to the high degree of heterogeneity in electron transfer rates and chemical compatibility commonly
HO M O M O O HH O O M O O M O H H HO O OO M O M O OH HH OO M O

observed with oxide electrodes. Hydrolysis products on ITO remain strongly physisorbed (precipitated) to the electrode surface at greater than monolayer coverage, constituting a primary factor for the appearance of electrical ‘‘dead spots’’ on the oxide surface [24, 36, 37]. The so-called ‘‘dead spots’’ are regions exhibiting poor electroactivity or no electroactivity. Surface hydrolysis of metal oxide surfaces can be examined by comparison to solution equilibrium constants for hydrolysis and solubility. Indium oxide has a favorable equilibrium constant for hydrolysis [38–40]: In2 O3 + 3H2 O ←−→ 2In(OH)3 K = 4.3 × 101 (1) Whereas, the fully hydrolyzed In moiety, In(OH)3 , has a very low solubility product. In(OH)3 ←−→ In3+ + 3OH− Ksp = 1.3 × 10−37 (2) There is also the possibility for incomplete hydrolysis of an indium surface oxide creating the intermediate hydroxylated species, InOOH: In2 O3 + H2 O ←−→ 2InOOH (3)

This type of surface site may also arise by the nucleophilic attack of water on exposed oxide defects, which serve as sites for dissociative adsorption. In contrast, hydrolysis of tin oxide is significantly less

H H O O M

Fig. 3 Schematic view of an oxide O surface that has undergone hydrolysis,

producing hydroxylated sites, and even physisorbed metal hydroxide, O monomers or polymers.

1.1 Modification of TCO Electrodes through Silanization and Chemisorption of Small Molecules
Fig. 4

19

Schematic view of the O near surface region of the oxide M thin film with oxygen vacancies, producing electron-rich metal O sites and dopant sites of lower stoichiometry, and also creating electron-rich sites.

O

+n +n M M O

O M O

O D O

O D O

O +x M +n

O O

O

favored than for indium oxide, at any pH [38, 39]: SnO2 + 2H2 O ←−→ Sn(OH)4 K = 5.6 × 10−10 (4)

While the solubility of tin hydroxide is higher than for indium hydroxide: Sn(OH)2 ←−→ Sn2+ + 2(OH− ) K = 1.4 × 10−28 Sn(OH)4 ←−→ Sn4+ + 4(OH− ) K = 7.2 × 10−14 (6) (5)

The typical doped SnO2 thin film can therefore be expected to show monolayer (but not significantly higher) coverages of hydroxide species. Hydroxide species in excess of monolayer coverage would be expected to be more easily removed from the oxide surface through pretreatment steps. For titanium oxides and zinc oxides, similar hydrolysis and dissolution processes must be considered [39, 41]: Zn(OH)2 ←−→ Zn2+ + 2OH− Ksp = 3 × 10−16 Ti(OH)4 ←−→ Ti
4+

determining the surface coverage of the modifier. Rates of electron transfer/charge injection at the modified oxide surface are subsequently affected. Despite the uncertainties in oxide surface composition, several modification protocols have been developed over the last thirty years, which yield improved electrochemical performance of the TCO thin film. Two strategies have continued to be successful at modifying metal oxide electrodes; silanization, covalent bond formation to metal hydroxides, and chemisorption, using functional groups known to either hydrogen bond to M–OH sites and/or to coordinate to metal cation sites.
1.1.3

Chemical Modification of TCO Surfaces Using Silane Chemistries Introduction to Silane Modification Surface modification of TCO thin films with monofunctional, difunctional, and trifunctional organosilanes arose initially from protocols developed in modifying silica surfaces [42]. The covalent attachment of functional groups to the oxide surface through silanization involves the coupling of the functionalized silane to the metal oxide at hydroxylated sites, through a metal–oxygen–silicon bonded network with the release of one or more ‘‘leaving groups’’ as shown in Fig. 5. ‘‘Leaving groups’’ are generally chlorides or alkoxides (methoxide or ethoxide) yielding HCl or the corresponding alcohol as by-products.
1.1.3.1

(7)

+ 4OH

Ksp = 7.94 × 10−54 (8) Chemical modification of these oxides, therefore, needs to take into account the routes to formation and loss of surface hydroxide species playing a key role in

20

1 Preparation of Monolayer Modified Electrodes Schematic view of silane modification of an oxide R–Si–O–M + MeOH surface, using (as an example) a tri-methoxy silane. Reaction with only one surface hydroxide OMe site is shown, releasing methanol as the product. Unreacted hydroxide sites R remain, as do unreacted alkoxy OMe MeO OMe groups on the silane, which can Si further cross-link under H H appropriate conditions.
OMe
Fig. 5

R–Si(OMe)3 + HO–M

R MeO Si H O M O O O M O H O O M O OMe MeO O

R Si O M O

O

O

O O

O

M O

M O

M O

In the absence of water, silane modifiers can form multiple bonds to the surface creating a clawlike multidentate attachment, Fig. 6(a) [43]. Silanes with multiple leaving groups, however, will generally cross-link during the surface attachment process, or afterward during storage in high humid environments, to form a polymeric, hydrolytically stable layer, as shown in Fig. 6(b). The functional group (R) can be an alkyl or aromatic group terminating with a redox active molecule (ferrocene,
R Si O M O (a) R O H O M O (b) O O Si H O O Si R OMe H O O O O O M M M O O H Si R R O Si H O O H O R O O M O O M O H O O M O R OMe Si O H O M O O M O

viologen, porphyrin, phthalocyanine, etc.) or can simply be tailored to control the wettability of the TCO surface. It is desirable to start with a surface that has been mildly hydroxylated for surface modification, as opposed to the stoichiometric surface shown in Fig. 1, so that there are sufficient reactive sites for silanization. If the redox chemistry of an attached molecule is to be optimized, it is also desirable to work with monofunctional silanes. In this case, only one

MeO H O

R Si O O M O O

O

O Si H O O O
Fig. 6

O

Schematic view of cross-linking a silane surface modifier as it passes M M through the (a) multidentate/brush M O phase to the (b) fully cross-linked phase, O O with relatively few unreacted M−OH groups left on the oxide surface.

1.1 Modification of TCO Electrodes through Silanization and Chemisorption of Small Molecules

21

attachment site is created, thereby leaving the tethered redox group in close proximity to the electrode surface and promoting reasonable rates of electron transfer [1]. Control of surface hydroxylation, however, given the tendency of oxides to extensively hydrolyze, is problematic and affects the coverage of redox active groups that can be achieved through silanization reactions. Silane formation on SnO2 surfaces, where hydrolysis can be more easily controlled appears to be a more advantageous strategy. Silanization is generally performed in refluxing toluene or benzene with low concentrations of the desired silane. Silanes of the form X(R2)2 SiR1 have only one reactive bond and can therefore make only one bond with the metal oxide surface (see Fig. 5). X represents a chloride, methoxy, ethoxy, or other ‘‘leaving group.’’ R2 groups are typically small substitutents such as methyl groups, but can be changed to something larger such as phenyl groups to provide steric hindrance and blocking unsilanized surface sites. Large side chains would, however, also sterically reduce the number of silane molecules bound to the oxide. The energy barrier for the surface bonded silane to rehydroxylate, and the metal oxide to ‘‘heal,’’ with a bridging oxygen, is extremely low. Therefore, these brushlike phases are generally unstable and nearly all of the brushlike phases reported in the literature are produced with triply reactive silanes reacted under highly controlled dry conditions such that multiple bonds can be made with the surface, as shown in Fig. 6(a). According to Kirkov, there are 2.23 × 1015 Sn−O sites cm2 on SnO2 [44, 45], and similar site densities can be expected for ITO and TiO2 . Since not all sites will be uniformly reactive, a maximum surface coverage is approximately 10−10 moles cm−2 for a

brushlike silanized layer with tridentate attachment.
Examples of Silane Modification Trimethoxysilane molecules will covalently attach to ITO following a reflux of the electrode in a 10% (silane:toluene) solution for approximately 30 min [37]. Excess silane can be removed by sonication for 10 min in pure toluene. Water contact angle measurements on such modified surfaces immediately show increased contact angles, consistent with the addition of silane molecules with nonpolar functionality to the surface. On ITO, the contact angle can change from less than 30◦ before modification, to angles higher than 65◦ after modification, and even higher if cross-linking of the silane occurs [37, 46]. X-ray photoelectron spectroscopy (XPS) is also used to verify the presence of silicon on the surface. Shepard and Armstrong have measured the electrode interfacial capacitance at tin oxide electrodes modified with a series of silanes [47–50]. The capacitance studies showed the sensitivity of the electrical properties of modified surfaces to variations in reaction conditions during silanization, and to the types of functional groups attached to these surfaces. Untereker et al. used several methods for creating clawlike brush phase silane layers on SnO2 , TiO2 , and glass [43]. SnO2 was modified with γ aminopropyl-triethoxysilane, 3-(2-(aminoethylamino)propyltrimethoxysilane), and β-trichlorosilyl-2-ethylpyridine by exposing the electrodes to 2–10% organosilane solutions in refluxing benzene or xylene under N2 for up to 12 h. The electrodes were washed with dry benzene. A similar procedure was used for silanizing SnO2 and TiO2 at room temperature with lower silane concentrations.
1.1.3.2

22

1 Preparation of Monolayer Modified Electrodes

Another brief exposure was performed with 1% organosilane in benzene at 6 ◦ C under argon for 10 s. A more aggressive silanization procedure was used to modify glass with neat organosilane in a sealed tube at 90 ◦ C for 12 h. The authors evaluated their films via XPS to determine thickness and approximate surface coverages. Finklea and Murray accomplished the silanization of single crystal TiO2 following a 5 min exposure of the electrodes to 10% silane solutions in either toluene or benzene. Excess silane was removed with fresh solvent, while methanol was found to reduce the silane coverage [51]. The silanes evaluated in these studies were 3-(2-aminoethylamino)propyltrimethoxysilane, methyltrichlorosilane, and dimethyl-dichlorosilane. XPS surface analysis showed the presence of some cross-linking but could not conclusively characterize the homogeneity of the modified surface. Their photocurrent results indicated that the M−O−Si bond is oxidatively stable to photo-generated holes and, therefore, may provide a useful means of modifying TiO2 particles for use in dye sensitized solar cells DSSCs. Redox active and photoelectrochemically active metal phthalocyanines were attached to γ -aminopropyltriethoxysilane-modified SnO2 . Tetrasulfonated cobalt and copper phthalocyanines (CoTSPc and CuTSPc) were modified with thionyl chloride, to provide for attachment to the silanized surface via formation of sulfonamide linkages [47, 50]. Phenyl and diphenyl silane-modified ITO surfaces have been used to improve the physical compatibility with Langmuir–Blodgett thin films of phthalocyanine assemblies, where the direct electron transfer of the assembly with the ITO surface was of concern [46].

C60 has been tethered to ITO in a self-assembled network by exposing the ITO to basic conditions followed by a reflux in high concentrations of (MeO)3 Si(CH2 )3 NH2 in benzene for half a day [52]. The electrodes were then multiply rinsed before refluxing in a 1-mM solution of C60 in benzene for as long as 2 days. This scheme resulted in an ITOsilane-N-C60 tethered network and allowed for the formation of an organized C60 layer on the ITO surface. Quartz and glass were similarly modified for spectroscopic comparisons. Nearly, all monolayer coverage of C60 was determined electrochemically, 1.7 × 10−10 mols cm−2 . Reduction of C60 in these films is shifted more negatively, indicating a direct interaction between the underlying silyl-amine layer and C60 .
1.1.3.3 Silane Modification of Electrodes for Use in Devices Perfect cross-linking of silane molecules is unlikely in most circumstances due to a mismatch in the lattice spacing between the cross-linked silane layer and the underlying metal oxide substrate. A more accurate picture of a silanized surface would consist of some silane molecules attached via multidentate binding interspersed with cross-linked neighboring silanes as shown in Fig. 6(b). Extensive cross-linking of surface silanes may provide a stable modified surface; however, it also appears to impede electron transfer and, for optimization of solution redox processes, may not be desirable [1, 46]. Marks and coworkers have shown how extensively cross-linked silane monolayers and multilayers can be used to stabilize an electrode and regulate charge injection in a condensed OLED phase [14, 53–55]. Their approach has been to start with silanes functionalized with various redox active

1.1 Modification of TCO Electrodes through Silanization and Chemisorption of Small Molecules

23

groups and to terminate by functional groups, which can subsequently be converted to new reactive silanes, to produce a layer-by-layer ‘‘self-limiting’’ chemistry. Multilayer formation can be well controlled, leading to desired film thicknesses and orientation of the charge transporting core molecules [14]. In general, these modified electrodes show significantly improved performance as anodes in OLEDs, apparently due to the fact that hole injection into the tri-arylamine hole transport layer (which is the core molecule being cross-linked by these silanes), is impeded after modification. This allows for a more balanced injection of both holes and electrons in the device and results in the emissive state forming in the middle of the thin film device [14]. Chlorosilanes are often used to aid in the extensive cross-linking that is desired for the modification of anodes for use in OLED devices. Chlorosilanes liberate HCl as a by-product of silane attachment, which can degrade the TCO surface if low concentrations of base are not added for neutralization. No significant etching of the TCO anode surface has been noted, and surface analysis of the modified electrode generally indicates no entrapped chlorine [14, 51–53]. Silane modification of ITO and SnO2 electrodes has also been used to create nearly perfect ‘‘blocking’’ electrodes, such as thin films where rates of electron transfer are intentionally kept low, so as to provide for measurement in changes in interfacial potential of an additional overlayer, such as a bilayer lipid membrane, during ion transport, pH changes, and so forth. Hillebrandt and Tanaka have evaluated the effects of octyltrimethoxysilane (OTMS), octadecyltrimethoxysilane (ODTMS), and octadecyltrichlorosilane (OTS) on ITO for applications to lipid-membrane-based

biological sensors [56–58]. The authors found that the ITO electrodes can be effectively blocked from electron transfer by silanization. Silanization results in more uniform films suitable for the biological sensor platform, with ionic diffusion occurring almost entirely from pinholes in the film. Silanization was accomplished by sonicating ITO substrates in 5 vol% solutions of the silane in dry toluene with 0.5 vol% n-butylamine, followed by 30 min of incubation. Temperatures were held below 293 K for ODTMS and below 280 K for OTMS. Sonication in dry toluene for 2 min removed excess silane. Markovich and Mandler also derivatized ITO with ODTMS but derivatization was performed over a seven-day period [59, 60]. The long alkyl chain length and stability of cross-linked silanized surfaces also allows for their use as masks for patterning and etching TCO substrates. ODTMS has been used as a mask for patterning ITO [61]. Luscombe et al. have used perfluorodecyltrichlorosilane as a mask for etch resists for lithographic processing of ITO surfaces [62].
1.1.4

Modification of TCO Surfaces through Chemisorption of Small Molecules
1.1.4.1 Modification using Small Molecules Containing Carboxylic Acid Functionality Modification of electrode surfaces through chemisorption has been more in recent reports than silanization, and its discussion here is intended to contrast the strategies used for both types of surface modification. Chemisorption of small molecules to the TCO surface allows for robust modifications occurring over short distances and with relatively strong interactive forces ( H = ca. 200 kJ mol−1 ) through

24

1 Preparation of Monolayer Modified Electrodes

combinations of electrostatic, H-bonding, and metal ion coordination. Chemisorption processes generally have a high activation barrier for adsorption, may be irreversible, and can ‘‘self-limit’’ at monolayer coverage. Owing to the amphoteric nature of metal oxide surfaces, chemisorption of Lewis acids such as carboxylic acids, aliphatic and aromatic amines, and phosphonic acids are generally successful. Chemisorption typically anchors individual molecules in close proximity to metal cationic sites and may also compete for sites with surface hydrolysis products. Previous work has examined chemisorption to ITO, SnO2 , and TiO2 surfaces, with most of the studies reporting adsorption of either carboxylic or phosphonic acids or salts. Carboxylate functionalities have been used repeatedly and successfully as an anchoring group for molecular chemisorption to oxide electrodes proceeding through the formation of an ester linkage to the metal with the loss of water, or through hydrogen-bonding interactions to surface hydroxyl groups. Possible interactions for carboxylic groups are shown in Fig. 7. Binding constants for the carboxylic group
R O O M O O C O M O O H O M O H H O O M O C

for ITO and ATO have been determined to be as high as 8 × 104 M−1 [34]. Chemisorption is often as successful as silanization at obtaining monolayer coverages of small molecule modifiers. As an example, Davis and Murray attempted to couple iron porphyrins to amineterminated silanized SnO2 surfaces. The authors found that the surface coverage was independent of the apparent extent of surface silanization [63]. Silanized and unsilanized electrodes were soaked in 5 mM porphyrin dissolved in DMF, THF, or pyridine solutions overnight. Porphyrins with pendant carboxylic acid groups produced higher surface coverages (determined by coulometric analysis of the voltammetry of the surface-confined species) on bare, unmodified SnO2 than seen on SnO2 electrodes modified with 3-(2aminoethylamino)propyltrimethoxysilane. Zotti and coworkers adsorbed several carboxylated ferrocene derivatives on ITO: ferrocene-carboxylic acid (Fc(COOH)), ferrocene-dicarboxylic acid (Fc(COOH)2 ), and ferrocenylheptanoic acid Fc(CH2 )6 COOH [64]. Fc(COOH) was adsorbed from 1-mM solutions of the molecule in 5/95 ethanol/hexane for as
R

R H O M O (a) R H O M O (b) O O O M O O C O O M

O H O

H O O M

O

O

O M

O

O

Fig. 7 Schematic views of the possible interaction modes of carboxylic acids H with TCO surfaces. H O (a) ‘‘Metal–ester’’-like interactions; O OO O O (b) ‘‘bridging’’ coordination with metal M M M ion sites (created by formation of oxygen vacancies in the lattice); O O O O (c) ‘‘chelating’’ interaction – one (c) carboxylate per open metal site [30].

R

R

1.1 Modification of TCO Electrodes through Silanization and Chemisorption of Small Molecules

25

long as 16 h, followed by a rinse with acetonitrile. Higher solution concentrations were found to yield higher surface coverage, following a Langmuir adsorption isotherm, with saturation coverage (ca. 1 × 10−10 mols cm−2 ) occurring at approximately 10 mM solution concentration. The saturation coverage, however, was 25% of the expected monolayer coverage (4 × 10−10 mols cm−2 ) based on the geometric area [65]. Fc(COOH)2 was adsorbed from ethanol, while Fc[(CH2 )6 COOH] was adsorbed from hexane. Adsorption of these molecules appears to be kinetically limited. Recent work has shown that time for adsorption is required to remove hydrolysis products (e.g. In(OH)3 ) or other nonelectroactive species adsorbed to the ITO surface [66]. Fc(COOH)2 has been used successfully to increase electron transfer rates and for enhancing the performance of organic light emitting devices and organic photovoltaics [24, 37]. In addition to modifications of electron transfer rates, carboxylic acid-modified small molecules have been used to introduce dipole fields at the surface of TCO substrates. For example, benzoic acid derivatives have been used to modify the interface dipole at ITO surfaces, attached to the oxide surface via formation of a Langmuir–Blodgett thin film. Changes in work function closely relate to changes

in the dipole induced by the derivatized modifiers [67]. Dye molecules possessing carboxylate functionalities have been extensively explored as sensitizers of semiconducting oxide electrodes toward visible light in photoelectrochemical cells [4, 32, 68]. Dye sensitization was first explored as a means of enhancing the photocatalytic properties of TiO2 [69–72]. Spitler and coworkers investigated dye sensitization of ZnO electrodes using carboxylic acid functionalized dyes [4–6]. The authors found that the photocurrent produced by dye sensitized TiO2 and ZnO crystals closely resembled the absorption spectrum of the dye, indicating that the dye is in close proximity to the crystal and, upon excitation, injects charge into the semiconductor from energy levels that are relatively unperturbed. The observation of photocurrent from dye sensitized planar semiconductors led to the evolution of the DSSC, on the basis of extremely high surface area nanoparticulate oxides, usually TiO2 . The most successful dye for sensitization, N3, cis-bis(isothiocyanato) bis(2,2 -bipyridyl-4,4 dicarboxylato) ruthenium (II), employs several carboxylic acid groups for adsorption to TiO2 , ZnO, SnO2 , and/or ITO from an ethanol or acetonitrile solution over a several-hour period [32]. Electron injection from the excited state of this dye to the conduction band
R R HO O H O M O O M O O (b) O O M O C O H H O O M O

Schematic views of possible hydrogen-bonding interactions of protonated carboxylic acids to an ideal TCO surface. (a) Interaction mode where the protonated carboxylic acid H-bonds to a bridging oxygen. A hydroxylated metal site also H-bonds to the second carboxylic oxygen. (b) A single hydrogen bond is also plausible.
Fig. 8

C O
H H O O

O M O (a)

O

26

1 Preparation of Monolayer Modified Electrodes

of the oxide is believed to occur on a femtosecond timescale [73, 74]. Binding constants for the carboxylated dyes assuming an ester linkage are 8 × 104 M−1 on SnO2 from chloroform [73]. A similar carboxylated ruthenium complex has been evaluated on ATO, ITO, TiO2 , and SiO2 [34]. The authors argue for ester linkages on all substrates except silica. On silica, adsorption occurs through a chelating carboxylato link with a second carboxylate group hydrogen bonding to the surface. Hydrogen-bonding interactions for protonated carboxylic groups to TCO surfaces can also be envisioned as shown in Fig. 8. Notice that physisorption can occur to metal oxide surfaces, which are not hydroxylated, by formation of hydrogen bonds to bridging oxygens.
Modification Using Phosphonic Acids and Other Chemisorbing Functionalities Phosphonic acids are known to chemisorb strongly to oxides such as ITO and have been used to help produce lithographically patterned ITO surfaces [75, 76]. The schematic view of the adsorption of such materials is shown in Fig. 9. Adsorption of hexylferrocene phosphonic acid (Fc[(CH2 )6 PO(OH)2 ]) has been investigated by Vercelli et al. from ethanol to silanized and unsilanized ITO surfaces
1.1.4.2
R HO HO M O (a)
Fig. 9

[77]. A maximum surface coverage was obtained at 4.2 × 10−10 mols cm−2 , approximately four times the surface coverage obtained with the analogous carboxylated ferrocene. Cyclic voltammetry (CV) of the adsorbed (Fc[(CH2 )6 PO(OH)2 ]) exhibits a symmetric voltammogram about the x-axis (applied potential axis). The high degree of symmetry suggests fast, reversible electron transfer at the interface. Additionally, the modifying molecules were found to be very robust to CV cycling. An amine derivatized ferrocene molecule, Fc[CH2 N(CH3 )2 ], was used to modify ITO, although less successfully than the carboxylic derivatives [64]. Modification with amines tends to create a less robust modification, where the molecules can be easily removed with solvents. CV cycling can also lead to the loss of amine modifiers. This phenomenon is clearly a result of the weaker Lewis base characteristics of the amine for the Lewis acid sites on the metal oxide surface. Han and coworkers, however, were able to design a dense self-assembled monolayer of 1,12diaminododecane from methanol onto ITO after 60 h of immersion [78]. The terminating amine group allowed for the subsequent addition of a monolayer of phosphomolybdic acid to provide redox active centers. The diaminododecane, at
R OH
–H2O

R OH OH O M O O O (b) HO M O O O M O
–H2O

P O M

P O M O O (c) O HO M O O O M

P O M O O O

O O

Schematic views of the possible interaction modes of phosphonic acids with TCO surfaces; (a) monodentate attachment (b) unidentate attachment and (c) multidentate attachment.

1.1 Modification of TCO Electrodes through Silanization and Chemisorption of Small Molecules

27

6 × 10−10 mols cm−2 , provided a platform for one-third as much redox active acid. This protocol may allow for the modification of oxide surfaces through chemisorption to obtain surfaces similar to those obtained through silanization; however, the robustness of this platform was not evaluated. Cyanuric chloride has been used to modify oxide and graphite electrodes [79]. The linkage, an ether bond through surface hydroxyls, is short and strong, allowing for a robust surface and enhanced electron transfer between the surface and the aromatic terminal group. Another modification scheme of note is the selective addition of tin-phenoxides on an ITO surface, a process developed by Schwartz and coworkers for the modification of the effective work function of ITO surfaces [13, 80]. Because of the low concentration of tin sites on such surfaces, this modification scheme, which does not modify exposed indium sites, places the functional groups at some distance from each other, a type of modification not afforded by other modification schemes based on covalent bond formation, or chemisorption. Heme proteins have also been adsorbed to TCO surfaces as ‘‘modifiers’’ of their electrochemical properties. These adsorption processes are undoubtedly a combination of electrostatic forces, H-bonding, and metal ion coordination in the TCO surface, and produce reasonably robust and active modifying layers. Cytochrome C (cyt C) has been the most extensively studied adsorbed heme protein. Hawkridge and coworkers have examined the electrochemical behavior at gold, platinum, and metal oxide electrodes [81]. Electron transfer rates as high as 10−2 cm s−1 were obtainable at ITO electrodes. Bowden and coworkers have determined that the

electron transfer rates are associated with a conformational change of the molecule in the adsorbed state at the electrode surface [82, 83]. Above a certain scan rate, the conformational change can be overcome. More recently, Runge and Saavedra showed that cyt C forms a sufficiently stable adsorbed state such that it can be microcontact printed on ITO surfaces, while retaining high electron transfer rates [84].
1.1.5

Conclusions

The modification of TCO surfaces can clearly be used to enhance the electrochemical performance of oxide electrodes. There are, however, issues yet to be resolved regarding the initial surface composition of the oxide, especially for ITO, which prevent realization of the full electrochemical and electronic potential of these electrodes. In some cases, the modification chemistries produce a surface, which is sufficiently robust to be used in various sensor platforms or condensed phase devices. However, it is not yet clear whether long-term stability can be achieved in those cases where the oxide is exposed to solutions that also promote the hydrolysis of the oxide unless an extremely strong covalently bonded network, or chemisorption interaction can be produced. These modification strategies will continue to evolve with the increasing need for viable interfaces between electroactive materials and the metal oxide electrode.
Acknowledgments

Work cited in this review from our laboratories was supported in part by the National Science Foundation (Chemistry); the Office of Naval Research; the

28

1 Preparation of Monolayer Modified Electrodes

Department of Energy, National Renewable Energy Laboratories Program, Photovoltaics Beyond the Horizon; the Department of Energy, Basic Energy Sciences, and the National Institutes of Health.
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a silane-based SAM is one of the most popular SAMs for modifying a silicon surface covered with a naturally grown oxide film [7. The thiol substituent is a soft binder effective to specific surfaces.2. is a thiol-based SAM on gold. a thiol substituent and an alkane chain. A typical example of the former.1.2 Encyclopedia of Electrochemistry. The alkane chain is a building block to form a monolayer and can serve as the structural unit that enables the spontaneous organization of the tightly packed monolayer through van der Waals interaction (or hydrophobic interaction in water) between the alkane chains.Fujihira. and J. it was well known in the 1940s. Bard and M.1. Stratmann Vol.J.Rusling Copyright  2007 Wiley-VCH Verlag GmbH & Co. that is. Japan 1. such as DNAs or proteins. This looks as if biomolecules in nature. 12–19] and also for chemically modified electrodes [14.Edited by A. to which the component molecules can be chemically adsorbed from the solution or gas phase [5]. 11. 12].2.2. or liquid. 5].1. Self-assembled monolayers (SAMs) on substrates belong to the latter organized system because these monolayers need to be supported by the surfaces of solid. Around that time. Yokohama. they are members of a kind of supported organic monolayers [4. 10 Modified Electrodes. Two different types of SAM adsorption processes on solid substrates are well characterized: all of the component molecules are chemically bonded one by one to the substrate.ISBN: 978-3-527-30402-8 . The essence of these self-organization processes is that no external intervention is necessary to guide the processes once the assembling processes start [1. 1 [1]. and the other is a system that organizes at a heterogeneous interface.1 1.2. The structure of molecular self-assembly can be divided into two types of organized systems: one is a system that organizes in a homogenous medium.Rubinstein. KGaA. Historical Background on SAMs Bringing together two concepts of supported organic monolayers and spontaneous organization (or self-assembling) was of crucial importance for the advent of SAMs [6. the code is set in two structural parts. Edited by M.1. In 1. In the case of an alkanethiol-based SAM.1. A schematic of alkanethiol-based SAM structure is shown in Fig. are coded by the structural specificity to express their functions.1 Preparation of Self-assembled Monolayers (SAMs) on Au and Ag Uichi Akiba and Masamichi Fujihira Tokyo Institute of Technology. or they are themselves polymerized on the substrate [1]. For the latter instance. Weinheim. that is. 20–29]. We can synthesize various component molecules in which predesigned structures are specifically coded with the rules necessary for the molecular assembly. the self-assembling of supported organic monolayers had already been studied using acid/base interaction for the monolayer adsorption on substrates.F. The idea of forming SAM on a substrate is not new.2 SAMs on Au and Ag Electrodes 1. such as gold.1 Introduction Molecular Self-assembly at Surfaces Molecular self-assembly is a process in which an organized superstructure or pattern is spontaneously formed from an ensemble of the component molecules that are uncorrelated to each other in a liquid or gas phase [1–3]. 2]. which involves the specific interaction of sulfur–gold coordination as the principal driving force for assembling the organosulfur compound from the solution or gas phase onto a gold surface [6–10].30 1 Preparation of Monolayer Modified Electrodes 1. I.

and alkylcarboxylic acids adsorbed to substrates of glass. 1 Au A schematic of alkanethiol-based SAM structure depicted using a structural model of an n-dodecanethiolate SAM (C12-SAM) on a gold (111) substrate [1]. 31]. and metal oxide [5. nevertheless. the idea of self-assembling of supported organic monolayers was taken over by the following researchers [34–36]. no rapid progress was made in the preparation technique of SAMs. Zisman and coworkers performed the first systematic studies of self-assembly of monolayers of long alkane chains of alkylalcohols. we have long known that ordered. studied the structure of a variety of molecules adsorbed on an electrode. from the standpoint of fundamental understanding of well-defined structural surfaces in vacuum and at the solid–liquid interface [15]. could be controlled by changing the terminal functional groups. Therefore. The driving force for the assembly. 8. however. However. which afforded only modest stability similar to those formed by the L–B method [5. 32]. the supported monolayers created by them had low energies of adsorption (5–15 kcal mol−1 ).2 SAMs on Au and Ag Electrodes Φ 31 Terminal group H C Alkyl chain S Film thickness Head group Substrate: Au(111) Fig.1. 33]. The definition of film thickness and tilt angle (φ). They found that the systems were enabled to form spontaneously oriented monolayers. alkylamines. although the molecules used . and we have had to await the advent of a new methodology for SAM formation that enables us to generate a wide variety of stable SAMs. Afterward. 8. Their studies also suggested that the interfacial properties of SAMs. which have properties similar to the corresponding films formed by the Langmuir–Blodgett (L–B) techniques [9]. As a result. metal. On the other hand. the potentiality of interest was not recognized at that time [8]. Hubbard et al. 30. evidence for the spontaneous organization of supported organic monolayers on platinum surfaces has been obtained [16]. 30. The difference was demonstrated using the change from methyl group to trifluoromethyl group [5. was not strong because physisorption or weak bonding between the functional groups and the substrate surfaces was used in this adsorption [6. 31]. thermally stable organic overlayers can be formed on a metal surface in vacuum by exposing a clean surface to a small amount of volatile molecules [37–39]. These SAMs have a potential necessary to self-assembly. 8. 1946 and 1947. such as wetting and adhesion.

43]. 42]. The characterization of the structure of simple SAMs on gold is also an important subject for our understanding of the SAMs at atomic level. 41. which has proved to provide a new methodology for spontaneous formation of supported organic monolayers with a variety of functional groups [6. the L–B techniques can be used to fabricate the supported monolayers [40–42]. many studies had used gold only as a substrate in the experiments for reversible physisorption of organic molecules. Moreover. 7]. 43–47]. The excellent feature of this system is that this model has the ease of preparation and the structural definition required to provide a firm understanding of interfacial phenomena [43. 37. form densely packed. is extremely convenient for the formation of SAMs with a wide variety of functional groups. This character. The ω-substituted long alkanethiols adsorbed on gold. 28. Since the first report by Nuzzo and Allara [6]. In 1983. Thus. X(CH2 )n SH with a wide variety of functional groups at the terminal. Thus. The use of gold as a substrate is unique because. the L–B films on substrates usually have no good thermal stability. Platinum surfaces were used widely in surface science. These characteristic features of the sulfur–gold bond formation in the new type of SAMs also triggered extensive studies by surface scientists using a large number of physical surface-analytical methods [37. but less for chemisorption [6. because most functionalities react readily with the platinum surface used as the substrate [37]. That is. which is largely restricted to polyfunctional molecules bearing only one polar substituent [37]. 43–47]. 47]. X [43. The specificity and stability of organosulfur compounds chemically adsorbed to a gold surface are of crucial significance for the study of the formation of a variety of model SAMs and the characterization of their structure and properties by various physical and chemical methods [37. Although the order of molecules in the L–B films can be quite good. 48]. in addition to the inertness of the gold surface against polar functional groups. 44. Consequently. 44. this is potentially a nonequilibrium and difficult procedure.32 1 Preparation of Monolayer Modified Electrodes here were not surfactants. until that time. the self-organization of a variety of organic surfaces was difficult as long as platinum surface was used as a substrate for adsorbates. 7. similar to the case of simple long alkanethiols. a stable monolayer with a high surface-free energy is difficult to form with this technique [8. These systems. they . Bain and Whitesides focused their interests on systematic studies of modeling organic surfaces made of a variety of SAMs based on ω-substituted long alkanethiols. Nuzzo and Allara reported a useful technique for preparing supported organic monolayers of disulfidebased molecules with a variety of functional groups [6]. In contrast with the platinum surface commonly used as a substrate so far. a gold surface was recognized to be one of the least active metals in the chemisorption of many organic molecules [6. 47]. 7. This technique extended the previous approach in a dramatic way. early researches have been concerned with the physicochemical properties and structural characterization of basic alkanethiol-based SAMs on gold [37. Especially. oriented monolayers. they focused on chemisorption based on a strong and specific coordination bond between sulfur and gold. In contrast to these systems of molecular adsorption on metal surfaces. however. 29]. because a number of molecules can be strongly adsorbed on the surface. lack variations in the functionality of molecules for controlling the surface structures of the overlayers.

The second is a surrounding phase/SAM interface. which is a structural spacer at the interior of the monolayer. 69–71] and grazing incidence X-ray diffraction (GIXD) [48. in which we have a basic problem regarding the reaction sites between organosulfur compounds and a gold surface to generate a sulfur–gold chemical bonding.2 SAMs on Au and Ag Electrodes 33 could explore the relationships between the microscopic structure of the monolayers with the variety of functional groups. Subsequently. 64]. The most important consensus established by these measurements is that alkanethiol-based SAMs basically have enough characteristics to be considered structurally well-defined organic surfaces at the molecular level. 79]. 74]. mainly focusing on alkanethiol-based SAMs on gold [48. 47. many research groups have studied the kinetics of SAM formation (more quantitatively) using various spectroscopic techniques [48. Reaction chemistry is also one of the important aspects of SAMs from both fundamental and application issues. electrochemical quartz crystal microbalance (EQCM: see Shimazu) [81]. such as second-harmonic generation (SHG) [76. which include ultrahigh vacuum scanning tunneling microscopy (UHV-STM) [48. the understanding of growth kinetics and dynamics in SAM formation processes on gold from the gas phase and solution phase is essentially significant for the fundamental perspective. 63. Accordingly. a progressive advance has been made to understand in depth the static structure formed on gold. using diffraction techniques [48. surface plasmon resonance (SPR) [82]. Later. at the terminal of the SAMs and their macroscopic properties. These instruments have provided complementary local and nonlocal probes for structural information on SAMs on gold. Many kinds of surfaceanalytical techniques used in vacuum and at the solid–liquid interface have been applied to the studies of SAMs. photopolymerized SAMs can be prepared [84]. 72]. sum-frequency generation (SFG: see Ye & Uosaki) [78. if the spacer has a reactive structural unit of diacetylene at the interior part. SAMs consist of three parts. The first is a SAM/substrate interface. similar model studies have been extended using the SAMs on silver [60–62] or copper [60. As described above. The kinetic experiments of SAM formation on gold from the gas phase (under vacuum) have been carried out actively by Schreiber et al. in which a variety of reactions are possible because we can modify the surface of SAMs with a variety of functional groups at the terminal. The third is an intermediate part between these two interfaces. whereas relatively little is known on the dynamics of the self-assembling process on gold at the molecular level [73]. . They studied in detail the relation between wettability and the structure of the monolayers [43. X. The kinetics from the solution phase have been carried out by Bain et al. 75]. Many physical and chemical researchers have challenged the structural issues of SAMs formed from a gas phase in vacuum or a liquid phase. The interface can be used alternatively to adsorb a variety of functional biomaterials. 73. For example. near edge X-ray absorption fine-structure spectroscopy (NEXAFS) [80].1. 44. 77]. which are another variable structural factor of interest for understanding the influence on self-ordering of SAMs. The excellent features of SAMs on gold may provide an invaluable opportunity for the understanding of self-assembly process at the molecular level. 65–68]. 49–59]. using ellipsometry [47]. and Fourier transform infrared reflection absorption spectroscopy (FTIRRAS) [83].

Among these materials. Hill [87].2. gold is the most frequently used substrate. sputtering [127. First.2 Preparation Techniques of Substrates Used for Forming SAMs Gold as a Substrate Material There is a wide range of choice for substrate materials that can be used for SAM formation of organosulfur compounds. 1. Taniguchi [28. 29]. The prominent features of the SAMs on gold as well-defined organic interfaces provide means to be amenable to fundamental sciences and a variety of interdisciplinary applications. there are a large number of subjects in which SAMs have been used as materials for organic functional surfaces [9. 129. These impacts have extended the availability of SAMs into almost all surface sciences. R−S−R R−SH R−SH R−SH R−SH R−SH R−SH R−SH R−SH R−SH R−SH R−SH Surface materials Metal Semiconductor Oxide .1. the melting point of gold is 1064 ◦ C. biosensor devices [116–119]. and biocompatible materials [9. Further.1. 85. This feature enables us to prepare easily a thin film of gold onto a flat base by physical vapor deposition (vacuum evaporation) [124–128]. 130].2. electrodeposition [131]. the gold thin films prepared on a substrate are exceptionally useful to make patterns at micrometer scales by a combination of lithographic tools and chemical 1. 1 SAMs on gold are called golden interfaces [69]. 133]. and electroless plating [132. physical organic chemistry [93–97]. it is understandable that Tab. R−SS−R. In such a sense. including. Handmade preparation of a gold single-crystal electrode is widely used among electrochemists as described below. 86]. biochemistry and biology [102–104].34 1 Preparation of Monolayer Modified Electrodes Regarding the application issue of SAMs. and of course electrochemistry [105–109]. which is not as high as that of platinum (1770 ◦ C).1 Chemical systems of organosulfur compounds and substrates that form SAMs Substrates Au Ag Pt Pd Cu Hg GaAS (III–V) InP CdSe (II–VI) ZnSe (II–VI) Tl−Ba−Ca−Cu−O ITO Organosulfur compounds R−SH. 120–123]. the SAM formation techniques have played a critical role in the understanding and controlling of molecular electronics [110–115]. In recent years.2. for two reasons [9]. physical chemistry [98–101]. especially in nanoscience and nanotechnology [9]. materials chemistry [89–92]. as summarized in Table 1 [86]. A wide variety of interdisciplinary researches with SAMs have been performed since early studies by electrochemists. and Weaver [88]. which are being developed rapidly at present.

the cells adherent to the gold surface can effectively function without evidence of toxicity [9].5-nm depth [124]. The deterioration of the widely . demonstrated that decreasing the evaporation temperature to 150 ◦ C resulted in smaller plateaus surrounded by grooves of 5. QCM [140. 10].05 nm s−1 . and various electroanalytical techniques [106. gold does not readily form an oxide surface and. 9.2. The evaporation rate should be 0. followed by the second 50-nm gold film at a rather slow rate of 0. 142–145]. Such a gold substrate prepared on mica has mechanical stability enough to be used in experiments in vacuum and in various liquids. In fact. The first 150 nm of gold film is deposited at a high rate of 5 nm s−1 . The thickness of the gold films is usually 100–250 nm. electrochemical-surface plasmon resonance (EC-SPR) [138.99% purity grade.2 SAMs on Au and Ag Electrodes 35 etchants [86. It is recommended that such a flat gold substrate just prepared. 126]. finally the deposited gold films are annealed for 12–24 hours at 300–350 ◦ C in the chamber. Chidsey et al. 139]. an improved procedure for the vapor deposition of gold onto mica has been reported.2 Preparation Method of a Flat Gold Surface on Mica One of the most popular techniques for preparing an atomically flat gold surface is the epitaxial growth of gold onto muscovite mica. in addition. 141]. 120–123. The commonly used evaporation procedure of (111)oriented gold surface on muscovite mica is as follows [124–127]: Freshly cleaved mica is set in a chamber of the highvacuum evaporation instrument. scanning tunneling microscopy (STM: see Itaya) [149. 1. including SPR spectroscopy [82. EQCM [81. This feature is. After gold evaporation under these conditions. 146.1. Recently.0 to 7. 89]. so that the desired gold films with a large area of atomically flat faces on the surface can be obtained.1–0. 156] for cells and proteins. should be used to modify the surface with SAMs as soon as possible. Heating the mica at 300–350 ◦ C is common during the evaporation.2. Temperature control of the mica substrate during gold evaporation is another important parameter if one needs a preferable gold film surface with widely spreading (111)-oriented terraces [125. the gold thin films have been prepared as a substrate on which SAMs are deposited and characterized by a variety of surface-analytical instruments. IRRAS [83. so that a size of (111)-oriented terraces of more than 100 nm2 can be obtained. unlike other metals. The vacuum pressures are required to be 10−8 to 10−9 Torr. ellipsometry [47. of importance in biological applications of SAMs chemisorbed on gold. 148]. 153–155]. where a two-step deposition process is performed for the formation of atomically flat gold thin films of 200-nm thickness on mica [157]. The smoothness of the gold surface depends largely on the growth conditions [128]. Thus. atomic force microscopy (AFM: see Fujihira) [150–152]. in particular.1. The gold for the evaporation usually requires at least 99. 103. Second. with its biocompatibility [102. Thin gold films less than 100 nm in thickness have a lot of trenches of ∼3-nm deep by which the individual domains are separated from each other [5]. or reannealed before use. The mica is baked for 12 or more hours at ∼500 ◦ C before gold evaporation [126]. 147]. 150]. The evaporation with high speed tends to reduce the size of (111)-oriented terraces. 134–137]. is not contaminated readily even upon exposure to the atmosphere owing to its inertness for ionic (hard) interaction [5–7.5 nm s−1 or so.

various further-improved procedures were proposed. after the procedure (2) is performed. 165]. Later. 1. Moreover.7). and thus it contaminates the gold surface. However. and (3) chemical or consecutive mechanical stripping of the mica down to the freshly appearing gold surface [164]. 2): (1) epitaxial growth of gold on mica (the same procedure as described in Sect. these gold films on mica could be kept in absolute ethanol for preserving it from the oxidative atmosphere [158. 1. has been developed as an improved method for preparing a widely flat gold surface on mica [164. usually convenient adhesives. a titanium or chromium layer of 1–10-nm thick is used as a binder between the silicon surface and the gold film. (2) gluing the fresh gold surface to a piece of silicon wafer or glass substrate.2). 1. and stripping techniques in (3).1. and used by other researchers [162].4 Template-stripping Technique as Another Route for Preparation of Flat Gold Substrates This technique.2. Instead of mica as a template of TSG. This procedure generates large areas of the smoothest gold surfaces known to date [166].2.1.1. where trapped air bubbles and solvent pockets in these adhesives are not compatible [169]. Gold Substrate on Silicon Wafer As an alternative to mica substrate for preparing a gold thin film. 130.2.2.2. 131]. 168].. the application of (3-mercaptopropyl)trimethoxysilane as a molecular adhesive in the gold vapor deposition on silicon wafers or glass substrates was demonstrated by Majda [160] and Bard [161]. it is believed that chromium tends to move more easily to the outer surface of the gold film. If the fresh gold films prepared are not used soon.2. such as epoxy or ceramic glues have been used so far. Rabe .3 1. This technique was also applied to the nanotransfer printing method [163] (see also Sect. The other is caused by out-gassing problems under ultra high vacuum (UHV). As an alternative to the titanium or chromium layer. this technique is termed a template-stripping technique and the obtained gold surface is termed a template-stripped gold (TSG) surface.2. 9.2. Thus.2. first reported by Hegner et al. 127. To improve adhesion between a silicon surface and a gold film. These adhesives give rise to some problems during experiments using the TSG substrate. a silicon wafer has been used similarly [167]. gluing techniques in (2). It allows not only improvement of the flatness of the gold surface but also storage of the mica/gold/silicon multilayer for a long period after its preparation.36 1 Preparation of Monolayer Modified Electrodes spreading area of (111)-oriented faces in the freshly prepared gold surface can be followed by STM.7. The method is based on three procedures (Fig. In the gluing procedure (2). the substrate can be stored for several months without loss of quality.1. a silicon wafer covered with a native oxide film has been used widely as a base [5. that is.1. and later the procedure (3) is performed just before use for modifications with organic materials [167. These include the use of alternatives to the mica substrate in the procedure (1). 1. One of the problems is caused by the limited stability against a variety of solvents especially when epoxy is used as an adhesive.2. The basic idea is to use the first deposited gold layer directly in contact with the mica surface rather than the top surface of the deposited gold film as described in Sect. this metal has a potential toxicity to cells adsorbed to the SAM in the application of biological interface [9]. 159] (see Schneeweiss and Rubinstein).

Removing of the mica by soaking in THF 5. Removing of the mica by soaking in THF TSG (a) Fig. Ulman et al. This character will be extremely important in the application of TSG substrates to sensors and electronics [169]. Glueing onto a glass coverslip 3 hours at 80 °C 5. Blackstock et al. reported the utilization of organothiols as a stripping technique. have been demonstrated by several researchers. and coworkers developed an adhesivefree TSG supported on nickel. Cleave of muscovite mica 37 2. Nickel of 200-µm thickness was deposited on the gold surface on mica by electroplating in place of a piece of silicon wafer in procedure (2) described above [167. 170. which involves the problem relating to mechanical stress in the stripping step. Glueing onto a piece of silicon wafer 1–2 hours at 150 °C 4. Deposition of 200-nm gold by thermal evaporation 3.1.2 SAMs on Au and Ag Electrodes 1. Improvements of the procedure (3). thus lowering the adhesion between these two surfaces [166]. This method is based on the gold cold-welding technique. 2 TSG (b) Typical preparation procedures of template-stripped gold surfaces supported (a) by a piece of silicon wafer and (b) by a glass coverslip [165]. 171]. Covering with epo-tek R301-2 20 µl cm−2 4. recently demonstrated a new type of template-stripping technique without any adhesives in the procedure (2) [169]. which can also solve the conductivity problem of the TSG substrates produced by the conventional technique or Rabe’s method. A more simple and reliable method for the stripping procedure (3) is demonstrated by Gooding and coworkers. Thiols can intercalate between the mica and gold layer of the TSG. Covering with epo-tek R377 10 µl cm−2 3. in which mica can be removed by immersion of the .

TSG substrates. 1.2. 202].5 annealing method. including silver [171]. is actively studied from the application viewpoint [199–203]. Single Crystal Bead of Gold A handy. 194]. 200. at present. and titanium oxide [185]. more than 300 nm in size. If necessary. this method was also applied to the preparation of gold and silver single-crystal electrodes by Hamelin et al. 184].6 Single Crystal Cut of Gold Such a single crystal bead itself is not amenable to various measurements that require a larger area of flat gold surface. Preparation Techniques of Alkanethiol-based SAMs on Gold 1. the most prominent semiconductor alternative to silicon. are observed by STM after flame annealing by a hydrogen torch just before use. suggesting that the chemical bonds of RS−As (R = alkyl chain) form on the surface [199.2. 1.1.2. the area where we can use the (111)-oriented gold surface for experiments is limited to a small facet (usually less than 0. Only a gold wire (99. The cut electrode has an exposed (111)-surface prepared from the single crystal bead by mechanical polishing of a (111) face that is parallel to the facet of the bead [196.5 mm in diameter) with a (111) face. but it is very easy to try because expensive instruments such as physical vapor deposition are not required for making a single crystal bead. 193. The crystallization needs skill.2. However. and we have to set up the experiment to directly use the small facet only. Namely. This cryogenic stripping method is based on the difference in contraction between mica and gold. 195–198]. as explained above. and inexpensive method of preparation of a (111)-oriented gold surface is to use a single-crystal gold bead [10. gallium arsenide (GaAs).99%) with ca 1 mm in diameter and a Bunsen hydrogen flame is necessary to make a single crystal bead by crystallizing the end of the gold wire.3. Allara et al. The cut bead is usually 3–5 mm in diameter. SAMs 1. 198].3 Preparation from Solution Phase The most outstanding feature of SAMs is their ease of preparation. Clavilier and coworkers first demonstrated with platinum the effectiveness of a simple preparation of clean and well-defined low index surfaces by the flame annealing method. the types of surfaces fabricated according to this TS technique have increased. [189. Later. and can be repeatedly used after removing the adsorbates and doing flame annealing again.1. A number of atomically flat and wide terraces of a gold (111) face. and Motoo et al. one can use a single crystal gold cut electrode [189.38 1 Preparation of Monolayer Modified Electrodes sample into liquid nitrogen [172].1 .7 Other Substrates of Interest As a new class of substrates for forming thiolbased SAMs. resulting in clean separation to leave large atomically flat planes.1. have been extensively used as a widely flat substrate for a variety of applications. timesaving. In addition.1.2. These single-crystal techniques are very familiar to electrochemists as the so-called Clavilier method or the flame 1. as well as patterned features without any change in substrate quality. which was performed by heating the platinum wire in a Bunsen flame for minutes [186. being rapidly expanded to not only physical chemistry [173–176] but also biochemistry and biology [176–182].2. 186–192]. platinum [183.2. demonstrated that GaAs (100) could provide well-ordered organic surfaces of thiol-based SAMs. The availability is. 190].2.1.

Therefore.3 and +0. 49. the immersion for a longer time will be recommended as described later.1 V vs Ag/AgCl [207]). its concentration of the solution. cyclooctane [47]. but SAMs can be prepared by using a variety of solvents. toluene [47]. tetrahydrofuran [47. it may depend on the structure of the organosulfur compound. The process of SAM formation is determined from energetics and kinetics for adsorption of SAM [48]. Studies on how an applied potential affects the SAM formation and its structures are of extreme importance for techniques of molecularly functional organization. 52]. Stratmann et al. 205] focusing on the former will be described here and. demonstrating that the electrode potential affects the kinetics and mechanisms of SAM formation on gold [207]. including hexadecane [46. Ron and Rubinstein [159]. reported that octadecylthiol (C18)based L (Langmuir) films formed on an aqueous subphase were transferred to gold substrates under the control of various electrode potentials. Recently. 52.2 Electrode Potential Control of Gold substrates for SAM Deposition chemisorbing SAMs are a kind of electrode. These studies have been performed from two viewpoints: (1) the potential control of SAM formation process and (2) that of already-formed SAM structures. 52]. When holding the electrode potential at slightly positive to the point of zero charge (pzc) of gold [192] in ethanol (varying between −0. In particular. 61]. If a more ordered monolayer is required for the experiment.2. the thiol molecules were attracted to the gold surface through the chemical bond between the negatively charged sulfur and the substrate. Ma and Lennox demonstrated that this potential control technique for SAM formation is critically effective to deposit two-component mixed SAMs with various compositions otherwise inaccessible using deposition under open-circuit potential . which depends on the compound structure and the purpose of the SAM formation. such as wettability and thickness [44]. isooctane [52.3. 205]. and dimethylformamide [47]. the SAMs generated with these solvents show almost the same macroscopic behavior in their characteristics. 47. carbon tetrachloride [47]. and compared it with the data on the basis of the corresponding SAM on gold [206]. so that it may be natural for us to assume that the electrode potentials could affect the formation process of SAMs. Porter and coworkers demonstrated this possibility by taking into account reductive desorption and oxidative readsorption peaks observed in cyclic voltammograms of the SAM on gold [204. The studies [204. First. Ma and Lennox [208]. Later they also reported that. 47.01–1 mM solution of the organosulfur compound for an adequate period. as for the latter.2 SAMs on Au and Ag Electrodes 39 are easily obtained by exposing a clean gold surface to a 0. usually for few minutes to 1 day.1. Nonetheless. and later Sumi and Uosaki [209] showed that the potential-assisted deposition of alkanethiols on gold could lead to a faster deposition and ultimately more complete SAM formation process than the common SAM deposition process. it has been found that the control of SAM formation onto gold by electrode potentials is effectively available as a SAM deposition technique. The most frequently used solvent is ethanol [46. 1. 49. and the polarity and structure of solvents used. 61]. the interested reader is referred to [206] (see also Kakiuchi). at cathodic potentials. chemisorption of thiol molecules and the development of the highly ordered structure have slowed down significantly. acetonitrile [47.1. 61].

Another electrochemical technique applicable for SAM formation has been studied in several groups. Lukkari and coworkers demonstrated this strategy using alkyl thiosulfates (Bunte salts) as a precursor [216]. 211] (Fig. the common procedure with no applied voltages [210.2. 1. closed circles). precursors of thiols must be designed in advance. 3 conditions. Lines are drawn to assist data visualization [208]. This technique was immediately applied to the microelectrode by Ferguson et al. This electrochemical mechanism was also discussed in detail. When the precursors are used for SAM formation under an applied voltage. that is.3. 4 [218].1. expressed as the percent HSC15 COOH in mixed SAMs with C16 SH.3 SAM Deposition from Aqueous Recently. A proposed mechanism for the formation of SAMs on gold by electrochemical oxidation of alkanethiosulfates is shown in Fig.40 1 Preparation of Monolayer Modified Electrodes 7 6 5 Current [µ A cm−2] 4 3 2 1 0 0 20 40 60 80 100 % HSC15 CO2H Dependence of SAM composition on the solution composition. They successfully demonstrated selective SAM formation in specific locations on the gold microelectrode using this electrochemical method [217].6 V for 10 minutes. 3). These findings are also very important for further understanding of the property of gold–sulfur bonding indispensable for SAM formation [215]. Fig. First. This acceleration effect in the kinetics of SAM formation has recently been applied to the SAM formation on gold with nonalkanethiols. open squares) and passive incubation (24 hours. Therefore. and ferrocenyl peptide disulfides [214]. Current was measured at −0. In this strategy. an interMicellar Solution esting idea for deposition techniques of SAM from solution phase has been . these are successfully transformed to the corresponding thiols in situ on the gold surface by an electrochemical reaction.3 V versus Ag/AgCl in a 2 mM Ru(NH3 )6 Cl3 /1 M KBr solution for SAMs formed by potential deposition (at 0. such as thioacetyl-terminated oligo(phenyleneethynylene)s [212. 213]. this method can be called electrochemical self-assembly on gold.

has typically been performed under UHV conditions. More recently. such as the defect density by simply altering the composition of the mixed solvents [226].1.2. and X-ray photoelectron spectroscopy (XPS).3.4. 4 0. defect-free. which is of crucial importance in the structural characterizations of model SAMs because thermal fluctuations of the adsorbate structure can be reduced by low temperature [48]. [220–223].5 number. The vapor concentration of an adsorbate in the UHV chamber can be precisely controlled through the dosage valve at the submonolayer level. enable us to achieve in situ analyses of the structure of as-prepared SAM without exposing it to the atmosphere [10.4 Structural Characterization and Chemical Properties of SAMs 1.2 SAMs on Au and Ag Electrodes − CH3(CH2)n SSO3 41 −e− · CH3(CH2)n SSO3 CH3(CH2)n S· + SO3 H2O Au surface Au surface SAM Fig. yielding dense.2. Vapor deposition of adsorbates.5[CH3(CH2)n S]2 H2SO4 A proposed mechanism for the formation of SAMs by oxidation of alkanethiosulfates at a gold [218]. They have demonstrated that environment-friendly mixed solvents such as supercritical carbon dioxide–ethanol can be used to control the properties of SAMs. 48]. [225. In addition to these features.1 Structure of Alkanethiol-based Since Nuzzo and AlSAMs on Gold lara demonstrated the idea of SAMs on .1. It is a technique for SAM formation based on deposition from aqueous micellar solutions. such as alkanethiols and dialkyl disulfides with less than 10 in carbon 1. Preparation from the Gas Phase Adsorption from the gas phase is another technique of critical importance for SAM formation. The study of this micelle-assisted SAM formation technique has been reported first by Kaifer et al. demonstrated. 226]. directly connected to the UHV chamber. 1. and is available for surface scientists. [219]. STM. This situation is essentially different from the solution deposition in which the adsorbate molecules are always surrounded by solvent molecules.2. this technique has been examined in detail by Jennings et al. it has been demonstrated that this technique is versatile for the SAM formation of insoluble component.3.1.1.4 Preparation from Liquid and Supercritical Carbon Dioxide A novel type of SAM preparation technique with liquid and supercritical carbon dioxide has been developed very recently by Weinstein et al. such as low-energy electron diffraction (LEED). especially as a sophisticated deposition technique. 1. The SAM in UHV can be kept all the time in the clean environment inherent to the UHV condition [10]. Afterward. and ordered SAMs [224].1.2. Temperature is also another controllable parameter. one more indispensable advantage of the UHV technique is that various analytical tools.

A comprehensive survey of these results was reviewed recently by Schreiber [48. corrosion. the full-coverage structure of alkanethiolbased SAMs with a variety of long alkane chains have been thoroughly characterized chiefly by using spectroscopic [37. the top. . (b) The structure of the gold–sulfur bond which includes two structural issues: the bonding mode. lubrication. Here. (d) The structure of SAM surfaces with the terminating groups of the alkane chains. diffraction [72]. 5). or the hollow sites. 68]. 66]. The third is on the structure of SAM surfaces that is organized with the terminal groups of the alkane chains. among the top. 5 Upright structure (d) gauche conformation Depiction of four parts of interest in the structure of simple alkanethiol-based SAMs.42 1 Preparation of Monolayer Modified Electrodes gold–organosulfur chemical bonding [6]. the bridge. The first is on the structure of the full coverage of SAMs formed on gold (111). we bring into focus the four parts that are of interest in the structure of simple alkanethiol-based SAMs (Fig. and which is the sulfur-binding site on a gold (111) surface. (c) The conformational structure of assembled alkane chains. The second is on the structure of the gold–sulfur bond that involves two structural issues: whether the bonding mode is alkanethiolate–gold. and scanning probe microscopic [69–71. or hollow sites. and so on. such as wetting. 65. The fourth CH3 Terminal group Alkyl chain Head group Au(111) (a) S CH3 CH3 CH3 Hollow site Bridge site Top site or Disulfide bond Thiolate bond S S Au (111) S Au (111) H3C (b) CH3 Au(111) Au(111) Tilt structure S Au(111) all trans conformation Au (111) S (c) Fig. 150] methods. The order and orientation of the terminating groups are of particular importance as these can play a critical role in determining the macroscopic properties of organic surfaces. 67. and which is the sulfur-binding site on a gold (111) surface. alkanethiolate–gold or dialkyldisulfide–gold. (a) The overall structure of the full coverage of SAMs formed on gold (111). adhesion. bridge.

where the ˚ decanethiolate molecules are arranged to be packed 5 A apart with their alkyl chains tilted 32◦ from the surface normal in a trans-zigzag extended conformation [9.884 Å Gold atom Sulfur atom Approximate projected surface area occupied by each alkyl chain 4√3 4. Fig. The light gray circles with dashed lines indicate the approximate projected surface area occupied by each alkane chain. 1. (a) Top view. Here. presenting a hexagonal close-packed gold (111) surface (open √ √ circles).995 Å 32° 4.1. and the formal c(4 × 2) superlattice unit cell is marked. 10].2 SAMs on Au and Ag Electrodes 43 is on the effect of intermediate backbone spacer on the SAM structure. (b) Side view. The structure of a c(4 × 2) superlattice is not presented here. and longer 2√3 2.2 Å S (b) Side view S S Au(111) S Schematics depicting from two different perspectives for the structural models of the arrangement of a close-packed adlattice structure of decanethiol-based SAM on a gold (111) surface.2 Close-packed Structure of SAMs Full-coverage on Gold (111) Surface structure of long-chain alkanethiol-based SAMs.1. these structural aspects of importance for characteristics of SAMs prepared on gold (111) will be summarized. 6 .2. such as octanethiol (C8)-SAM.995 Å (a) Top view 4. and the SAM overlayer of a ( 3 × 3)R30◦ structure with respect to the underlying gold (111) surface where sulfur atoms (dark gray circles) are assumed to be positioned in the threefold hollow sites of the gold (111) surface. decanethiol (C10)-SAM.4.

The alkane chains.3 Superlattice Structure of SAMs on Gold (111) The IR spectra also provided the evidence for a superlattice structure from the hexagonal close-packed structure of the C22-based SAM.1. This crystalline order of SAM formed on gold (111) was previously suggested in electron diffraction studies by Strong and Whitesides [229]. can be illustrated with two different perspectives (Fig. This surface density shows that there are 4. [47]. and electrochemistry [46]. as determined by the spacing of the sulfur atoms chemisorbed on the gold (111) surface. Very low current detective STM was also used to observe the superlattice of C12-based SAMs by Anselmetti et al.184 nm2 . Later. 6a). [236].216) ∼32◦ with respect to the surface normal (Fig. which means an area per alkanechain molecule of 0. 65]. 6b). [7. 230. except for an essentially difficult issue of sulfur–gold positioning. and demonstrated the detection of crystalline order of the SAM surface [227. This structure corresponds to a neighboring alkane-chain spacing of 0.44 1 Preparation of Monolayer Modified Electrodes docosanethiol (C22)-SAM on gold (111). The result arrived at by Chidsey and Scoles unambiguously revealed that the SAMs were closely packed in a hexagonal arrangement with an √ √ overlayer of a ( 3 × 3)R30◦ structure with respect to the underlying gold (111) surface.63 × 1014 chains cm−2 . there was an unambiguous splitting of the methylene scissors when measured at 80 K [37. which are fully extended in a nearly all-trans conformation. this superstructure was assigned to a c(4 × 2) superlattice structure.216 nm2 /molecule. These structural views are generally accepted at present.184/0. 43.16 × 1014 chains cm−2 ) [37]. 231].4. 6a. If the chains exhibit an upright structure. For a shorter chain of a C6-based SAM. 6b). which is identified from several experimental results obtained using helium diffraction measurements for a C18-based SAM by Chidsey and Scoles and their coworkers [232] and a GIXD study by Fenter et al. optical ellipsometry. and are commensurately ordered on a (111) oriented gold substrate (Fig. must be filled keeping the area per alkane–chain constant so that van der Walls chain–chain attractive interaction becomes maximum. that is. Thus. [235]. 43. 1. 6). the molecular occupied area is expected to be 0. 228]. and also for a C8-based . Porter et al. These features were provided from IR data with C16-SAM studied by Nuzzo et al. Chidsey and Scoles performed a more sophisticated analytical experiment of the C22-SAM cooled to below 100 K by using low-energy helium diffraction (LEHD). have characterized the structure of a C22-SAM based on the average structural information obtained by infrared spectroscopy. the alkane chains in a SAM are forced to a structure tilted by arccos(0. together with the trans-zigzag segment of an alkane chain rotated by ∼55◦ from the plane established by the chain axis and the surface normal vector [37. The thickness of these SAMs increasing linearly with chain lengths from 9 to 21 in carbon number has been measured using ellipsometry by Bain et al. therefore. which is roughly consistent with the results of tritiumlabeling studies (∼4. The result provides a fairly good linearity between the measured SAM thickness and the alkanethiol chain lengths.4995 nm.2. as illustrated in Fig. The side view illustrates the tilted and twisted longchain structures of alkanethiols. 43]. [233]. [234] and by Delamarche et al. The top view explains the structural characteristics of the fullcoverage SAMs (Fig. it was performed by Bucher et al.

1. ellipsometry. 231. low-energy atom diffraction (LEAD). [44] comprehensively demonstrated earlier experiments on model surfaces using a variety of SAMs with the functionalterminating groups.2. it is believed that the features responsible for the formation of the superlattice structure are located in a very thin layer of the gold–sulfur interface [65]. The reason for √ √ exhibiting the ( 3 × 3)R30◦ structure can be explained intuitively. This method makes it possible to characterize such local . such as IR.2. order and orientation of the functionalterminating groups situated on top of the SAMs are indispensable for their structural specifications. (1) polarity and hydrogen-bonding characters of the terminating groups and (2) the length of the alkyl chains connected to the terminal groups [37. as a candidate for the sulfurbinding site on gold (111). XPS. Evidence that the sulfur atoms cannot be situated at such a single site but must be in a mixed arrangement is proposed spectroscopically using infraredvisible SFG by Yeganeh et al. However. Following Dubois et al. [237]. and the top site. Bain et al. Recently. the bridge. there are three types of binding sites. while the reason why the superlattice is produced is thus far not obvious.1. but can involve various functional-terminating groups. 1.11). 65. 65. indicating that these surfaces are highly ordered [37. We can use this flexible capability for SAM preparation to understand the fundamentals of organic surface chemistry and to engineer new technological applications. a number of studies have been performed on the structures of a variety of functional-terminating groups on the SAMs. 65. the energy difference between the hollow and bridge sites is not so large [66] that it makes it difficult to definitively prove the evidence for the binding mode even by using up-to-date powerful analytical tools [65]. and so on. 230.4.1. that is. GIXD.4. that is. NEXAFS. the hollow. [238]. If a functional-terminating group has a similar size as a methylterminating group. 1. 240–242] (see also Sect.4 SAM Surface Structure Model organic surfaces that SAMs can form are not limited to hydrophobic surfaces with methyl-terminating groups on alkanethiolbased SAMs.1. Accordingly. the order and orientation of the functional-terminated SAMs strongly depend on the balance between the two structural parameters. This feature is the most important consequence obtained by developing a methodology of SAM-modified electrodes.2 SAMs on Au and Ag Electrodes 45 SAM by Poirier et al. STM is capable of observing the appearance of local disorder or molecular pinholes as a real-space imaging with atomic resolution. STM. These experiments are carried out using analytical tools. 247]. Moreover. However. The reason is that it is difficult to measure only a very thin gold–sulfur interface. there have been numerous experiments for simple alkanethiol-based SAMs with methylterminating groups. cyclic voltammetry. 71]. There is an unsolved problem related to the gold–sulfur bond as described above.2. 243–245]. Schreiber [65] summarized these experimental results systematically.1.5 Characterization of Defects by All thiol-based SAMs assembled STM spontaneously on gold have never exhibited perfect crystalline domains with single molecular lattice. Until now. which were followed by many chemists who have made challenges to such issues [37. In parallel with this characterization of the methyl-terminated SAMs. Kelvin probe technique [246. 228. [239].

A SAM formed from a mixed solution of this amide-containing long-chain alkanethiol with a commonly used alkanethiol results in the phase separation [258].46 1 Preparation of Monolayer Modified Electrodes molecular and mesoscale defects on the SAMs. The investigation has been carried out from two viewpoints.25 nm.1). On the other hand. Here. The other is a structure design to have some advantage of the functional applications of SAMs.1. particularly providing additional details of domain shapes and domain size dispersion [71]. In addition. gold vacancy islands. in this SAM a domain boundary between two tilted alkane-chain domains with different azimuth angles cannot be seen (Fig. and molecular vacancies observed by low current UHVSTM [71]. The formation mechanism by which the gold vacancy is created at the domains of SAMs remains to be solved. 1. 254]. The flexibility in orientation of alkane chains tends to cause some defects. one of which is based on the boundary due to different azimuth angles of the tilted alkane chains on the gold surface [248]. 257]. indicating that the pit area is also covered with the alkanethiol monolayer [249.6 Structural Variation in the Backbone Unit of SAMs Structural variations of alkane-chain backbone in SAMs have probably been examined first by Ulman and coworkers from fundamental viewpoints of the effect of the structural variations on molecular packing and orientation of the SAMs [8. 8) [256. but a possible mechanism is provided by Poirier [71]. the adlattice structure of the monolayer within a pit was confirmed by STM [251. which can be easily measured by STM. STM images indicated that the SAM could be formed and each molecule was clearly discriminated at the molecular level.2. . different azimuth angles) of alkanethiol-based SAMs on gold (111) [248]. One is a structure design to provide structural perfection of SAMs with few defects. The pit depth is 0. This result indicates that bicyclooctane(BCO)based SAM exhibits no tilted structure. Fujihira and coworkers succeeded in avoiding this type of defect by using cage molecules as a SAM component as shown in Fig. 250].4. In fact. When these cage structure-based disulfide compounds are chemisorbed onto gold (111) surfaces. the typical two of which are pure orientational domain boundary and translational domain boundary [71. Poirier has presented an excellent account in which the characterization of defects of a C12-based SAM on gold (111) is introduced by exhibiting high-resolution images of domain boundaries. 7c). but a closely packed upright structure on gold (111) surface (Fig. 252]. 1. 253.e. gold vacancy are usually observed using STM as single gold atom deep pit defects with a variety of sizes and shapes in the domains of SAMs on gold [71]. as well as domain boundary occurred because of difference in tilt direction (i. 7a [255].1. The other typical example is a SAM formed of alkanethiols with an amide bond in the interior of a single alkane chain (Fig. ordered 2D lattice is determined mainly by the size of BCO spherical backbone rather than the commensurability of the sulfur-binding site to the (111) oriented gold substrate.2. 237].9. Such a SAM has stability based on the lateral interaction not only due to van der Waals chain–chain interaction but also due to hydrogenbonding interaction between neighboring amide moieties. Formation of highly ordered closepacked structures was realized in this SAM with a thickness less than 1 nm (see also Sect. 7b). SAMs usually result in several types of domain boundaries on gold.

and (b) the schematic side view presenting the structure of the BCO-SAM on gold (111). 8 Au substrate The structural formula of an alkanethiol compound containing an amide bond in the interior (a). HS H N (CH2)14CH3 (a) O O N H N H O O N H O N H N H O S S S S S (b) Fig. 7 (a) The structure of BCO disulfide compound synthesized.5 nm 0.0 nm (c) 10 nm Fig. sample bias voltage = +1 V) [255].1. and the schematic side view presenting idealized SAM structure of the amide bond-containing alkanethiol-based SAM (b) [256].2 SAMs on Au and Ag Electrodes 47 S S S S (a) S S (b) Au(111) 0.3 nm 0. . (c) Constant-current STM image of a 20 × 20 nm2 area of a BCO-SAM on gold (111) (tunneling current = 50 pA.

9 Dialkylthiocarbamate Surface-active organosulfur compounds that form monolayers on gold [8].2. even in the case of such simple models as alkanethiolbased SAMs. it is not easy for us to decide the most suitable preparation conditions in terms of solvent. Whitesides and coworkers compared HS Alkane thiol S S S Dialkyl sulfide Dialkyl disulfide O S S− S N S− Alkyl xanthate Fig. solution concentration of the component. 10. This is because different structures and properties of component organosulfur compounds themselves strongly influence the energetics and the mechanism of the SAM formation on the surface. These examples are described in a separate section below (see also Sect.1. advanced studies on nonaliphatic SAMs have been done intensively. probably resulting in chemisorption through the alkanethiolate–gold bond [8. 260].2. and immersion time.1. Understanding the chemistry of SAM formation. oligophenylenes. 1. In addition. 76. adsorption temperature. we describe here the fundamental issues relevant to the adsorption chemistry and energetics for the formation of alkanethiol-based SAMs on gold.5 Chemistry and Energetics of the Formation of Alkanethiol-based SAMs on Gold 1.1.10) to explain the trend of these SAMs briefly. that is. .2.1 Overall Reaction and Energetics of Chemical Adsorption at the Gold/Thiol Interface When we prepare SAMs onto gold substrates by the solution deposition method. Organosulfur compounds interactive to the surface of gold to form SAMs are listed in Fig. 9 [8]. In particular. 60. Therefore.48 1 Preparation of Monolayer Modified Electrodes Recently. these two organosulfur compounds give indistinguishable SAMs on gold when examined by ellipsometry and XPS. a large number of structural variations have been designed for their potential applications. and so on can be used as an important component of molecular electronic devices. However. oligothiophenes. because these have been most intensively investigated so far. 1. alkanethiol and dialkyl disulfide. 259. SAMs formed from thiols with the backbone structures of acetylenes. provides some clues actually helpful in choosing the better preparation conditions. here we focus on two types of organosulfur compounds.5.

By measuring the temperature dependence of the value. 261].5 kcal mol−1 for C18) [261]. finally followed by a reductive elimination of the hydrogen [8]. They also demonstrated that the rate of SAM formation from alkanethiols and dialkyl disulfides were indistinguishable. For decanethiol (C10) in the bulk one would expect ∼16 kcal mol−1 (66 kJ mol−1 ) based on the heat of vaporization [48]. The fact that SAMs can be prepared from gas-phase deposition in an environment completely free of oxygen strongly supports this overall reaction mechanism [8. by a factor of 50 [60. In the discussions in the literature. the adsorption reaction onto a clean gold surface may be considered formally as an oxidative addition of the S−H to the gold. 1. 263]. The physisorption energy for decanethiol (C10) on gold (∼25 kcal mol−1 (∼104 kJ mol−1 )) can be comparable to the corresponding chemisorption energy (∼30 kcal mol−1 (∼126 kJ mol−1 )) due to the additive contributions of van der Waals interactions of the entire chain [48.2. 10. 266]. 268].2 SAMs on Au and Ag Electrodes 49 SAMs formed from solution of disulfides with those of thiols.3 Stabilization of SAM Structure due to Alkane Chain–Chain Interaction within the Densely Packed Monolayers For densely packed monolayers of alkanethiol-based SAMs. which means this chemisorption reaction is an exergonic process.5. 76. 262. (−5. of course.1.2. and the latter interaction is derived from the chemical bond between the sulfur head group and the gold surface. In the case of dialkyl disulfide. while the rate of replacement of molecules from SAMs by alkanethiols was much faster than that by dialkyl disulfides. physisorption and chemisorption.5. 1. 264–266]. 267.1. This relatively large amplitude and negative value of entropy apparently reflects the great degree of ordering that occurs as the alkanethiols change from randomly distributed orientations in solution to highly oriented SAM lattices on the surface [10]. Consequently.1. free energy of this overall reaction can be calculated to be −5 kcal mol−1 . 267.2 Chemisorption Energetics for Gold– Gold/Organosulfurs Interfaces organosulfur interaction involves two adsorption regimes. 1. They also estimated the free energy of adsorption for dioctadecyldisulfide to be −24 kcal mol−1 . discussed quantitatively the comparison of these interactions by taking account of a large variety of structures of alkanes and the corresponding alkanethiols [48. RS−Au (−40 kcal mol−1 ). 268]. Blanchard and coworkers estimated the molar enthalpy of adsorption (−20 kcal mol−1 ) and the entropy of adsorption (−48 cal mol−1 K−1 ) [264.4 Structural Effects on SAM ForThe structures mation and Stability of the SAM forming components. Schreiber et al. The bond dissociation free energies for the chemisorption reaction process of RSH on gold are as follows: RS−H (87 kcal mol−1 ). the reaction is probably a simple oxidative addition of the S−S bond to the gold surface [8].2. probably through the hydrogen atom on the surface. This value is quite similar to that calculated by Schlenoff et al. the chain–chain interaction will become more and more important [48]. The former interaction is one between the gold surface and the adsorbate.5. In the case of alkanethiol. and 1/2H–H (−52 kcal mol−1 ) [8.1. there has been confusion between enthalpy ( H ) and free energy ( G). may have a strong effect on the .

Another unique system related to this issue is reported by Fujihira and coworkers using a single alkane chain inserted in a rigid BCO-based SAM matrix [270]. Later. less closely packed SAMs result in gauch defects of the alkyl chains.6 kcal mol−1 ) [48].2.5 kcal mol−1 ).6 Growth Mechanisms of SAMs 1. 271]. the growth of an ordered monolayer film follows the first regime.022 eV (∼0. The second regime. have a direct impact on the growth of SAMs. the energy cost for a gauch defect in an isolated hydrocarbon chain is ∼0. The first regime. In this regime.2. When further continuous self-assembly in solution proceeds.50 1 Preparation of Monolayer Modified Electrodes formation and stability of SAMs.1. For instance.6. a very fast step that proceeds within a few minutes and strongly depends on solution concentrations used in the measurements. a slow step in which final macroscopic properties of SAM were reached only after several hours [76]. alkyl chains are highly ordered to assemble together. During the second process. 1. 10. The energetics of SAM formation. Bain et al. 47. 10. contact angle goniometry and ellipsometry [8. can be described approximately by the Langmuir growth curve for adsorption. films thicker than just monolayer are always formed. it was presumed that alkyl chains get out of the disordered state and into ordered unit cells [8. 76]. These chains straighten from the highly kinked conformations to the transextended zigzag conformations predominantly [80]. first studied the kinetics of alkanethiol-based SAMs onto gold in the solution phase of ethanol by measuring the wettability and thickness using ex situ macroscopic analytical methods. The first regime corresponds to the adsorption process onto gold. Difference in the timescale of these two regimes is at least ∼2 orders of magnitude [81. 82]. it was analyzed in detail that this slow step can be further divided into two processes [10]. This is exemplified by Shon and Lee using uniquely designed chelating alkanedithiols [269]. Such a rinsing procedure with a solvent is indispensable for a procedure for preparing complete . and inevitably influence the formation and stability of SAMs. In the second regime. that is. indicating that the physisorption process proceeds continuously onto the monolayer films [272]. 48]. in which alkyl chains possess a high number of gauche defects on the surface [10. Comprehensive understanding at molecular levels on the detailed growth processes of SAMs has been revealed using several in situ analytical tools [10].1. was described as a surface crystallization process. 80. which can be thermally activated at room temperature (RT = ∼0. the physisorbed adlayer produced by a procedure of a long time immersion into an ethanol solution has to be removed by rinsing with ethanol solvent after the solution deposition procedure. A subsequent process occurs at a rate of 35 times slower than the chainstraightening process [10]. The results revealed that at least two distinct kinetic regimes could be characterized in the SAM formation process at the macroscopic resolution of such methods [8.1 General Profiles for SAM Formation Process Understanding the growth process of SAMs as well as the energetics of SAM formation is of fundamental importance for the advance in physical chemistry of molecular self-assembly and also for preparation of various structured SAMs on gold. as discussed above for alkanethiol-based SAMs as a model case. 47]. Therefore. which was first identified quantitatively ex situ using NEXAFS [80]. Hence.

The substrate surface and solution themselves should be clean enough to secure no effect of contaminants during the timescale of the growth process. comparisons between the solution and the gas-phase deposition of SAMs are very useful and are summarized in table 2 of Ref.1. and FTIRRAS [83]. that is.2. 1.6. SPR [82]. In addition to wettability. The fast step begins with the condensation of low-density crystalline islands with the alkanethiol molecular axes aligned parallel to the surface. The major difference between the two phases is the solvent being present in solution phase. it is not necessary for us to use an expensive UHV equipment. in comparison with the gas phase. 273]. such as SHG [76. depending on their structural characters and polar properties. UHV-STM seems to be extremely effective for understanding comprehensibly the growth process at the molecular levels. and UHV-STM described above. .3 Growth Studies from Solution Phase The most convenient preparation method for SAMs is the solution deposition method. These powerful techniques reveal information on the growth processes of SAMs as well as on their structural characterization.2 SAMs on Au and Ag Electrodes 51 SAMs on gold surface. but the solvent effect may not be negligible in the succeeding steps toward the final structure of the SAM. For details of these useful techniques. SFG [78.6. The fast and slow regimes of SAM growth onto gold in the solution deposition method first proposed by Bain et al. This situation is very different from the case of characterizing SAM structures. and a more detailed and comprehensive description on these issues is found in a review [10]. These images are clearly obtained as a sequential molecular evolution of the SAM growth.. NEXAFS [80].2 Growth Studies from the Gas Phase UHV technique allows precise control of the cleanliness of the substrate and the use of a wide range of surface-analytical techniques. In this method. using UHV-STM [48.6. Competitive physisorption between the sulfur compound and the solvent onto the gold surface may influence mainly the first step of the growth process. Solvent molecules.1. numerous studies on the growth processes of SAM formation have been conducted using several instrumental techniques. 77]. have a direct impact during the growth process of SAMs. because strong effect of the contaminants on the process of the SAM growth is expected [48]. However. has now gained consensus. the interested readers are referred to the review by Schreiber [48]. The following phase transition results in a denser phase by realignment of the molecular axes parallel to the surface normal.1. various other techniques. For a comprehensive understanding of the growth of SAMs from solution phase. in which only the structure of the finally formed SAM requires the absence of contaminants. ellipsometry. 71. the solution method has a shortcoming regarding the substrate cleanliness. and thus understanding of the SAM growth with this method is informative for the SAM preparation. In particular. 48. 79]. the fast step and subsequent slow step could be observed at the molecular levels.4 Further Techniques for Investigating the Growth of SAMs on Gold Until now.2. The selfassembly mechanism of alkanethiol-based SAM of C10 on a gold single crystal (111) surface was observed by Poirier et al.2.1. They revealed unambiguously that the previously mentioned two-step process. 1. 1. EQCM [81].

276.7. so-called nanotechnology is intensively being pursued [9. in nanobiotechnological interfaces [9.1. The realization of the techniques available to molecules can be inspired since it has been found that nature has already accomplished similar technology almost completely by using selforganization.2). Fujihira and Morita [275] prepared deliberately patterned SAM samples having HC and FC domains by utilizing photolithographic and liftoff techniques. These include spontaneous phase separation of mixed SAMs as an example of the bottom-up method for fabricating patterned SAMs.1. development of techniques for tailoring such patterned SAMs and controlling their functions at the molecular level is of critical importance in a future technology. since it has been successfully applied to patterning semiconductor surfaces using various lithographic and chemical etching techniques. this technique could be naturally combined with SAM materials that have a potential to make patterned nanostructures on various surfaces via molecular self-organization. Therefore. The results are reviewed in Refs 48. in our daily life. techniques for fabricating patterned structures onto a local surface of a substrate at the molecular scale are classified into two approaches. This type of technique in nanotechnology is referred to as the bottom-up approach.2. These techniques . 1. One is a processing technique that is widely recognized as a traditional pattern formation method. Therefore. If such a purpose could be accomplished. yet a premature one as compared to the topdown approach. Nature exquisitely architects many systems of predesigned nanostructures and effectively uses lots of molecular devices in the systems. 86]. and several techniques of lithography. We have to scale down the macroscopic architectural technique to the molecular scale. 1. in particular. in which specific self-assembling components have a deliberate spatial distribution on the surface.2. many elaborated devices have been made of a large number of small components and all buildings can be constructed step by step on the foundations. Generally.2. The other is a kind of architectural technique that could be imagined from its analogy to our macroscopic world. A unique technique using AFM cantilever as a substrate is recently introduced in Ref. That is.1 Two Approaches for Fabricating Patterned SAMs: the Top-down Method and the Bottom-up Method Patterned SAMs. are generated to fabricate nanoscale architectures and to provide well-characterized supports for physicochemical and biochemical processes [86]. and so on. 277].7. such as genetic coding and decoding systems [278].7 Patterned SAMs 1. A wide variety of investigations using such a technique have also been extensively undertaken from the viewpoint of fabrication of organized molecular interfaces. To confirm the origin of the friction contrast of the phase-separated domain between hydrocarbon (HC) and fluorocarbon (FC) in L–B films described below (Sect. 75. 76.1. printing. and nanohandling as examples of the top-down method. 274. Such a set of techniques will be referred to as the top-down method for fabricating patterned SAMs. Toward such a goal. the fabrication techniques of molecular patterns would provide a direct impact on the preparation of chemically modified electrodes with such patterns. photosynthetic reaction center systems [279].52 1 Preparation of Monolayer Modified Electrodes have been applied to this issue. Such studies on the two approaches will be briefly described here.

IR. The analysis is required for characterizing the spatial distribution of molecules on the 1–100-nm scale [281]. molecules of similar alkane-chain length but with differing terminal groups (i.e. 291]. 288]. Spontaneous Phase Separation Multicomponent SAMs. as the location of the probe tip can be placed on the surface at a specific set of coordinates and the resolution of the patterns can approach the molecular scale [86]. and variation of the buried functional group [258]. STM is a powerful tool that meets the requirement [281–283]. which is also called near-field scanning optical microscopy (NSOM). 280. which is referred to as scanning probe lithography (SPL). The simplest case is a mixed SAM of two components.1. was found to be useful for optical patterning of SAMs [292]. 282. optical patterning was readily achieved [292]. 1. if the molecular features of the components are quite different phase segregates may result in mixed SAMs.1. can be applied to a wide variety of functional . Whitesides and coworkers reported recent unconventional methods for fabricating and patterning nanostructures [280]. In addition to STM and AFM. In FFM.2.7. The phase separation of SAMs has been characterized so far by various analytical techniques such as XPS. alkyl fluoroalkyldisulfides [284.2. Friction force microscopy (FFM) is also useful for the purpose [284–286]. are usually formed by a solution deposition method. 290]. Their performance and intrinsic limits are summarized in tables in Ref. Such a SPM technique for lithography.3 Scanning Probe Lithography Using SAMs Patterning of surfaces with SPMs. such as AFM and STM. Such systems include the coadsorption of short and long-chain alkanethiols (i. as described later. By controlling tip-sample separation of SNOM by AFM [293–295]. In the latter case. G untherodt and Fujihira and their coworkers demonstrated for the first time that FFM can be used to image the chemical contrast between the phase-separated do˚ mains with a resolution of ∼5 A [287. both species adsorb on the substrate surface [86]. has been explored.2 .e. SPMs among them. Many studies on spontaneous phase separation of alkanethiol-based SAMs have been conducted using different types of variation in the molecular composition [86]. ellipsometry. have sufficient lateral resolution and therefore appear the most promising for direct imaging of nanometer scale patterned SAMs [281]. On the contrary. variation of the alkylchain length) [55.. both the normal and the lateral force were measured simultaneously during the scanning. 62.1. The readers interested in near-field optical microscopic manipulation and a local optical observation should be referred to a review article [296].2 SAMs on Au and Ag Electrodes 53 are useful as methods for preparation of chemically modified electrodes. so-called mixed SAMs. and scanning probe microscopes (SPMs). 56. When a substrate is exposed to a mixed solution with two different adsorbates. Although studies were conducted using L–B films. variation of the terminal functional group) [281]. The resultant SAM is presumed to have domains of the two adsorbates uniformly mixed at the molecular level if the molecular features of the components are quite similar. in particular. scanning near-field optical microscopy (SNOM). 1. the two components are separately adsorbed on the surface to form domains of different features depending on the component structure and properties. 289.7.

From the observations based on the molecularly resolved images by UHVSTM. 307]. it was demonstrated that by applying a bias voltage of 2. 303]. that is. 297. 297. Crooks and coworkers established some of the early considerations in STM-based elimination lithography of SAMs under ambient conditions [297. 305]. 306]. Xu and Liu developed an alternating technique of the substitution lithography . An in situ replacement of one organic component by another in a SAM was reported by Chen et al. Alkanethiols can play a critical role in SPL on SAMs. They studied an alkanethiol-based SAM of noctadecanethiol (ODT) on gold using STM in air. elimination lithography. Gorman et al. 301]. The mechanism of this removal was argued to be similar to that reported by Crooks et al. nonpolar solvent (dodecane. SAM component molecules could be extracted. 305]. 304. 299].3–3 V to the sample. Alkanethiols are often called molecular inks. mistylene) is due to the fact that we can avoid the use of coated tips that would normally have to be employed to avoid a high leak current (greater than 1 pA) from the tip into the surrounding solution [297. have also been conducted by AFM [86. 300. Zhou and Uosaki employed a current sensitive atomic force microscopy (CS-AFM) for localized removal of a SAM [86. With CS-AFM. 10). conducted a study on nanoscale reversible molecular extraction and healing of n-nonanethiol (C9)-based SAM on gold (111) using UHV-STM [297. 304. reported an in situ localized removal of a decanethiol (C10)-based SAM and subsequent replacement by dodecanethiol molecules using substitution lithography under an applied voltage in a nonpolar dodecane solution of 10 mM of dodecanethiol [297.c-2) [297]. substitution lithography is subdivided into via in situ addition and via terminus modification (Fig. the idea of which has been already recognized as reactive chemical ‘‘ink’’ of microcontact printing (µCP) [9]. they proposed that the patterning mechanism for the SPL induced removal (or deposition) of ink from SAMs in air was faradaic electrochemical in nature [297. An early demonstration of SPL was reported by Kim and Bard [298]. 10c-1. Further. and observed that the tip mechanical force induced etching of the SAM resulted in defect sites (pits) with diameters of 5–10 nm under a low bias and high tunneling current. Mizutani et al. Many investigations of elimination lithography. Later. 299]. 302]. The use of a low dielectric. that is. For instance. they could compare the topography and current images of the resulting pattern of an ODT (C18)-based SAM simultaneously [297. 307]. Substitution lithography is of extreme importance because this process can provide a direct means applicable to in situ nanoscale surface modification on SAMs to create a variety of specific patterned SAMs. localized removal of a SAM. and substitution lithography (Fig.54 1 Preparation of Monolayer Modified Electrodes SAMs [297]. The SPL on SAMs embodies several elementary procedures of molecular manipulation in molecular surface engineering. [297. For the experiment under a vacuum. which resulted in holes with diameters of 2–5 nm in the SAM [302]. who used STM to replace conjugated molecules into a dodecanethiol (C12)-based SAM on a gold surface [297. 297]. Gorman and his coworkers have classified these into three types of manipulation procedures by SPL. Liu and Salmeron observed that molecules could be displaced with an AFM tip under a high applied load (up to 100 nN) [86. addition lithography.

. (c) substitution lithography.1. 10 Schematic diagrams illustrating three types of the manipulation procedures by SPL [297]: (a) elimination lithography.2 SAMs on Au and Ag Electrodes STM tip Scan direction 55 Substrate (a) Elimination STM tip Substrate Scan direction Substrate (b) Addition Substrate STM tip Substrate (c-1) Substitution via in situ addition STM tip Substrate Substrate (c-2) Substitution via terminus modification Substrate Fig. (b) addition lithography. the substitution lithography is subdivided into via in situ addition (c-1) and via terminus modification (c-2).

Mirkin and coworkers have pursued their investigations for fabricating a wide variety of patterned SAMs. They emphasize that the ability to control surface properties using SAMs is most useful when combined with spatially defined patterns. The fundamentals of DPN are intensively discussed. is approximately 4000-years old and has been used extensively throughout history to transport molecules on macroscale dimensions [315]. reported the investigation of approaches for the fabrication of protein patterns by SPL [314]. In particular. Soft lithography allows the creation of useful . Dip-pen technology.1. 308]. 1. SAMs can be removed by mechanical means using an AFM tip followed by in situ replacement with a second component. 297]. and the application of electrochemical potential to the AFM tip in the DPN process [324]. and molecules with a chemical affinity for the solid-state substrate as ‘‘ink’’ [315]. 315–318]. Porter et al. it is naturally expected that DPN can become an extremely powerful technique as a SPL tool of nanotechnology [315. Several improvements of the DPN technique are also discussed. Addition lithography using SPMs on SAMs for fabrication of nanoscale patterned SAMs is extremely important as a technique of SPL methodologies. The traditional dip-pen technology and DPN are analogous in style. and a multiple-pen nanoplotter [322]. 297. We will describe this technique in the next section. DPN uses an AFM tip as a ‘‘nib (penpoint)’’.7. in which ink on a sharp object is transported to a paper substrate through capillary forces. such as parallel and serial writing [321]. still not fully understood [297.2. Their results are reviewed in [309]. Some of them can be used for biochemical and diagnostic purposes [324–329]. They referred to this technique as nanografting. 11).7. as depicted in the schematic representation of DPN (Fig. The most typical application of addition lithography with organothiols as ink on gold is well-known as dip-pen nanolithography (DPN) [86. This expectation is based on a conspicuous advantage of the methodology of organothiol-based self-assembly on gold. 315. the flexible chemistry in respect to the terminal groups. 316].2. In this method. 330]. that is. a solid-state substrate as a ‘‘paper’’.1. however.56 1 Preparation of Monolayer Modified Electrodes using an AFM tip in a solution containing another thiol [297. when the methodology of DPN is combined with that of organothiolbased self-assembly on a gold surface.5 Microcontact Printing by Use of Organosulfur Inks Whitesides and coworkers have developed a set of techniques called soft lithography that offers tools for micropatterning that complement and extend the conventional fabrication methods [89. 1. The mechanism governing DPN is. together with charming demonstrations of its application [297. 319. Further intensive investigations related to the application of this technique to the fabrication of nanometer-sized protein and DNA patterned SAMs have been reported by Liu and coworkers [310–313]. Similarly. but are different in scale and transport mechanism. Other researchers have demonstrated several optional techniques: the use of the tapping mode AFM rather than the commonly used contact mode [323]. 320].4 Dip-pen Nanolithography DPN was developed by Mirkin and coworkers as a kind of SPL (‘‘direct write’’) [86. DPN is used to direct ‘‘write’’ patterns consisting of a relatively small collection of molecules in submicrometer dimensions [315]. 316].

and registration with other surface features [86].1. and copper [336]. Using STM and wettability measurements. affects the ODT transport rate. they also compared dodecanethiol (C12)-based SAMs on gold (111) prepared by µCP and by the solution deposition method. 89]. and found that both the characteristics of these SAMs were indistinguishable [339]. elastomeric stamps to print chemical patterns onto gold substrate [338]. SAMs are formed naturally in the regions of contact between a topographically patterned elastomeric stamp and a bare surface of metal. such as gold [331]. metal oxide. n = 17: 1-octadecanethiol H H H H Writing direction H H H H Water meniscus H H Au substrate Fig. Michel and coworkers describe a strategy for µCP that uses planar. the effective tip-substrate contact. or semiconductor [9. Whitesides and coworkers described the use of SAMs as ultrathin resists [331–334]. µCP can also be used in the form of nonplanar surfaces. 332].2 SAMs on Au and Ag Electrodes 57 AFM tip H H H S H H H H H H HS(CH2)nCH3 . such as n-alkanethiols. silver [335]. and other compounds forming SAMs. 11 Schematic presentation of DPN.5 µm can be routinely generated on gold [331. such as. Here. in particular. The size of the meniscus. and DPN resolution [315]. which is controlled by relative humidity. 330–333]. the replication accuracy of the contact pressure that is applied to the substrate. patterned surfaces using a combination of SAMs and µCP [330]. 89. µCP can be applied to many substrates. The stamp was wetted with (or containing dissolved) reactive chemical ‘ink’. 330–334]. curved substrates [337]. The details of the techniques can be found in the several papers and reviews described by the pioneers [9. Xia and Whitesides described a number of approaches that have been employed to reduce the size of features of SAMs generated using . µCP is a method for patterning SAMs on surfaces which is operationally analogous to printing ink with a rubber stamp on paper [9. 86. This character is. we will briefly describe some important points of µCP for fabrication of patterned SAMs as well as the comparison between µCP and SPL. The technique of µCP is generally costeffective because no expensive instrument is needed to conduct the experiment. unique [89]. Using µCP. A water meniscus forms between the AFM tip coated with 1-octadecanethiols (ODTs) and the gold substrate. SAMs consisting of patterns having dimensions less than 0. The reproducibility of the µCP process is dependent on the stamp’s resistance to degradation. 89.

µCP can be applied to the top surface of a SAM. 354]. 363]. which maps the force between an AFM tip and a patterned sample surface just before contact (in noncontact) in air or in liquid. To achieve the quantitative analyses of the adhesive forces for chemical differentiation on the patterned surface by PFM-AFM. 351] (see chemical force microscopy. 330. 362. Michel and coworkers reported a high-resolution printing technique based on transferring a pattern from an elastomeric stamp to a solid substrate by conformal contact.7. 360] and chemical modification of the tip surfaces [361] as well as the precise environmental control. On the patterned surface. in which the oxides were dipped [353. 344. Recently. they investigated the change of the surface charge on various oxide surfaces as a function of the pH of the solution. Fujihira and coworkers demonstrated imaging of a patterned surface with electrostatic charges with opposite signs in aqueous buffer solutions [350]. Fujihira and coworkers extended PFMAFM to adhesive force mapping on a patterned SAM [356–358]. alkanethiols substituted with anionic and cationic end groups. such as electrolyte concentrations [292. 1. Using the force mapping with PFM-AFM. Using µCP with two types of ink. 343]. which are controlled by electrostatic and lateral capillary interaction. CFM [352]. They also measured the forces between a gold-coated tip and a gold plate in aqueous solutions.1. pulsedforce-mode atomic force microscopy (PFM-AFM) designed by Marti and coworkers [349] is useful as scanning force microscopy with chemical recognition capability [350. 341]. that is. coined a word for such an SPM. where electrode potentials of the tip and the plate were the same [355]. Electrostatic interaction on patterned SAMs fabricated using µCP are investigated. difference in the adhesive force between the −CH3 and −COOH terminated regions on the µCP patterned SAM was mapped simultaneously with its topographic image.2. Before this study. Patterned SAMs on gold can be prepared by the combination of µCP and the subsequent solution deposition methods [342]. Whitesides and coworkers have demonstrated the microfabrication of chemically charged patterned SAMs using µCP [347]. Frisbie et al. fabricated a chemically patterned SAM with anionic and cationic regions [346].2. In this mode of PFM-AFM. CFM: Fujihira).58 1 Preparation of Monolayer Modified Electrodes µCP [340]. that is. CFM was originally based on FFM due to its chemical recognition ability [287] as already described in Sect. and humidity [364] are indispensable. which leads to a new type of lithographic approach to prepare patterned SAMs using a locally selective catalytic reaction [341. 345].and nanoscale patterning technologies [91. As an analytical tool for such a chemically patterned SAM surface. and described the potential for emerging micro. Aizenberg et al. Patterning of proteins and cells using µCP is reported by Whitesides and coworkers [117. they directly observe the process of patterned colloidal deposition and assembly. Bohn and coworkers used PFMAFM to map the adhesion force between an AFM tip and samples of ω-substituted alkanethiol monolayer terminated with −CH3 and −COOH prepared by µCP . They expanded this idea to directed self-assembly of two oppositely charged particles on patterned electrode controlled by an applied electric field [348]. Several new approaches using µCP have been reported. accurate information about the tip and substrate geometries [359.

they are well known as UV photolithography. SFINKS combines elements of DPN and µCP to generate patterns. multiple copies of the pattern can be produced using straightforward experimental techniques [89. the readers can refer to a recent review by Zarnikov and Grunze [367]. Recently. In the case of µCP. Alkanethiolate formed by the adsorption of alkanethiols are oxidized on exposure to UV light in the presence of air to alkylsulfonates: Au-SR(CH2 )n X + 3/2O2 − − −→ hν Au + X(CH2 )n SO3 + − (1) The mechanism of this reaction has been the subject of some debate.1.6 Photolithography for Fabricating Patterned SAMs Lithography has long been developed as a common technique for fabricating microelectronic devices. plays a central role for the nanoscale fabrication. The process underlying photopatterning of SAMs on gold and silver is well known at the phenomenological level [368. Here we will discuss UV photolithography for fabricating patterned SAMs. Orden and coworkers demonstrated an alternative patterning technique. a prepatterned stamp displaces the scanning tip. Namely. The development of photosensitive resists capable of replicating patterns written by photons or electrons with resolution below 10 nm remains a challenge for chemistry and materials science [9. SPL has a patterning feature that can be determined in situ and easily changed. UV-photolithography can be classified into two methods. This contrast is the same as that between the photomask and the SNOM tip in the near-field irradiation [292]. 371. in SFINKS multiple tips with different inks deposit inks to individual stamp features and then the different inks are transferred to the different locations on the substrate by µCP. Notably. once the stamp is available. However. µCP can generate many features simultaneously on the surface in a single step. 1. Correspondingly. 86. and X-ray lithography respectively [9.7. whereas SPL is a serial technique that writes only one feature at a time [9].2. and plays a central role in the nanofabrication of patterned SAMs [9. 275]. whereas µCP requires a prepatterned stamp that has to be made in advance.25 nm2 and (2) they are very thin (<3 nm). the two techniques are complementary to each other. but Leggett and coworkers showed that oxidation can . Patterned SAMs are candidates alternative to the polymer resist used in the techniques. One is a straightforward method for photopatterning alkanethiolbased SAMs on gold and silver surfaces with micron-scale resolution [368–372]. in which the placement of the tip is three dimensionally controlled at the nanometer scale to fabricate patterned SAMs. here. e-beam lithography. For modification of SAMs by e-beam lithography and X-ray lithography. which they refer to as Single Feature INKing and Stamping (SFINKS) [366]. 372]. 330–333]. Whitesides and coworkers [9] describe that two characteristics make SAMs potentially useful as resists for lithography: (1) they consist of individual molecules that occupy areas smaller than ∼0. 275]. The scanning tip. and X ray. SFINKS can pattern multiple components with complex structures without cross-contamination.1. A key difference between SPL and µCP is as follows.2 SAMs on Au and Ag Electrodes 59 and to study electrochemically generated gradients [365]. electron-beam (e-beam). 89. The SPL described above is applicable to a variety of patterning techniques using a small STM or AFM tip end. Therefore. 330–333]. 369. using UV.

since successive oxidative oligomerization would generate insoluble poly(disulfides). The method allows us to transfer metal films from the raised regions of a stamp onto various oxide surfaces. 385–387].7. Using nTP.2.2. which defines the geometry of the pattern. a wide range of patterns can be printed in parallel with nanometer length scale resolution over large areas.1.8 Other Methods The bottom-up approaches intrinsically have numerous possibilities by means of the hybridization of techniques compatible with each other for fabrication of patterned SAMs. and nanofabrication using a nanopipet addressing [391]. Moreover. that is. in particular. They describe that using nTP.7 Nanotransfer Printing of Patterned Gold Thin Films While µCP offers fast and low-cost approaches for patterning flat or curved surfaces over large areas in a single processing step. Tour and coworkers have also found a thiocyanate to be an excellent precursor for .7. Acetyl-protected thiols are most commonly used for organothiols. orthogonal self-assembly of electroactive monolayers [57. The in situ deprotection immediately followed by the deposition of the deprotected sulfur compound onto gold surfaces under acid or alkaline condition of the solution would be better than the stepwise reactions of deprotection and deposition as the preparation method of SAMs from chemically unstable thiols. 1. ω-dithiols.1. especially for aromatic and π-conjugated thiols. etching procedures. The other is the fabrication of SAMs by using photochemical reaction of photoactive pendant groups. silicon wafer) substrates. it is generally subtractive in operation. onto both conformal (thin poly(dimethylsiloxane) film supported on plastic) and rigid (e. is expected to be useful in the fabrication of the electrical components of functional organic transistors and complementary inverter circuits [377–382]. and by Wrighton and coworkers [374. and recently by Turro group [376].2. such as micromachining [383. This technique.g. enzymatic nanolithography [388–390].60 1 Preparation of Monolayer Modified Electrodes occur in the absence of ozone with use of a UV source emitting principally at 254 nm [373].8. They noted that the use of disulfides (Ar−SS−Ar) as precursors. they found that the acetyl-protected thiols can adsorb directly on the gold surface without the use of an exogenous base. Tour et al. as demonstrated in 1993 by Fujihira and coworkers [292].1 Protecting Groups for Unstable When we prepare a Organic Thiols SAM of chemically unstable organic thiols that are easily oxidized to the disulfide molecules in the air. 384]. protecting the thiol group is important during preparation. have found that acetyl-protected thiols provide an excellent method to alleviate the problem of isolating and using the oxidatively unstable thiols [392]. we are able to transfer the metal pattern from a stamp with the relief feature. although higher concentrations of the thioacetyl compounds are required than those of thiols [392]. Such approaches will be combined with other methods. 375].8 Advanced Modification Technique of SAMs 1. or postpatterning deposition steps.1.1. it typically requires the use of sacrificial resists. 1. is impractical for the α. which has been developed by Rogers and coworkers [377]. 1. Nanotransfer printing (nTP) is a purely additive printing technique that has nanometer resolution.2.

The most straightforward approach for obtaining such a SAM surface terminated by free thiol groups would be the use of alkanedithiols.8. The difference can be interpreted by higher van der Waals molecule–molecule interactions of the cage hydrocarbons than those of the linear single alkane chains [402. . stable SAMs could be formed from disulfides with these cage hydrocarbon units in spite of their short molecular lengths. We can adopt their structures into the backbone units of component molecules of SAMs. we are able to divide SAMs into two classes of flexible SAMs and rigid SAMs. such a spacer is called a geometrical buffer [403].6 using BCO-based SAMs [255]. The most important characteristics of these cage hydrocarbons are their higher boiling points than those of single alkane chains with similar molecular lengths. In other words. and distillation columns [396]. for molecular design of the backbone of the component molecules of SAMs.2.1 Rigid SAMs BCO and Adamantane SAMs Chemical structures are among the trademarks of our profession. However. Analogously.2. The structural difference between the two adamantanebased components of the SAMs is the presence or the absence of a methylene spacer connecting between a rigid adamantane unit and a thiol head group.2 SAMs on Au and Ag Electrodes 61 thiolate assemblies [393].2. the protecting groups can be removed by immersion into a NaOH solution.1.9 1. it is useful to see the chemical structures in terms of flexibility or rigidity. when these spherical cage components formed . ω-dithiolderived molecules. Therefore. This strategy was already described in Sect. Fujihira and coworkers also demonstrated that a stable adamantanebased SAM was formed successfully on a gold (111) surface [402]. 403].1.2 Modification Technique of SAMs The generation of organic of Dithiols surfaces terminated by specific functional groups is significantly important for the application of SAMs. They described that these easily synthesized molecules can be assembled on gold surfaces directly in a variety of solvents and are an excellent complement to free thiol and protected assembly procedures. 1.2. are two typical examples of rigid hydrocarbon molecules [397–401]. 1. beakers. in particular. HS–(CH2 )n –SH. Recently.1. After formation of the organothiolate adlayers. Cage molecules. 1. which are comparable to those prepared directly from alkanethiols [394].9. Schreiber described that such an extra methylene spacer plays a critical role for removing the steric hindrance in the SAMs [48]. illdefined alkanethiolate adlayers. In addition. This technique is ideal for aromatic systems and α.1. Therefore.4. W oll and coworkers demonstrated that high-quality organothiolate adlayers exhibiting a SH-terminated surface could be prepared using dithiols where one of the thiol groups was protected by a thioester group [395]. just like alkane chains in alkanethiol-based SAMs. it has been shown that this straightforward approach leads to the formation of disordered. Weiss and coworkers have also examined the property of a SAM using an adamantanethiol derivative [403].. with only a small number of free −SH groups at the surface of the SAM.1. Hutchison and coworkers have reported that in situ deprotection and assembly of S-tritylalkanethiols on gold yield monolayers. as surely as chemical flasks. such as BCO and adamantane.

As to early studies using cage compounds with thiol head groups. These studies were followed by recent researches by Grunze and coworkers [440.2. which were first prepared on gold as a new family of SAMs by Rubinstein and coworkers in 1993 [415]. The most distinct attribute of this structure is its electrical properties due to π electrons. The most typical family of aromatic SAMs is composed of a series of 1. Tokumoto and Fujihira [426–428]. that is. which exhibits rich molecular chemistry. The short heights allow us to use these organosulfur compounds for formation of SAM matrices. 41]. and thus. which do not require the molecular axes to be tilted in the SAMs [402]. using such systems [270. They revealed that such aromatic SAMs certainly exhibited a close-packed structure in a hexagonal arrangement with an overlayer of a √ √ ( 3 × 3)R30◦ with respect to the underlying gold (111) surface if the component molecule. in this introductory account. the readers are referred to Refs 411. 414]. it is impossible to take up all subjects of the aromatic SAMs studied by many researchers. 441].9. 421]. Early STM investigations by other groups using thiosalicylic acid as a component molecule forming a SAM were reported [419]. 413. The result was rationalized by the spherical shape of the cage backbones. Many studies have been conducted using various aromatic SAMs.2. phenyl-. by W oll [422–425]. The structure was also discussed using molecular dynamics simulation [418].1. The studies using cholesterol-based SAMs were reported by Yang et al. and Terfort [431. biphenyl-. Aromatic SAMs A different type of rigid molecule is the aromatic molecule. After that.62 1 Preparation of Monolayer Modified Electrodes SAMs on a gold (111) surface. Here we will describe only some aromatic SAMs of interest from the viewpoints of SAM preparation. The families of terphenyl-based SAMs have been studied . in which other thiol molecules can be inserted into the single molecular defects as upright single molecules. the fabrication and characterization of structures and properties of various aromatic SAMs on gold and/or silver have been extensively investigated using a wide variety of instruments. Biphenyl-based SAMs were intensively investigated by Ulman and coworkers [433–439]. the structures of SAMs of aromatic-containing thiols on gold or silver were characterized by Tao and coworkers using IR [416] and STM [417]. Many other relevant studies have been performed . After the early successful investigations. [5. 412..1. 430]. They first studied aromatic SAMs to investigate the influence of aromatic units incorporated in long alkane chains of alkanethiol-based SAMs on gold [8. only single molecular defects instead of the defects due to the grain boundaries were seen in the SAMs [404]. the grain boundaries observed in the linear alkanebased SAMs were not observed. The single molecular electronic and mechanical properties were measured by STM and noncontact-AFM. Studies on the kinetics and stability of aromatic SAMs have been undertaken [420. respectively. and terpheny thiols. which is present widely in biological membranes. In consequence of the absence of the tilt.3 oligophenylenethiols.2 Cholesterol SAM Cholesterol is another type of rigid molecule. 404–410].9. Zharnikov [429. has a methylene spacer connecting the thiol head group and the aromatic unit. that is aromatic thiol. 432] and their coworkers. 1.

in which some aromatics. The πconjugated SAMs have been intensively investigated by Tour [392]. Here we will describe the recent new modification strategy. Recently.12. van der Waals interaction. and molecules needed for biology and biochemistry [9]. . described that there are three general strategies for engineering the composition of the exposed surfaces [9]: (1) Synthesis of functionalized thiols for forming single-component or mixed SAMs by (co-) adsorption. and later by others [472–474]. SAMs formed from alkanethiols and aromatic thiols have well-ordered structures. 452]. 12). this field of bio-SAMs has been extremely well realized in biophysical chemistry and electrochemistry [101] (see also Sect.and phenylmethyldisulfides adsorbed on silver [449] were undertaken as early as 1982.2. we can perform a rich chemistry on the exposed surface of SAMs. The foresighted idea of fabricating bioaccessible interfaces of SAMs was first demonstrated in 1982 by Taniguchi and coworkers [29]. Nonphenyl types of aromatic SAMs are also the subjects of importance. indicating that this offers a convenient method to modify well-defined electrode surfaces [97]. 445]. and the studies by Szafranski et al.1. and others [446–448].2 SAMs on Au and Ag Electrodes 63 by Zharnikov and coworkers [442. such as phenyl and thiophenyl. They demonstrated that this reaction proceeds completely at room temperature in aqueous solvent.e. and followed by the study on copper. and Chidsey first applied this chemistry to the exposed surface of SAMs (Fig. hydrogen-bonding.1. This reaction uses the formation of triazoles through the classic . we can realize that both covalent and noncovalent interactions (i. or alternately conjugated with ethynyl or acetylene units. and (3) modification of the structure composition of a preformed SAM. Methods for modifying SAMs after their formation are critical for the development of surfaces that present the large. early intensive studies by Crooks and coworkers [466–471].1. are conjugated in a series. Devaraj. The reaction is extremely specific with high yield. silver.11 Chemistry on SAMs 1. 443].1. Otsubo [462]. We can see that there are a number of studies on the reactivity of SAM surfaces. Love et al.2. although the substrates for SAMs are limited to a few metals such as gold and silver.1 Click Reaction on SAMs SAMs provide ideal molecularly defined bases to study reactions in two dimensions [464].3). 1. (2) insertion of synthesized thiols into defect sites of preformed SAMs.2. π -Conjugated SAMs This category is defined as a structural expansion of the aromatic SAMs described above. and gold [450]. Surface-enhanced Raman study of phenyl. This new strategy is the application of Sharpless ‘‘click’’ chemistry [475]. Therefore. and Bao [463] and their coworkers. clicking functionality onto exposed surfaces of SAMs [97].1. and allow a wide range of functionalities to be incorporated into the monolayers [465].11. These SAMs have been intensively investigated recently because of their potential applications in molecular electronic devices [457]. complex ligands. for example. W oll and coworkers [444. 1.. Sita [458–461]. Through these studies. [451.2. and metalligand bonding) can generate new interfaces of SAMs [9].10 1. Several groups have investigated pyridinethiol-based SAMs [453–455] and thiophene-based SAMs [456]. Collman.

. Choi and coworkers reported the reactivity of acetylenylterminated SAMs on gold toward ‘‘click’’ chemistry. CH3 Au Fig. Functionalization of SAMs on gold through cycloadditions has already been demonstrated with Diels–Alder chemistry [477]. 475]. Almost simultaneously.64 1 Preparation of Monolayer Modified Electrodes Huisgen 1. Direct interfacial reactions of exposed functional groups are listed in [9].3-dipolar cycloaddition [9. 12 (a) Depiction of a mixed SAM-modified gold electrode surface before and after ‘‘click’’ chemistry between azidoundecanethiol (inserting into the SAM) and ferrocene propynone (dissolving in aqueous ethanol solution) [97]. leading to the formation of a similar modification as described above [476]. O N − N + N N − N + N Fe N N N H N N O Fe N H O Fe S S S S S S S S S S S S S S S S S S Au (a) Au O NH N − N + N − N + N O NH X X X X X N O S O H H O NH N S O H H O O S O N N N H N N H H H N H N N H H DNAO H DNAO X X X X X H H DNAO H S S S S S S S S S S S S S S (b) Au X = OH. Further. Devaraj et al. demonstrated this method to apply to the fabricating oligonucleotide functional SAMs [478]. (b) Depiction of a similar ‘‘click’’ reaction to (a) except for the coupling of an oligonucleotide probe in aqueous dimethyl sulfoxide solution [478]. (c) Depiction of a acetylenyl-terminated SAM on gold surface before and after ‘‘click’’ chemistry between the SAM terminated with acetylenyl groups and 3’-azide-3’-deoxythymidine dissolving in aqueous ethanol solution [476].

SAMs play a vital role in mediating between electrodes and abundant chemical and biological interactions or reactions generated at the surfaces.1. 153. that is. We can take advantage of this fundamental principle of electrochemical reactions to provide a wide variety of specificity into the nanoscale electrochemistry on the exposed 1.2 surface of SAMs. SAMs themselves are also able to couple to electrochemical reaction processes aggressively depending on their structure [480]. Thus.11. As a nanoscale foundation. If these chemical processes are fast relative to the electrontransfer reactions. 105–107.2. In such a system. the overall electrode reactions are kinetically characterized. Many experiments relevant to electrochemistry on SAMs ranging from the fundamentals to the applications have been reported so far. The experiments on the fundamental issues include electron-transfer model systems [88.2 SAMs on Au and Ag Electrodes R N N N 65 R-N3 : O O O HN O O HO O O H H H H N3 N O O O O R-N3 H O N3 OH S S O N3 O O NH2 Au (c) Fig. this system involves various issues of electrochemical reactions coupled to chemical and biological reaction processes [108]. Electrochemistry on Thiol-based SAMs Modified at Electrodes Electrode reactions consist of the combination of elementary processes. 98. electrontransfer reaction processes between redoxactive species and electrodes coupled to the preceding and/or succeeding chemical processes [479]. the chemical processes are thermodynamically reflected in the overall electrode reaction. 12 Au (continued). Therefore. The field of electrochemistry on SAMs modified at electrodes have an emergent possibility for accessing chemical and biological molecules at the nanoscale through the exposed surfaces of SAMs. . 99.1. If these chemical processes are slow. the electrode reaction can express the specificity depending on the characteristics of the chemical processes spatially and temporally coupled to the electron-transfer reaction.

receptors biomembranes. such as Ringsdorf and Knoll and their coworkers [136. that is. oligonucleotides [520–522. cells. Until now. 525. 541]. Liu and Barton have demonstrated DNA electrochemistry by developing methodology to assemble DNA duplexes onto gold surfaces with SAM techniques and to use daunomycin as a redox reporter intercalating to DNA through covalent cross-link to guanine residues [521]. 103. 528. 551]. 527. demonstrating that this method using the redox cycle amplification is extremely useful in an ultrasensitive DNA detection system [522]. such as proteins. a central activity of modern chemical biology [520]. numerous experiments have been reported for the functional SAMs. which may be defined as SAMs that make it possible to interact actively with biomolecules and systems. Mrksich [102. there has been a growing tendency toward the development of this technology. and structural control of electroactive molecules on SAMs [519]. High sensitivity. Electrochemical control is another important technique in this field [102. the expression of porphyrin functions in supramolecular systems [510–518]. biofunctional proteins [524. a redox cycle of Ru(NH3 )6 3+ /Fe(CN)6 3− . Biocompatible SAMs are defined as SAMs that make it possible to inhibit the adsorption of nonspecific biomolecules and cells onto the surface.11. biomembrane [550. Oligo(ethyleneglycol) terminated alkanethiol-based SAMs (OEG-SAMs) on gold is a well known typical example and is the prototype of the biocompatible SAMs.66 1 Preparation of Monolayer Modified Electrodes 481–492]. and so on. Early leading studies of the biofunctional SAMs were reported by several research groups. for instance.3 Bio-SAMs Biomaterials are of great importance for many medical and bioanalytical applications [529]. 123] in a sense that these materials do no mischief to life and biosphere. low costs of instrumentation. Kelley and coworkers have reported a nanoscale approach to DNA biosensing that uses oligonucleotide-functionalized gold nanoelectrode ensembles coupled to electrocatalytic system. oligonucleotides. 535]. a ready capacity for miniaturization. The other is the so-called biocompatible materials [104. 536–538]. and biomolecular recognition [498–506].1. One is biofunctional SAMs. Electrochemical techniques offer attractive approaches to the detection and identification of nucleic acids. enzymes. Plant [533]. 539]. 523–526]. and cells [526. and Yang and Kwak [528] and their coworkers have intensively demonstrated the importance of electrochemistry on SAMs through a series of interesting experimental challenges to the issue on electrochemically induced coupling reactions and releases of the attached molecules and cells. antibody [540. Two families characterizing biointerfaces by using SAMs can be referred to as bio-SAMs. 1. electrochemical STM [493–496]. Whitesides [527]. 542–549]. 493]. oligosaacharides. tissues. 553]. Recently. and Whitesides and coworkers [534. enzymes [116.2. 103. ionic recognition [497]. scanning electrochemical microscopy [155. This type of SAMs is intriguing because we can realize that structural disorder and flexibility of organized surfaces at the molecular . 109]. The experiments for the applications include electrochemical polymerization of electrically conducting polymers on the surfaces of SAMs [507–509]. 530–532]. and direct electronic readout offer strong motivations for the development of this field [520]. receptors [552].

It is also suggested that the penetration of water molecules in the interior of the SAM is a necessary prerequisite for protein resistance [555]. Cell-surface carbohydrates play a fundamental role in important biological processes such as cell–cell recognition for adhesion or communication. and ellipsometry [121]. and the tissue growth and repair [559]. the data of which are shown for adsorption of fibrinogen and lysozyme onto singlecomponent SAMs [122]. some carbohydrate-terminated SAMs have been prepared to use a model system for studies of carbohydrate–protein interactions by several researchers [560–564].2 SAMs on Au and Ag Electrodes 67 level are also of extreme importance as a variety of functionalized surfaces. They concluded that both internal and terminal hydrophilicity favor the protein resistance of an oligoether monolayer [555]. and conformational flexibility (such as OEG groups) is also not a prerequisite for protein resistance of a surface [122].1. It is now realized that carbohydrate–protein interactions provide the key to an understanding of such biological recognition phenomena [559]. This strategy has been used for numerous experiments and the availability has been exemplified [102–104. contact angles. Whitesides [122] and Grunze [555] and their coworkers have focused on the mechanism of protein resistance by OEG-SAMs. OEG-SAMs are not unique in their ability to resist the adsorption of proteins. Whitesides and coworkers have discussed this issue by examining it on the basis of a survey of ∼50 organic functional groups (X-) terminating in X-(CH2 )n SH for the components of protein-resistant SAMs. The kinetics of the adsorption of proteins on a variety of functional-terminated SAMs. Whitesides and other groups have adopted the feature of OEG units into the architecture of a wide variety of structured surfaces relevant to biocompatible SAMs as well as biofunctional SAMs for various targets. 156]. the studies of the adsorption of proteins at the model surfaces formed using mixed SAMs containing hydrophobic (methyl-terminated) and hydrophilic [hydroxyl-. Therefore. maltose-. the interactions of bacteria. carbohydrate modified SAMs can be added as a new family of bioSAMs. . were scrutinized using SPR spectroscopy. and hexa(ethylene glycol)-terminated] alkanethiols on gold have been performed [120. and cancer cells with hosts. Whitesides and coworkers first prepared OEG terminated alkanethiol-based SAMs on gold and the formation was characterized by XPS. 123. 117. Grunze and coworkers have systematically investigated protein resistance of oligoether-terminated SAMs on gold and silver surfaces to elucidate structural factors that determine whether a SAM will be able to resist protein adsorption [555]. we will briefly describe the course of development in the following text. Therefore. Subsequently. They revealed that these SAMs have substantial disorder in the OEG-containing segment. 556–558]. They noted that several different types of X. demonstrating no protein was adsorbed on the surface of hexa(ethylene glycol)-terminated alkanethiol SAM [554].can form the basis of surfaces that resist protein adsorption. Finally. viruses. 116. 524–527. the working of the immune system. The structure of such carbohydrate-SAMs was studied by highresolution AFM [565]. SAMs presenting other functional groups are also protein resistant. containing a hexa(ethylene glycol)terminated SAMs.

in which the techniques of SAM preparation are prerequisite to the arrangement of the experiments. J. 4481–4483. S. is only for height direction with respect to the substrate surface and not for lateral directions over the two-dimensional surface. 4. Langmuir 1990. We have omitted another important topic of the preparation and applications in SAMs useful to studies on molecular electronics (molectronics-SAM). which are based on chemical. G. electrochemical. electrochemical. D. Am. Mathias. B. Allara. G. R. In this section.: A. T. M. E. and biological new approaches. Chem. C. 6. Soc. D. relatively stable forms presenting functionalized organic surfaces. such as OEG-SAMs. 24. Allara. These include the convenient techniques for preparation. through the simple preparation principle of self-organization on substrates. This finding is also of importance in the fundamentals and applications of SAMs. Seto. Vol. Several techniques described here for fabricating patterned SAMs are effective approaches to have access to the issue on the technique for the lateral control at the nanoscale. B. 2418–2421. M. Advanced organic chemical approaches are also intriguing as a solution. 10. M.2. Laibinis. which is of a higher level. 1–41. 2358–2368. Allara. F. Whitesides.68 1 Preparation of Monolayer Modified Electrodes Concluding Remarks The idea of supported SAMs on gold and the concept of chemically modified electrodes have naturally fused to produce a new field of interdisciplinary researches as described here. electrochemical and biological nanotechnology. 2. Another order of SAMs.. 1312–1319. Bioelectron. we can realize that such new researches stem from unique characteristics of SAMs on gold.1. 3. It is because the SAMs and their preparation techniques have already been providing fruitful opportunities to allow us to challenge future technology. Ulman). in which 1. 105. 87–96. J. Chem. is the molecular order being present in the well-defined adlattice structures of SAMs. 1998. 254. . The structural order of SAMs that we can certainly control at the molecular level. L. P. Biosens. R.-W. L. 771–783. This order depends on the underlying surface structure of the supporting substrates as well as the bulkiness and shape of the molecular components. Academic Press. organic. On the other hand. Nuzzo. and the capability of variations in the backbone structures. G. Nuzzo. G. Lee et al. Grzybowski. Palmer. Finally. 1995. 295. in Thin Films (Ed. Am. 7. A. Whitesides. Soc. L. not simple but relatively precise identification of structures like that of molecules themselves. Whitesides. Science 1991. 5. pp. D. San Diego.12 structurally unique molecular components themselves would serve an essential role in the controllable lateral order of molecules. it is no exaggeration to say that supported SAMs can play a central role as a ‘‘mediator’’ connecting our experimental tools and nanoscopic phenomena. physical. E. J. 1983. G. P. J. in particular. Laibinis. Fusco. and biological fundamentals and techniques. 1987. We have described here only three topics. 6. P. References 1. Science 2002. we realized that SAM surfaces presenting disordered hydrophilic property are extremely effective for fabricating practicable bio-SAMs. The well-ordered structural feature of SAMs is available to the numerous experiments conducted so far for demonstrating various intriguing applications. from the aspect of chemistry on SAMs. The availability of such a molecularly ordered arrangement remains the subject of future preparation techniques. 109.

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Rubinstein. Sapporo. have been extensively studied because of their potential applications in many fields. whose terminal group synthetically changes to the functional group. 2] was generally used to construct the ordered molecular layers on a solid surface. Stratmann Vol. KGaA.) in a solution containing the appropriate alkylthiol derivatives allows us to prepare the molecular layers on the substrate surface. is very simple. I. that can easily form a bond with a terminal group of other functional molecule is formed Encyclopedia of Electrochemistry. with gold as the substrate. Cu. Japan Kohei Uosaki Hokkaido University. the self-assembly (SA) technique has become one of the most popular methods of constructing ordered molecular layers during the last two decades. Edited by M.Fujihira.Rusling Copyright  2007 Wiley-VCH Verlag GmbH & Co. In this case. especially on gold. There are two methods to introduce the functional group into the SAM.2.1 reaction of alkoxysilane on an oxide surface [3. For example. Functionalization of the SAM-modified electrodes is also simple. The preparation of alkylthiol SAM on a solid surface. however. The SAMs of alkylthiols on metals. because the self-assembled monolayers (SAMs) are chemisorbed onto the solid surface and therefore their molecularly ordered structure must be more stable. Bard and M. One is the synthesis of the alkylthiol derivatives. Because the molecules are physorbed onto the solid surface in LB films. we can easily observe a molecular image by scanning probe microscope (SPM). Previously. especially gold. although this has the disadvantage that the synthesis of the alkylthiol derivatives with the functional group is rather difficult.Edited by A. ITO (indium tin oxide).2 Photoelectrochemical Properties of Electrodes Modified with Self-assembled Monolayers (SAMs) of Various Alkylthiol Derivatives Toshihiro Kondo Ochanomizu University. we have to clean the substrate and flatten its surface on a molecular level before the preparation. 4]. we must arrange molecules in order on a solid on a nanometer level. Weinheim. This method has the advantage that a surface with several functionalities is easily prepared just by dipping the substrate into the solution as described above. and J. corrosion inhibition. and molecular electronic devices [3–5]. and biomolecular. On the other hand. before the preparation.1.ISBN: 978-3-527-30402-8 . wetting control. the Au(111) surface is generally used as a substrate and it should be annealed by a flame and be quenched both for cleaning and flattening before dipping it in the solution. Just dipping the solid substrate (Au. Tokyo. Pt.2 SAMs on Au and Ag Electrodes 51 1. Japan Introduction In order to achieve modern nanotechnology.F. We can easily introduce functional groups into the SAM. The other method is a sequential multilayer formation. here we concentrate only on the alkylthiol SAM. 10 Modified Electrodes. such as sensors. etc.2. Ag.2. To arrange the molecules in order. the Langmuir–Blodgett (LB) method [1. The SAM-modified electrodes play very important roles in these fields because we have to arrange the molecules in order onto the solid surface for these applications. Although there is another SAM constructed by the silane coupling 1. First. such as a scanning tunneling microscope (STM) and atomic force microscope (AFM) [6–8] even in solution.J. an alkylthiol SAM with a terminal group. their structures easily change and soon become random.

who used lipid bilayer membranes [49. and then the thicker the multilayer.2. the alkylthiol SAM with a wide variety of functionalities is a good candidate for constructing the elaborate molecular machinery. especially for the SAM-modified electrodes. than the redox potential of the quinone moiety (curve (a) in Fig. have extensively investigated the electrochemical properties of the alkylthiol SAMs in detail since 1990 [2. 48]. molecules of various functionalities. respectively. For future nanotechnology. and application of luminescence. and thiol as the surfaceactive group was synthesized and its SAM was constructed on a gold surface. control of electron transfer by photoisomerization. and Fujihira et al.. 1. is one of the most important fields in this research area.5%) [49. are well organized with molecular dimensions so that very efficient photo-induced charge separation and photo-induced electron transfer are achieved with a minimum reverse electron transfer [47. Unfortunately. The application in photoelectric devices. the quantum efficiencies of these systems were quite low (0. 50] compared with that of the natural systems because the molecular arrangements of these systems were not enough to achieve a highly efficient photo-induced electron transfer. In natural systems. including our group. 51–55]. anodic and cathodic photocurrents were observed at potentials more positive and more negative. Photo-induced Electron Transfer at SAM-modified Electrodes Construction of a very efficient artificial photoelectric conversion device mimicking a natural photosynthetic system is one of the dreams of scientists. the lower the surface density.2 such as a photon absorber like chlorophylls and electron donors and acceptors like pheophytins and quinones. regarding the photochemical properties and review the photochemical characteristics of the alkylthiol SAM-modified electrodes. 6–46].52 1 Preparation of Monolayer Modified Electrodes on a substrate and then the functional molecule. respectively. is synthetically attached to this SAM-modified surface. This concept was first employed by Moore et al. . the SAMs with many functionalities have been extensively employed. 3. to arrange molecules in order. it is of great interest to mimic the elaborate molecular machinery of natural systems for the realization of a highly efficient artificial photosynthetic system. PQSH with porphyrin as the photon-absorber. although this has the disadvantage that the synthetic yield of such a surface reaction is usually not high enough to form a perfect monolayer. Thus. and many research groups. In this section. indicating that the photoinduced electron transfer direction can be controlled by the electrode potential [56]. 2). For this purpose. This method has the advantage that multilayer formation is easy. as described above.4–1. we should arrange the molecules on a solid surface at a molecular level. respectively. we focus on photo-induced electron transfer.2. which has the terminal group for the bond formation with the terminal group of the SAM. 57]. especially to sensors. quinone as the electron relay. We have achieved for the first time the construction of an alkylthiol SAM for an artificial photosynthetic system using a porphyrin–quinone–thiol coupling molecule (PQSH) as shown in Fig. 50] and the LB films [4. Thus. In an electrolyte solution containing methylviologen (MV2+ ) and ethylenediaminetetraacetic acid (EDTA) as the electron acceptor and donor. 1(a) [56.

2 SAMs on Au and Ag Electrodes 53 When the pH of the solution increased. 1 Alkylthiol and disulfide molecules with functional groups used in this section. the potential dependence of the photocurrents also shifted in the negative direction (curves (b) and (c) in Fig.1. 2). (a) NH N O N HN O O SH PQSH (b) NH N O (CH2)8 Fe C (CH2)10 SH O PorFcSH (c) N HN NH N HNOC N CH 3 N HN FuPorFcSH CONH O (CH2)11 SH Fe SH (d) S N S CH 3 S SH (e) N N N N Ru2 + N N CH3 2 S SH (CH2)7 N+ + N (CH2)2 S Fig. the redox potential of the quinone moiety shifted in the more negative direction and. accordingly. indicating that the photoinduced electron transfer direction can be controlled by the pH of the electrolyte solution [57]. .

57]. the quantum efficiency of this system is relatively low (ca. This stable photocurrent flowed for more than 3 h without any signs of deterioration.3–3%).1 M Na2 SO4 + 50 mM EDTA + 5 mM MV2+ at a pH of 3. and 5. showing that MV2+ was reduced to the methylviologen cation radical (MV+• ). A novel molecule (Fig. the orders of the molecular layer was low. 2 Potential dependence of photocurrents of the PQSH SAM-modified gold electrode measured in a phosphate buffer solution containing 0. we have achieved the up-hill transport of electrons of more than 1. and thiol groups as the photoactive.5 (b). Although we could achieve the construction of the photo-induced electron transfer system using the SA technique as described above. Ag/AgCl Fig. separated from each other by alkyl chains (PorFcSH) was then synthesized and its SAM was constructed on gold [58]. because PQSH has no alkyl chains and/or the adsorbed amount of the molecules is low. respectively. and surface binding groups.5 (c) [56.5 (a). Ag/AgCl). which has porphyrin. which coincides with the redox potential of the ferrocene moiety in the PorFcSH SAM (Fig. the color of the solution in front of the electrode changed to blue. 3). and therefore. Ferrocene was chosen as the electron relay group because the electron transfer of this group is known to be very fast [38] and the alkyl chains were introduced to form a well-ordered SAM so that the reverse electron transfer and energy transfer from the excited porphyrin to the gold electrode can be reduced. a stable photocurrent flowed if the potential was more negative than +650 mV (vs. When the gold electrode modified with the SAM of PorFcSH was illuminated by monochromated light (430 nm) in the solution containing MV2+ as an electron acceptor. Since the redox potential of MV2+ /MV+• is −630 mV. The photocurrent action spectrum of the PorFcSH SAM-modified gold electrode matched well with the absorption spectrum of the PorFcSH SAM. ferrocene. 1b).54 1 Preparation of Monolayer Modified Electrodes 40 30 (c) (b) Photocurrent density/nA [cm−2] 20 10 0 −10 −20 −30 −40 −400 −200 0 200 400 (a) 600 Potential/mV vs. 0. After prolonged illumination of this SAM-modified electrode. confirming that the porphyrin group in the SAM . electron transport or relay. 4.2 eV by visible light illumination.

After our reports.7 × 1013 photon s−1 cm−2 ) [58]. Imahori et al. in Fig. and the electrode surface flatness dependence that the reason for the achievement of this very high efficiency is the relatively high orientation of this SAM and then the reverse electron and energy transfer are minimized [59–61]. synthesized a fullerene–porphyrin–ferrocene–thiol coupling molecule (FuPorFcSH.1. It is demonstrated by the results of the alkyl chain length dependence. there were a large number of photo-induced electron transfer studies using alkylthiol SAMs [62–79]. As a result of a comparison of their photocurrent generation efficiencies. the highest efficiency among them was achieved at 20 to 25% by the gold electrode modified with the SAM of FuPorFcSH. 1c). really acted as a photoactive site. and porphyrin as a photon-absorber between them.2 SAMs on Au and Ag Electrodes On Off On Off +700 mV +600 mV +500 mV +400 mV Current density +300 mV 100 nA cm−2 +200 mV 55 0 mV −200 mV 20 s Time Fig. and many derivatives similar to it. such as ferrocene and fullerene. then constructed their SAMs on gold and indium tin oxide (ITO) [62–71]. 3 Time course of the current at the PorFcSH SAM-modified gold electrode held at various potentials when the electrode was illuminated with 430 nm pulsed light (40 µW cm−2 . 8. They concluded that utilization of the fullerene group with the small . The quantum efficiency of this system was more than 10%. a structural study by angle-resolved X-ray photoelectron spectroscopy (ARXPS). which has two electron relay groups.

6). 4 Constructed photoactive SAMs using surface-confined oligonucleotides 1 and 2 associated with their pyrene end-labeled complements 3 and 4 by Reese and Fox [80].2 -bipyridine) (Ru(bpy)3 2+ ) -viologen-thiol derivative (Fig. 4) [80]. The alkylthiol SAM can also form on a semiconductor surface [83–88]. constructed the SAM of a ruthenium (II) tris(2. Thompson et al.6 to 1. They observed a photocurrent at this SAM-modified gold electrode in a solution containing MV2+ as the electron acceptor. They constructed the mixed SAM with FuPorFcSH and a pyrene-thiol linked molecule as an antenna group to mimic the natural systems and achieved light harvesting with a photocurrent generation efficiency of 0. Ishida and Majima observed a much more intense photocurrent by the surface plasmon excitation than that provided by conventional direct photoexcitation at the SAM of a porphyrin-thiol linked molecule [75]. Reese and Fox constructed the SAM of a thiol-terminated oligonucleotide on gold and then an oligonucleotide duplex with a pyrene end-labeled oligonucleotide was constructed on its SAM-modified electrode (Fig.5% [72]. also constructed the multilayer of fullerene-cationic homooxacalix[3]arene inclusion complex and anionic porphyrin polymer on an ITO electrode modified with the SAM of a sulfonateterminated thiol molecule (Fig. leading to a high efficiency even at the metal electrode. Shinkai et al. Yamada et al. 5) [81]. They also constructed the SAM of a fullerene-olligothiophenes linked molecule (Fig. 1e) on gold and ITO. and photocurrent generation was observed. 74]. 1d) and observed a relatively large photocurrent [73. it is not easy to prepare it at room temperature as compared with the case O 5' 3' S (CH2)3 O P O AAAAAAAAAA O O O TTTTTTTTT T O P O (CH2)6 HNC (CH2)3 3' 5' O 1 3 O 5' 3' S (CH2)3 O P O AAGAAGAAGA O O O TTCTTCTTC T O P O (CH2)6 HNC (CH2)3 O 2 3' 5' 4 Fig. also observed photocurrent generation at the photoactive multilayers constructed on the porphyrin SAM-modified gold electrode using the electrostatic interaction between a zirconium cation and a phosphate anion (Fig. There are examples of photocurrent observations at the multilayer-modified electrodes using the SAM as an underlayer.56 1 Preparation of Monolayer Modified Electrodes reorganization energy satisfies the severe requirement for the photocurrent generation. . A ruthenium complex was also used as a photon-absorber [76–78]. A report that fullerene was used as a photon-absorber is also available [79]. and a relatively large photocurrent was observed [82]. However.

1. 5 Me ZOR ZOR (a) Schematic side view of the photoactive multilayers developed by Thompson et al. using the molecules shown below. − − − + − + + − − − + + − − + + + − + − − 3 or 4 2 + − S + − S + − S − + + − S + − S − + + + − − −S(CH2)2SO3−Na+ S S S S ITO electrode . fullerene-cationic homooxacalix[3]arene inclusion complex 2 (second layer). 6 Schematic view of the photoactive multilayers of sodium 3-mercaptoethanesulfonate (first layer).2 SAMs on Au and Ag Electrodes x S Au substrate S S S D D D D S Cu S S Cu S S Cu S S Cu S PO3 PO3 PO3 PO3 O3P O3 P O3 P O3 P n HS D SH = ZOR or POR PO3H2 = PV Me PO3H2 N+ N HS N Zn N N SH HS N HN N+ PO3H2 PV NH N SH A A A A PO3H2 PO3H2 PO3H2 PO3H2 57 Zn Zn Zn Zn (a) H2O3P Me A Me (b) Fig. anionic porphyrin polymer 3 or 4 (third layer) on an ITO electrode [82]. Fig. (b) Structures of the porphyrins and the viologen derivative used to construct the above multilayers [81].

observed the photocurrent at the ITO electrodes modified with the multilayer of gold nanoclusters and porphyrin-tetraalkylthiol molecules (Fig. ZnS [105]. whose surfaces were covered with the alkylthiol SAMs. A relatively ordered monolayer of the alkylthiol can be prepared by heating the solution containing the appropriate alkylthiol and simultaneously by dipping the semiconductor substrate in it for several hours. the SAM forms on the semiconductor nanocluster surface. and CdSe [108]. semiconductor nanoclusters. whose surface is covered with the SAM of a porphyrin-viologen coupling molecule [100].2. which were prepared by the above procedures shown in Fig. in the dithiol SAMs on gold is covalently bonded to the surface atoms of the semiconductor nanoclusters [102] and. They suggested that of particular interest is the ability of the alkylthiol SAM-modified electrodes to probe the distance dependence of the electronic coupling. There is an interesting preparation method by which the tellurium nanoclusters were electrochemically deposited on the gold electrodes modified with the SAMs of molecular templates. 7) [96]. investigated the photophysical properties of gold nanoclusters modified with the SAM of a porphyrin-thiol coupling molecule [97. and then the layers of the semiconductor nanoclusters were prepared by dipping the dithiol SAM-modified gold in a nanocluster dispersion (Fig. Yamada et al. First. Gu and Waldeck constructed the n-InP semiconductor electrode modified with the SAMs of n-alkylthiols having several different alkyl chain lengths and observed the photocurrent [84–88]. a unique preparation procedure is employed. The principles of the photocurrent generation at the semiconductor electrodes were well studied and summarized in the literature [89–92]. Imahori et al. Relatively large photocurrents were observed at the gold electrodes modified with many kinds of semiconductor nanoclusters. Li et al. which are covered with the surfactant sodium bis(2-ethylhexyl) sulfosuccinate (Aerosol OT. whose surface is covered with the mixed SAMs of porphyrin-thiol and fullerene-thiol coupling molecules [99]. 98] and observed a photocurrent at the SnO2 electrode modified with electrophoretically deposited layers of gold nanoclusters. whose terminal group is β-cyclodextrin [109]. After this the dithiol SAMs were prepared on the gold surface. such as CdS [103–106]. 8) [102–108]. were prepared in reverse micelles [101]. also observed a photocurrent at the gold electrode modified with electrostatically deposited layers of gold nanoclusters. many studies on photo-induced electron transfer using alkylthiol SAM-modified metal or semiconductor nanoclusters were reported [96–111]. PbS [107]. are stable and easy to introduce to functional groups by a place-exchange method [93–95]. which is not connected with the gold. 8.58 1 Preparation of Monolayer Modified Electrodes of the alkylthiol SAM on a metal surface. AOT). as a result. They investigated the alkyl chain length dependence on the photocurrent and demonstrated that the studies of the photocurrent versus chain length of the alkylthiols can be used to examine how the electron transfer rate constant depends on the thickness of the insulating layer.2. 1. For the gold electrode modified with the semiconductor nanocluster layers.3 Photo-induced Electron Transfer at Electrodes Modified with SAM-covered Nanocluster Layers Since Brust et al. It was confirmed by XPS that the terminated thiol group. Woo . reported that the gold nanoclusters.

1. n HD (P/Au)nP/ITO (n = 0. Each component is drawn in size according to the CdS CdS CdS CdS estimation from experimental results [102]. (d) formation of a second CdS CdS CdS-nanocluster layer (Au-dt-CdS-dt-CdS). 8 Schematic illustration of binding (a) Au-dt (b) Au-dt-CuS of the CdS nanoclusters from reverse micelles onto gold via dithiol and the CdS CdS formation of alternating layer-by-layer dithiol structure: (a) dithiol SAM on a gold substrate (Au-dt). (c) Au-dt-CdS-dt (d) Au-dt-CdS-dt-CdS (c) adsorption of dithiol layers on CdS nanoclusters (Au-dt-CdS-dt).2 SAMs on Au and Ag Electrodes P P ITO P P P Au colloid aq. (b) CdS nanoclusters Au attached on the SAM (Au-dt-CdS). 6.6 9) and (Au/HD)9 /ITO [96].3. 3. Fig. 7 O(CH2)12SAc (Au/HD)9 /ITO P : Porphyrin (P) : Au particle (Au) P O(CH2)12SAc Schematic illustration for the fabrication of multilayer assemblies./THF 3 (Step 1). 9) HS C2H5OH SH(HD) (Step 2) ITO ITO (Step 3) (Step 2) ITO 9 AcS(H2C)12O N NH HN N AcS(H2C)12O Fig. HS-(CH2)n-SH O CH2-CH3 CH2-C-O-CH2-CH-(CH2)3-CH3 Na O3S-CH-C-O-CH2-CH-(CH2)3-CH3 O CH2-CH3 . (Step 2) P P ITO P P P (Step 2) (Step 1) P P ITO P P P P P P P P 59 P ITO NH aq. (P/Au)n P/ITO (n = 0.

(2) Substrate et al.60 1 Preparation of Monolayer Modified Electrodes : SO3-CdS nanocluster Substrate PAH in water for 5 min (1) Substrate SO3-CdS in water for 5 min (2) Fig. 9 Preparation procedures of CdS nanoclusters/PAH multilayers by the alternate two-step dip of the substrate into aqueous solutions containing CdS nanoclusters and PAH [111]. Multilayers of the semiconductor nanoclusters covered with the alkylthiol SAMs. however. 110]. 10(a) and achieved a photon-gated electron transfer at the gold electrode modified with the mixed SAMs of FcAzSH and an azobenzene-thiol linked molecule (Fig. These electrochemical and photoelectrochemical behaviors showed that they achieved a photon-gated electron transfer. 12c) around the redox potential of ferrocene. showing that ferrocene fixed in this mixed SAM plays the role of a catalyst. whose terminated groups are the charged groups. Substrate Repeat steps (1). 110. The electron source of this photon-gated electron transfer is ferrocyanide in the electrolyte solution. Another method was also employed to construct the multilayers of the alkylthiol SAMs-covered nanoclusters on the electrode surface [27–30. Relatively large and stable photocurrents were observed at this electrode and photoelectrochemical properties of the semiconductor nanoclusters were discussed on the basis of quantum size effect [109. a catalytic current due to the oxidation of ferrocyanide was observed (Fig. 12b). can be constructed on the basis of an electrostatic interaction (Fig. For the cis-form of the SAM-modified gold electrode. Figure 12(a) shows the cyclic voltammogram (CV) of the gold electrode modified with the SAM of a cis-azobenzene-thiol molecule (cis-AzSH). . only the redox peaks due to ferrocene fixed in the mixed SAM were observed (Fig. After doping of FcAzSH in the cis-form SAM.2. 12d). Mirkin et al. 9). reversible peaks due to the redox of both ferrocene fixed in this mixed SAM and ferrocyanide in the solution were observed (Fig. 111]. Introducing this group into the SAM-modified electrodes allows us to construct a photo-switching system. After photo-irradiation. Electron Transfer Controlled by Photoisomerization at SAM-modified Electrodes Azobenzene is one of the most popular groups to photoisomerize with 1. It is noted that no redox species such as ferrocyanide were contained in this case. After the addition of ferrocyanide to the solution. observed a photocurrent at this modified gold electrode. no peaks due to the redox of ferrocyanide in the solution were observed. 11) [112].4 a structural change and was often used even for the alkylthiol SAMmodified electrodes [112–124]. synthesized the ferrocene-azobenzene-thiol linked molecule (FcAzSH) shown in Fig.2.

found interesting electrochemical properties at the gold electrode modified with the SAM of the azobenzene-thiol linked molecule shown in Fig.2 SAMs on Au and Ag Electrodes Fig. Fujishima et al. 10 Alkylthiol molecules with functional groups used in this section. 10(b) [115–117] and with the LB films of the azobenzene derivatives [125–129]. They also showed that reduced . 61 N Fe (a) N (CH2)4 SH FcAzSH N (b) O2N N N Fe (c) (CH2)6 SH AzFcSH N O (CH2)10 SH N (CH2)2 C OH O HO (d) NO2 + Ferrocyanide electron source Ferrocyanide electron source e− >400 nm e− AU AU Fig. The reduction potential of cis-azobenzene to hydrazobenzene is much more positive than that of the trans-form. 11 Schematic illustration of control of electron transfer by photo-irradiation at the FcAzSH SAM-modified gold electrodes [112].1.

On the basis of the structural analysis results by in situ Fourier-transform infrared reflection absorption spectroscopy (FT-IRRAS). also showed that only the redox peaks due to ferrocene were observed in the potential range between +200 and +750 mV. 13c). 13a). that is. the redox potential and the charge transfer rate. These changes in the electrochemical characteristics of the latter electrode were reversible. (c) the two-component SAM (1 : 99 = FcAzSH: cis-AzSH) after addition of 0.5 mM K4 Fe(CN)6 .5 M K4Fe(CN)6 (b) Doping of 2 in cis-1 film 5 µA Current 5 µA (c) Addition of 0. however. (a) Anodic cis-1 film in 0. respectively. When the potential was scanned to 0 mV. The CV of gold modified with the SAM of 20% cisand 80% trans-forms AzFcSH (Fig.2 0. The geometric area of the working electrode was 0.5 mM K4 Fe(CN)6 to the cell.0 0. we concluded that the electrochemical properties.6 Potential vs. even if the original form is the cis-form.62 1 Preparation of Monolayer Modified Electrodes Fig. Ag/AgCl (V) hydrazobenzene is electrochemically oxidized only to trans-azobenzene around +200 mV (vs. after irradiation with >400 nm light for 1 h. disappeared. a pair of waves due to the redox of the azobenzene moiety appeared. 12 CVs for (a) a pure cis-AzSH SAM in the absence of light and in the presence of 0.4 0. in the presence of 0. 13c).5 mM K4Fe(CN)6 (d) After cis-trans conversion Cathodic 5 µA 5 µA Amplified response −0. In a CV of the gold electrode modified with the SAM of 100% trans-form AzFcSH (Fig.2 0.5 mM K4 Fe(CN)6 . Ag/AgCl).0 0. we can control the charge transfer rate at the gold electrode modified with the SAM of the azobenzene–ferrocene–thiol linked molecule (AzFcSH) shown in Fig. in the second scan (dotted line in Fig.6 −0. in addition to that of ferrocene in the first potential scan (solid line in Fig. Scan rate = 100 mV s−1 [112]. The electrolyte used in all of the above experiments was 0. and the redox potential and the peak separation of the redox wave due to ferrocene became more negative and smaller.21 cm2 . which was prepared from the solution containing AzFcSH after UV irradiation.2 0. Using this phenomenon.2 M NaClO4 . of the ferrocene group in the SAM-modified gold electrode can be reversibly controlled . (b) the cis-AzSH SAM after doping it with 1% FcAzSH (no K4 Fe(CN)6 ). (d) the two-component SAM.2 0. 10(c) [118]. The wave due to the redox of azobenzene.4 0. 13b). The redox potential and the peak separation returned to the original values after UV irradiation. only a pair of waves due to the redox of ferrocene in the potential range between 0 and +750 mV appeared and did not change shape after the potential scan or UV irradiation.

and 80% trans-AzFcSH SAM-modified gold electrode measured in the potential region between 0 and +750 mV. Ag/AgCl CVs of (a) the 100% trans-AzFcSH SAM-modified gold electrode measured in the potential range between 0 and +750 mV. Willner et al.3-dimethyl-6 nitrospiro-(indoline-2. 14).and 80% trans-AzFcSH SAM-modified gold electrode measured in the potential range between +200 and +750 mV. they achieved photo-switchable on/off bioactivities. 10d) and the amineterminated alkylthiol SAM (Fig. Ag/AgCl 20 Current density/ [mA cm−2] 10 0 −10 −20 0 200 400 600 800 (c) Potential/mV vs. Spiropyran/merocyanine photoisomerization was also used at the alkylthiol SAMmodified gold electrodes to gate/ungate electron transfer [130–133]. Using this SAM.2 -2H-benzopyran)] propionic acid (Fig.2 SAMs on Au and Ag Electrodes 30 20 10 Current density/ [mA cm−2] 10 0 −10 −20 0 (a) 200 400 600 800 (b) −20 200 400 600 800 Current density/ [mA cm−2] 20 63 0 −10 Potential/mV vs. constructed a spiropyran/merocyanine- terminated SAM-modified gold electrode using the synthesized β-1-[3. Note that the potential scan was started from +200 mV in the positive direction. (c) The first scan (solid line) and second scan (dotted line) of the CVs of the 20% cis.and photochemical structural conversions between the cis.1. The electrolyte and scan rate in all of the above experiments were 0. 13 by electro. 15). Fig. Ag/AgCl Potential/mV vs. (b) the 20% cis. respectively [118].1 M HClO4 and 50 mV s−1 .and transforms of the azobenzene moiety in the SAM (Fig. Figure 16 shows an example of their photo-switchable on/off bioactivity systems (redox of cytochrome c) .

[139] Bohn et al. constructed the protein-connected SAMs by using the procedures shown in Fig. In this case.64 1 Preparation of Monolayer Modified Electrodes S S S Au S S (a) 0/+ 0/+ 0/+ Fc Fc Fc N NN NN N NO2 NO2 Fc Fc 0/+ 0/+ NO2 N NO2 NN N NO2 ClO4− Fig. measured the fluorescence intensity from the polystyrene nanosphere doped as a . Potential scan to 0 mV UV irradiation S S S Au S S (b) Fc Fc Fc 0/+ 0/+ 0/+ N NN NN N NO2 NO2 NO2 ClO4− N NN N NO2 NO2 Fc Fc 0/+ 0/+ using this SAM-modified electrode [131]. they used the mixed SAM of spiropyran/merocyanine-terminated and 4-pyridine thiol. Fox and Wooten constructed the SAM of an anthracene-thiol linked molecule (Fig. 17b) by reconstitution of apomyoglobin in solution with the corresponding metalloporphyrin and investigated their fluorescence spectra [138]. 14 Schematic illustration at the interface (a) between the 100% trans-AzFcSH SAM-modified gold electrode and the electrolyte solution containing perchlorate anions and (b) between the 20% cisand 80% trans-AzFcSH SAM-modified gold electrode and the electrolyte solution containing perchlorate anions before the potential scan to 0 mV [118].2. measured the luminescent intensity and FT-IR spectrum of the SAMs. 1.5 and investigated dimer formation of the anthracene moiety in this SAM [137]. stilbene [135]. Guo et al. Fluorescence from the mixed SAMs of the ferrocene-thiol derivative and Zn tetraarylporphyrin-thiol derivative were measured under open circuit conditions and the amounts of the photo-storaged charge in the SAM were quantitatively examined by Roth et al. Application of Luminescence from SAM-modified Electrodes Luminescence from the SAM-modified electrodes has been extensively studied. 17a).2. (pyridylazo)benzene [134]. 18. and diarylethene [136] were used as the photoisomerization group in the alkylthiol SAM-modified electrodes. constructed the photoactive and electrochemical active myoglobin protein layer on gold electrodes modified with the SAMs of metalloporphyrin-thiol linked molecules (Fig. In addition to the photoisomerization of the azobenzene and spiropyran/merocyanine system.

O HO C + N CH3 CH3 OH NH2 O NHC + N S S S Au Au O 2N hv1 λ>475 nm Au OH (MR) O 2N NH2 HEPES. 15 Schematic modification procedure of a gold electrode by a photoisomerizable spyropyran SAM [130–133]. pH 7. + EDC O NHC + N NH2 CH3 CH3 −H+ S O 2N S NH2 S S S NH2 NH2 CH3 CH3 O− Au hv2 400 nm>λ>360 nm S S Au (SP) NH2 O NHC N O CH3 CH3 NO2 1.5.2 SAMs on Au and Ag Electrodes Fig. 65 .

(b) When the electrode is in the cationic merocyanine state. 141]. The electrochemical and electrogenerated chemiluminescence (ECL) from the gold and ITO electrodes modified with the SAM of tris(2. fluorescent label in the SAMs. 16 Schematic coupling model of the photo-switchable interactions between cytochrome c and the mixed SAM of spiropyran/merocyanine-terminated and 4-pyridine thiol with (a) the reduction of O2 by COx and (c) the oxidation of lactate by lactate dehydrogenase (LDH).66 1 Preparation of Monolayer Modified Electrodes Cyt c (red) S H N o N o COx (ox) 2H2O S S (a) N NO2 N e− Cyt c (ox) COx (red) O2 + 4H+ λ > 475 nm 320 nm < λ < 380 nm S S H N o N N +N Repulsion Cyt c (ox) HO NO2 S (b) λ > 475 nm 320 nm < λ < 380 nm S S H N o N N N o Cyt c (red) LDH (ox) Lactate S (c) NO2 Cyt c (ox) LDH (red) Pyruvate Fig. and investigated cellular adhesion and motility by measuring the surface composition gradients of extracellular matrix proteins such as fibronection [140. repulsive interactions disallow the functioning of the bioelectrocatalytic processes [130].2 -bipyridine) ruthenium(II) (Ru(bpy)3 2+ ) -thiol linked molecules .

Zn2+ 2+ N N Ru N N N (CH2)13 SH N (CH2)13 SH (PF6−)2 (c) 2+ N N Ru N N (d) CH2 SH S S S S S S S S CH2 SH CH2 SH N CH3 N (CH2)12 SH (PF6−)2 (e) CH2 SH S S S S CH2 SH CH2 SH S S S S S S S S (f) S S (g) Fig.1. 17 Alkylthiol and disulfide molecules with functional groups used in this section.2 SAMs on Au and Ag Electrodes (a) O (CH2)10 SH 67 N M N N N (CH2)2 O C O (CH2)12 O C O (CH2)12 SH (CH2)2 SH (b) M = Fe3+. .

19). which were exploited to couple the nanospheres to amine-terminated thiol SAMs through amide bond formation [140]. Thus. 17c [142] and Fig. and therefore. and observed ECL from the generated Ru(bpy)3 2+∗ at the SAM-modified gold and platinum electrodes [145.68 1 Preparation of Monolayer Modified Electrodes + Au O O OH O + EDC NHS N O O O N O + S NH2 S O N H HS NH2 S NH2 Schematic modification process of the fluorescent nanospheres containing a large number (∼106 per sphere) of pendant carboxylic acid moieties. Bard et al. 19) and luminescent spectrum (Fig. The potential dependence of the emission intensity (Fig. 144]) were reported. 18 (Fig. a monotonic increase in the anodic current was observed as the potential becomes more positive (Fig. electrochemically generated Ru(bpy)3 3+ oxidizes C2 O4 2− . Ru(bpy)3 2+∗ may directly donate an electron to the electrode (reaction (5)) or relax to Ru(bpy)3 2+ with a light emission efficiency controlled by the electron transfer rate of the reaction (5) which should be dependent on the distance between the electrode and the Ru(bpy)3 2+/3+ head group in the SAM. the Ru(bpy)3 2+/3+ head group in the SAM acts as a mediator for the oxidation of oxalate. 17d [143. and becomes Ru(bpy)3 2+ which again donates an electron to the electrode (reaction (1)). Fig. 20) were observed at the Ru(bpy)3 2+ SAM-modified electrode in a solution containing C2 O4 2− and the following reactions were considered to take place within the positive potential region where emission was observed [142]: −→ Ru(bpy)3 2+ − − Ru(bpy)3 3+ + e− Ru(bpy)3 3+ (1) 2+ + C2 O4 + CO2 2− − − Ru(bpy)3 −→ + CO2 + CO2 •− Ru(bpy)3 3+ • (2) 2+∗ − − − Ru(bpy)3 −→ 2+ + CO2 Ru(bpy)3 2+∗ (3) + hν (4) − − Ru(bpy)3 −→ Ru(bpy)3 2+∗ − − Ru(bpy)3 3+ + e− (5) −→ In these processes. forming CO2 and CO2 −• . 146]. also used the following oxidation reaction of tripropylamine (TPrA) and the above reactions (1) and (4). CO2 −• reduces Ru(bpy)3 3+ to Ru(bpy)3 2+∗ which has excess energy. TPrA − − TPrA•+ + e− −→ + TPrA•+ TPrA•+ − − TPrA• + H+ −→ (6) Ru(bpy)3 3+ + TPrA − − Ru(bpy)3 2+ −→ (7) (8) .

1 M Na2 C2 O4 [142].4 M Na2 SO4 + 0.1 0 (b) (a) 4 3 2 1 0 Current density [mA cm−2] 900 69 6 Light intensity [au] 4 2 0 0 200 400 600 800 1000 1200 1400 1600 Potential/mV vs.1. 0. 20 ECL spectrum of the Ru(bpy)3 2+ -thiol SAM-modified ITO electrode in a solution containing 0.15 V (dots) and the emission spectrum of Ru(bpy)3 2+ -thiol in CH2 Cl2 solution (solid curve) [142].4 M Na2 SO4 + 0. and (b) the ECL intensity of the unmodified (broken curve) and SAM-modified (solid curve) ITO electrodes in a solution containing 0.3 0. Emission intensity [au] Fig. 19 Potential dependence of (a) the currents of the unmodified (broken curve) and SAM-modified (solid curve) ITO electrodes.4 0.2 0.0 500 600 700 800 Wavelength [nm] .1 M Na2 C2 O4 at 1.2 0.4 Current [mA cm−2] 0.2 SAMs on Au and Ag Electrodes 0. Ag/AgCl Fig.

respectively. the ECL behaviors at the Ru(bpy)3 2+ SAM-modified electrodes were used to fabricate an optoelectrochemical microring array [147]. Both the current-voltage (I-V) and luminescence-voltage (L-V) curves of these devices shifted to higher voltages in the order of SAM(f). emission. 16. As a reference. on these SAMs by vacuum evaporation. Figure 21 shows the EL characteristics of these devices. 21 (a) I-V and (b) L-V characteristics of (1) SAM(e).4 -bis(3-methylphenylphenylamino)biphenyl (TPD). . (4) bare gold. used gold electrodes modified with the SAMs of the tripodshaped π-conjugated thiols and disulfide 103 102 Current [mA cm−2] (Figs 17(e)–(g)) and investigated enhanced hole injection from the EL of these SAM-modified electrodes [148]. Except for the above reports. They constructed layers of 4. (3) SAM(g). tris(8-hydroxyquinolinato)aluminum(III) (Alq3 ). these layers deposited both on the bare gold and bare ITO substrates were also used. the surface hydrophobicity [145] and immobilization of DNA and protein [146] were investigated. Yamashita et al. as a hole transport. 16 (2) SAM(f). There is a report that describes the application of a SAM-modified electrode in an electroluminescence (EL) device. < 101 2 1 5 4 3 100 10−1 (a) 104 103 Luminance [cd m−2] 102 2 5 1 4 3 101 100 (b) 4 8 Voltage [V] 12 Fig.70 1 Preparation of Monolayer Modified Electrodes Ru(bpy)3 3+ + TPrA• − − Ru(bpy)3 2+∗ −→ + products (9) Using this ECL behavior of the Ru(bpy)3 2+ /TPrA system. which means the SAM of the molecule (f) shown in Fig. and (5) bare ITO devices [148]. and Mg–Ag alloy. and electron transport layers.

When luminol and hydrogen peroxide were contained in the electrolyte solution.1 M NaClO4 /0. 22b). constructed Au and Au/Ni nanowires whose surface was modified with the SAMs of a porphyrin-thiol coupling molecule [151]. 22 (a) Linear sweep voltammograms of ferrocene-thiol SAM-modified gold electrode measured in electrolyte solution (0.2) with 100 µM luminol and 10 mM H2 O2 (solid line) and without luminol and H2 O2 (dotted line). Sato et al. pH 8. and of the disulfide SAM(g) very poor.2 SAMs on Au and Ag Electrodes 71 SAM(e) ≈ bare ITO < bare gold < SAM(g). These modifications influence the hole injection barrier height at the Au/TPD interface and then affect the EL characteristics of the devices. Fluorescence microscopy was used to optimize the functionalization of two-segment gold-nickel nanowires for selectivity and 8. It is quite important to apply the SAM-modified electrode to a biosensor using the fluorescence from it [149. investigated the electrooxidative chemiluminescence from a luminol/hydrogen peroxide system catalyzed by the ferrocene-thiol SAM-modified gold electrode (Fig. In contrast. Sweep rate: 2 mV s−1 . the catalytic oxidation current of luminol was observed (solid line in Fig. They applied this system to detect glucose in the presence of glucose oxidase [150]. for example. Ag/AgCl (NaCl) (a) Fig. 22a) and light emission was simultaneously observed (open circle in Fig. The different effects of the SAMs on the EL properties of the devices were concluded to be due to the modification density of the SAMs. . the SAM(g) device showed EL characteristics poorer than the bare gold device. leading to the vacuum level shift at the Au/TPD interface by the SAMs. (b) ECL intensities of ferrocene-thiol SAM-modified gold electrode (open circle) simultaneously measured with the linear sweep voltammograms.1. The ECL intensity depended on the pH of the solution. in addition to the oxidation peak due to the redox of ferrocene.0 2. although it is not on an electrode.1 M buffer solution.0 0 4. Reich et al. permitting much higher current. The results of the CVs at the gold electrodes modified with these SAMs showed that the packing of the tripod-shaped thiol SAM(f) was compact.0 1. Compared to the bare gold device. which is incorporated in a SAM.0 2. 150]. and better stability.0 Current [mA • cm−2] 6. of the thiol SAM(e) less. the SAM(f) device exhibited a significantly improved EL performance. yielding much greater maximum brightness.0 Light intensity (a u) (b) 3.0 0 0 200 400 600 750 Potential/mV vs. ECL intensity of unmodified gold electrode (closed diamond) [149]. 22). There is an interesting report about fluorescence from a porphyrin. greatly reduced operating potential.0 4.

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1.F. and J. The interface between an aqueous phase and the polar head region of lipid monolayers is equivalent to that between the same aqueous phase and lipid bilayers. no appreciable differences are expected. KGaA. this review covers the main aspects of the preparation. usually at a submonolayer level. Without having the pretension of being comprehensive. Phospholipid SAMs on Hg Phospholipid monolayers consist of a hydrocarbon tail region with a dielectric constant comparable with that of alkanes (≈ 2) and a polar head region containing ionizable groups (phosphate. in 1940 Kolthoff and Barnum [3] described a dc polarographic adsorption prewave for cysteine electrooxidation.Rubinstein. for their applications as models of biological membranes. Only recently. molecules of biological importance. featureless. amino. and proteins have been incorporated in Hg-supported phospholipid SAMs with the aim of investigating their behavior in an environment mimicking that of biological membranes. defect-free surface that lends itself to the formation of well-behaved self-assembled monolayers (SAMs). Thus. This finding started a series of electroanalytical investigations on the deposition of water-soluble thiol films on Hg.3. when Miller and coworkers [1.1. Weinheim. 1. Firenze. as long as interactions with foreign molecules are only confined to the polar head region. Much before the first applications of phospholipid SAMs on Hg.3 SAMs on Hg Electrodes and Si 105 1.1 SAMs on Hg Electrodes Rolando Guidelli Florence University. Edited by A. and mainly. lipophilic ions. aiming at exploiting the unique properties of this liquid metal. carboxyl groups) whose polarizability imparts to this region a higher dielectric constant (from 10 to 30). peptides. characterization. after the investigations on the interesting properties of alkanethiol SAMs 1.3.1.Fujihira. and properties of the above SAMs on Hg.2 1. which prefigured the formation of a monolayer of this amino acid provided with a sulfhydryl group. ISBN: 978-3-527-30402-8 . 10 Modified Electrodes.Rusling Copyright  2007 Wiley-VCH Verlag GmbH & Co.3 SAMs on Hg Electrodes and Si 1.1 Preparation Methodology and Procedures The first attempt to deposit a lipid monolayer on mercury was carried out by Miller and Bach [1] by causing an aqueous dispersion of dipalmitoylphosphatidylcholine (DPPC) to be adsorbed on Encyclopedia of Electrochemistry. phospholipid SAMs on mercury electrodes have been extensively investigated not only for their intrinsic properties but also. This is why phospholipid monolayers supported by mercury have been extensively employed as experimental models of biological membranes. on Hg this is mainly governed by intermolecular interactions.3. One of the first applications of Hg as a support for a monolayer dates back to the early 1970s. Stratmann Vol.3.1 on gold electrodes.1. From then on. Bard and M. I. Italy Introduction and Scope Mercury has a homogeneous. which represent the main constituents of biological membranes.J. 2] described the selfassembly of phospholipid monolayers on a dropping mercury electrode with a long drop time. While on a solid substrate such as Au it is the lattice structure that governs the organization of the SAM molecules. attention has been focused on analogous investigations on Hg. Edited by M.2. To this end.

organized monolayer from a Langmuir trough onto an electrode. although less than on other metals [7. in fact. as the adsorbing lipid molecules have to decide where to turn their hydrophilic polar head to attain a minimum in their adsorption free energy. thereby creating more favorable conditions for the attainment of adsorption equilibrium. where it can form hydrogen bonds with the adjacent water molecules. The drop is formed after positioning the HMDE about 0. the film was less than monomolecular. by ‘‘self-assembly’’. Pagano and Miller [2] transferred Langmuir–Blodgett (LB) films of different amphiphilic molecules at their equilibrium spreading pressure from a deaerated Langmuir trough onto a dropping mercury electrode. and to continue growing for other 10–15 seconds before falling off the capillary. namely. Because of the very low solubility of DPPC and its gel state at room temperature. However. they choose to turn it toward the aqueous phase. at the potential of zero charge (pzc). A variant of this procedure was later adopted by . a well-organized monolayer is formed on its surface. could be obtained by a similar procedure not only at the equilibrium spreading pressure of the lipid film on the aqueous subphase but also with lipid surface concentrations at the nitrogen/water interface corresponding to two [5] or three [6] lipid monolayers. 8]. in agreement with a close-packed monolayer of fully extended molecules in a vertical orientation. to touch the nitrogen/water interface after 1–2 seconds. especially if it incorporates a lipophilic substance capable of decreasing its fluidity. Miller and coworkers found that well-organized phospholipid monolayers with a differential capacity of about 1. The technique was further improved by using a hanging mercury drop electrode (HMDE) in place of a dropping mercury electrode.2 to −0. Subsequently.106 1 Preparation of Monolayer Modified Electrodes the surface of a dropping mercury electrode with a long drop time.6 V/SCE. this was adjusted above the film in such a position as to start growing in the nitrogen atmosphere.2 mm above the lipid film previously spread on the aqueous electrolyte [5]. In fact. the water molecules adsorbed on mercury are slightly oriented with the oxygen turned toward mercury.2 V. twice that of solventfree black lipid membranes [4]. Subsequently. it is covered almost completely by a self-assembled lipid monolayer. A film of 3 H-labeled oleic acid on mercury obtained by this procedure had a surface concentration of about ˚ (1/19) molecules/A2 over the potential range from −0. At any rate. as this film comes into contact with the mercury electrode. This procedure. exploits the fact that mercury is the most hydrophobic metal. As the drop touches the film following its growth. while its neck remains in contact with the lipid reservoir previously spread on the surface of the aqueous electrolyte. which should be distinguished from the ‘‘LB transfer’’ of a preconstituted. This by no means implies that mercury has no affinity for the oxygen of water. exhibiting a high differential capacity C of about 8 µF cm−2 over the potential range from −0. the lipid monolayer may not adjust readily to an expanding mercury drop.1 to −1. The lipid film is obtained by spreading a solution of the lipid in an alkane (usually pentane or hexane) on the surface of an aqueous electrolyte and by allowing the alkane to evaporate. This lipid film can be regarded as a monolayer at its equilibrium spreading pressure plus a lipid excess in equilibrium with the monolayer.7 µF cm−2 .

9 to 1. Lipids that are not in the liquid-crystalline state cannot be transferred satisfactorily to the mercury drop because of lack of fluidity.3 µg cm−2 . Thus.4 to −0. A special home-made HMDE that uses an oleodynamic system for moving the electrode vertically inside a water-jacketed box and extrudes stationary drops maintaining a constant area for periods of up to 90 minutes. whereas with dioleoylphosphatidylserine (DOPS) it decreases from 1. A simple procedure for measuring the charge density σM on the surface of a lipid-coated mercury electrode consists in contracting the lipid-coated drop while keeping its neck in contact with the lipid reservoir spread at the water/argon interface [12].9 V/SCE. This procedure gives rise to a self-assembled phospholipid monolayer supported by mercury. at negative potentials this region is delimited by two sharp peaks that lie at about −0. dipalmitoyl PS.6 µF cm−2 as the pH passes from 8 to 2. this value. This procedure.3. 1) and by a third peak at about −1. A further.1. the drop was then slowly immersed in the electrolyte across the lipid film. while scanning the potential repeatedly from −0. more lengthy procedure to self-assemble a dioleoylphosphatidylcholine (DOPC) monolayer on an HMDE consists in keeping it immersed in an aqueous dispersion of DOPC liposomes for about 15 minutes.8 µF cm−2 . 10]: a commercial HMDE was used to form a mercury drop in a nitrogen atmosphere above a lipid film spread on an aqueous electrolyte in an amount >0. with dioleoylphosphatidylethanolamine (DOPE) the minimum capacity amounts to ∼1. The value of the minimum capacity and its potential range vary slightly with the nature of the phospholipid. The charge following the contraction divided by the decrease in drop area yields directly the charge density σM on the mercury surface.1. can be transferred to mercury only at higher temperatures [9].7 V/SCE until a constant value of 1. peaks 1 and 2 are replaced by a single peak [14]. 1. is not affected by changes in pH.2. At positive potentials the region of minimum capacity is delimited by a capacity increase that precedes mercury oxidation.85 µF cm−2 is attained [13].2 Structure and Physical Properties of Phospholipid SAMs on Hg 1. ionic strength. Thus. 1). as the drop is contracted. temperature.7 V/SCE (Fig. which exploits the free exchange of lipid material between the lipid monolayer that coats the mercury drop and the lipid film spread on the solution.2. With dimyristoyl phosphatidylcholine (PC) and bovine phosphatidylserine (PS).15 to −0. with a reproducibility better than 1%.2. which amounts to ∼1. 15]. If the area of a lipid-coated HMDE is expanded while keeping it immersed in the aqueous electrolyte.3.1. Since under these conditions the film expansion maintains the amount of lipid material on the .1 Differential Capacity of PhosThe differential pholipid SAMs on Hg capacity of a self-assembled DOPC monolayer attains a constant minimum value over a potential range from −0.3 [14].9 and −1.02 µF cm−2 . whose transition temperature from the gel to the liquidcrystalline state is about 42 ◦ C. including its thickness. ensures that the monolayer maintains its properties. was described by Moncelli and Becucci [11].15 to −0.0 V (peaks 1 and 2 in Fig. The transfer of a lipid monolayer on this electrode provides differential capacity values with an accuracy better than 0.35 V in the case of DOPC. and nature of the electrolyte. the minimum capacity varies proportionally to the drop area A [9.3 SAMs on Hg Electrodes and Si 107 Nelson and coworkers [9.7 µF cm−2 and ranges from −0. corresponding to about three monolayers.

5 −1.1 M solutions of TMACl.5 E [V] Fig. twodimensional phase transitions. A decrease in ionic strength broadens the potential range of the capacity minimum by shifting peaks 1 and 2 negatively and the capacity rise at the more positive potentials positively. whereas an increase in temperature from 5 to 60 ◦ C shifts peaks 1 and 2 negatively and peak 3 positively [17]. A is inversely proportional to d. and LiCl [16]. A decrease in pH from 8 to 1 causes a positive shift in peak 1 and a negative shift in peak 2. noting that. 1 Curve of the differential capacity C versus potential E for DOPC-coated mercury in 0. for a parallel-plate capacitor. the latter capacity rise is shifted negatively by those anions that are more strongly adsorbed on Hg. ε0 ε/d. for a constant volume V = Ad of the lipid material.9 −1.3 −1. this behavior can be explained by assuming that the drop expansion causes a progressive tilt of the lipid molecules. Peaks 1 and 2 of DOPC are capacitive in nature and are due to field-induced. KCl.108 1 Preparation of Monolayer Modified Electrodes 1 50 20 TMACl 10 40 a KCl 3 20 2 C [µF cm−2] 30 C [µF cm−2] 0 10 20 20 LiCl 10 10 −1. At constant ionic strength. and hence without altering the dielectric constant ε of the film.1 M KCl.8 E (SCE) [V] −2. where d is the film thickness and ε0 is the permittivity of the free space.3 −0. without incorporation of water into the lipid monolayer. the direct proportionality between C and A requires the constancy of ε.2 −1. The capacity C of the film can be approximately expressed by the Helmholtz formula.6 −0.1 0 0 −0. such as . drop surface constant. The inset shows C versus E curves for bare (dashed line) and DOPC-coated (solid line) mercury in 0.

χ. and that must be compensated for by a negative charge density on the metal to keep the applied potential on lipid-coated mercury at the same value as the pzc on bare mercury. for bare Hg in 0. as they are formed at sufficiently negative potentials. −23. and their replacement by a PC monolayer. coating Hg with a DOPC monolayer shifts the pzc toward positive values. whose surface dipole potential amounts to ∼−100 mV [19] (negative toward the mercury). however. the coating involves the removal of adsorbed water molecules. LiCl.450 V/SCE.1 M solutions of KCl. the subsequent backward scan exhibits smaller peaks 2 and 1 and a capacity minimum lower than the pristine one. This is due to the positive shift. peak 3 is shifted positively and.450 V/SCE is obtained [16].2 µC cm−2 − Q = −0. of total desorption in this electrolyte amounts to Q = −22.1 µC cm−2 .850 V/SCE on bare Hg from electrocapillary measurements [18]. −0. if the potential is scanned beyond peak 3 (say.3 SAMs on Hg Electrodes and Si 109 bromide and iodide ions. up to the desorption potential of −1. to a potential.1 M NaCl and CsCl is similar to that in 0. Complete desorption takes place at potentials negative enough to cause a merging of the curve of the differential capacity C versus the applied potential E recorded on lipid-coated mercury with that obtained on bare mercury. −23. If the potential is scanned from the capacity minimum beyond peak 3 and is then scanned back.85 V/SCE) and is then scanned back. which tend to heal the defects in the SAM.1 M TMACl. In this case. In fact. The charge at a DOPC-coated mercury electrode which follows a chronocoulometric step from the pzc. By knowing the charge density. On the other hand. The inset of Fig. in the surface dipole potential χ that accompanies such a coating. in the order of the increasing binding of these cations to the phosphate group of the polar heads of the lipid. whose polar heads have a surface dipole potential of ∼+200 mV [20]. at −1.1 µC cm−2 . revealing some defects upon readsorption. Therefore. namely. scanning the potential for the first time from the region of the capacity minimum to a potential just negative of peak 2 yields a capacity curve practically identical with that recorded with SAMs obtained by the spreading procedure. on DOPC-coated mercury at −0. . the charge density.1. most importantly.1 M TMACl.1 M KCl. 1 shows C versus E plots in 0. no peaks are observed in the reverse scan and the pristine capacity minimum is substantially recovered. probably because of a competition with the lipid for the metal surface. peaks 1 and 2 and the capacity minimum are fully recovered [13]. −1. On the other hand. This difference in behavior is due to the constant presence of liposomes. and tetramethylammonium chloride (TMACl) both on bare and on DOPC-coated mercury [16]. 1 exhibits hysteresis in the reverse potential scan [9] and is due to partial desorption of the lipid.8 ± 0. The best overlap is attained in 0.850 V/SCE.4 ± 0. The third peak in Fig. A different behavior is observed with SAMs obtained from DOPC vesicles.1 µC cm−2 . and may also fuse with the SAM. the behavior in 0. If a DOPC SAM obtained by the spreading procedure is subjected to a potential scan from the region of the flat capacity minimum to a potential just negative of peak 2 and the potential is then scanned back. peak 1 shifts positively in response to the electrolyte cation in the order: Ca2+ = Mg2+ > Li+ > Na+ > K+ > Cs+ . the capacity minimum is higher.2 ± 0. under otherwise identical conditions.

due to nonradiative energy transfer to the electrode. denoting a defectively re-formed SAM. the lipid molecules remain in close proximity to the mercury surface for hours as positively charged micellar aggregates. the presence of Ca2+ imparts a high stability to the SAM [24]. owing to the particularly strong interaction of the highly hydrated Li+ ion or of Ca2+ with the lipid film [25]. neither the fluorescence nor the capacity recover the pristine value. the fluorescent particles or aggregates on Hg are freely mobile. the various relaxation times often differ by less than 2 orders of magnitude. which is known to interact strongly with the phosphate groups of phospholipids.110 1 Preparation of Monolayer Modified Electrodes At potentials of complete lipid desorption. The inset in Fig. preventing an image analysis yielding their number density and size. Upon scanning the potential progressively in the negative direction up to film desorption. in the presence of Li+ or Ca2+ . even at far negative potentials at which complete desorption is observed with the other alkaline chlorides. the fluorescence quenching efficiency. the fluorescence intensity maintains a constant low level along the flat capacity minimum. this is probably to be ascribed to their high positive charge density. A similar behavior is observed in the presence of Ca2+ [24]. as distinct from a Au electrode. and spread back readily on the electrode surface with a positive shift in potential [16. upon scanning the potential back from −1. This indicates that. In particular. a large increase in fluorescence is observed at the far negative potentials. This plot is particularly suitable for representing a series RC network. This desorption/readsorption process was imaged using epi-fluorescence microscopy and including a small amount of an amphiphilic fluorescent dye molecule in the lipid SAM [22]. 21]. the pristine capacity minimum is recovered. In contrast to a similar gold system [23]. the lipid aggregates are not completely detached from the negatively charged mercury surface even at the most negative potentials. By scanning back the potential. where Y and Y are the in-phase and quadrature components of the electrochemical admittance and ω is the angular frequency. a series connection of R and C yields . it is well known that the same impedance spectrum can often be equally well fitted to different equivalent circuits. thus. the fluorescence decreases slowly down to the positive potential limit. fluorescence can be detected even if the fluorophore is at a small distance from the electrode. In fact. in contrast to experiments in the absence of Ca2+ . Thus. 1 shows that in 0.1 M LiCl the capacity remains constantly lower than that of bare mercury. Impedance spectra are frequently reported on a Y /ω versus Y /ω plot.85 V/SCE. which prevents the merging of the C versus E curve on PC-coated mercury with that on bare mercury. indicating a separation of the DOPC monolayer from the electrode surface. Impedance spectroscopy measurements Electrochemical impedance spectroscopy is extensively employed for the investigation of SAMs because the broad range of frequencies covered by this technique (usually from 10−3 to 105 Hz) may allow processes with different relaxation times taking place within the electrified interphase to be detected and sorted out. is 2 to 3 orders of magnitude lower on Hg than on Au. On a Hg electrode. thus requiring a certain amount of arbitrariness and of physical intuition for their separation. which are consequently ascribed to different relaxation processes. Unfortunately. In fact.

At any rate. a CPE is an empirical admittance function of the type A(iω)α . namely. is assumed to be sufficiently close to the electrode surface to slow down the migration of ions in response to the ac signal. of the solution adjacent to the film. At the desorption potential. Y = [R + (1/iωC)]−1 .1 M KCl over the potential range from the flat capacity minimum to peak 2 [26].e. a Cdl Q ‘‘mesh’’. with in series. This apparently anomalous behavior was tentatively explained by the presence of a lipid layer at some separation from the water-coated electrode surface. To investigate the behavior of a DOPC SAM on mercury at its desorption potential of −1. Incidentally. Cs and Cinf are capacities in the low. Setting a CPE in parallel with the film capacity Cdl has the effect of accounting for a depressed semicircular arc (namely.3 SAMs on Hg Electrodes and Si 111 a semicircle of radius C/2 in this plot. In Eq. (1).and high-frequency limits. this consisted of the resistance. The physical significance of these two CPEs is not entirely clear. they modified the expression of the admittance for a simple RC series circuit. A depressed semicircular arc may be simulated by a . over the potential range of the capacity minimum (i. a β value <1 was ascribed to a certain ‘‘roughness’’ at the interphase.85 V/SCE. Bizzotto et al. the parallel arrangement of a capacity Cdl and of a CPE Q.7 V/SCE) both α and β were found to be very close to unity. but the solution resistance Rsol is about 20% higher on the latter electrode. an arc whose center lies below the horizontal axis). at this negative desorption potential. This organic material. with center of coordinates (Y /ω = C/2. Nelson and coworkers used a series RC network to fit the impedance spectra of a DOPC SAM on mercury in 0. simulating the film. when α = 0 and to a pure capacity when α = 1. thus denoting that the behavior of the SAM approaches that of a simple series RC network closely. to account for all features of the spectra. Y /ω = 0) and a maximum characterized by an ω value equal to 1/RC. also revealed by epi-fluorescence measurements. the Cdl and Q elements are practically identical for the bare and the DOPC-coated mercury electrode. its use is justified if the relaxation time of the process under study is not single valued. Nelson and coworkers also analyzed the impedance spectra of DOPC-coated mercury in contact with different alkali metal chlorides with principal component analysis and regression [28]. Rsol . However. Depressed arcs are also reported in spectra plotted in a Z versus Z diagram (sometimes called a Nyquist diagram). while an α value <1 was ascribed to a continuous distribution of low-frequency relaxation phenomena. but is distributed continuously around a mean [27].1. between −0. a feature often encountered in the spectra of SAMs plotted in a Y /ω versus Y /ω diagram. which reduces to a pure conductance.4 and −0. [24] compared the impedance spectrum of this SAM with that of a bare mercury electrode at the same potential using a less involved equivalent circuit. respectively. by introducing two constant phase elements (CPEs) in place of iωC: Y = R+1 A(iω)β Cs − Cinf + Cinf 1 + B(iω)α −1 (1) Here. A = 1/R. where Z and Z are the in-phase and quadrature components of the impedance Z = 1/Y .

which × 105 5 4 were ascribed to the polar heads. revealing the presence of three dielectric slabs. at frequencies that are not too low. 2 cm−2] Plot of ωZ versus ωZ for a DOPC SAM on Hg in 0. In both cases. and the hydrocarbon tails. while it yields a semicircle with radius C/2 and center of coordinates (ωZ = C/2. and the whole SAM by an equivalent circuit consisting of a series of RC meshes.55 V/SCE. A single RC mesh yields a semicircle with radius R/2 and center of coordinates (Z = R/2. The dashed curves represent the contributions of the four different RC meshes to the solid curve. an RC mesh yields a semicircle even in the Y /ω versus Y /ω plot. under the assumption that it is generated by a continuous distribution of relaxation processes around a mean [27]. a resistance R and a capacity C in parallel). These relaxation processes may be attributed to the movement of ions across slabs with different dielectric properties composing the SAM.112 1 Preparation of Monolayer Modified Electrodes CPE in parallel with a capacity C. each slab may be represented by an RC mesh (namely. . The solid curve is the best fit of the experimental points to an equivalent circuit consisting of four RC meshes in series. However. the maximum of the semicircle corresponds to an angular frequency ω = 1/RC.1 M KCl at −0. Z = 0) in a Z versus Z diagram. the glycerol backbone. we obtain a frequency-dependent radius equal to C/2[1 + (ωRC)−2 ].55 V/SCE [31]. while the accumulation of charges at its boundaries is accounted for by its capacity. Consequently. Such an equivalent circuit was adopted to interpret the impedance spectrum of a bilayer lipid membrane (BLM) [29]. ωZ = 0) in a ωZ versus ωZ diagram [30]. a depressed semicircular arc may also be ascribed to a discrete number of relaxation processes whose time constants differ by 2 orders of magnitude or less. in the ωZ′ [Ω s cm−2] 3 2 1 0 0 1 2 3 4 5 6 × 105 ωZ′′[Ω s Fig.1 M KCl at −0. Roughly speaking. plotting the impedance spectrum in a ωZ versus ωZ diagram often allows a better separation of the different relaxation processes than plotting it in a Z versus Z diagram. In other words. In practice. Figure 2 shows such a plot for a DOPC SAM on Hg in 0. the movement of ions to and fro across each slab is accounted for by its resistance. If we force an RC mesh to satisfy the equation for a semicircle in a Y /ω versus Y /ω diagram.

Inhibitive Properties of Phospholipid SAMs on Hg The electroreduction of the Cd(II).1. Modeling of Phospholipid SAMs The experimental behavior of on Hg phospholipid monolayers on a metal substrate can be analyzed on the basis of a model of the membrane–solution interphase that accounts for the presence of any charged ionizable groups buried well inside the polar head region and is schematically depicted in Fig. in the presence of substances such as furosemide. which on bare mercury occur over the potential range of the capacity minimum of the DOPC-coated mercury. and its decay is interpreted on the basis of a model in 1. It can be written as: 1. of thickness γ and dielectric constant εγ .3 φ= β γ σM + (σM + σin ) ε0 εβ ε0 εγ N µdip ε0 εγ + φd (c. However. Phospholipid films inhibit the two-electron reduction of O2 to H2 O2 [10]. The hydrated Cd(II) ion permeates the monolayer more easily than the chloro and sulfate complexes. and the aqueous solution adjacent to the film. such an electroreduction can take place [33]. the hydrocarbon tails. 3 [34]. which depends on the charge density σM on the metal. are inhibited by the lipid monolayer and initiate at potentials somewhat positive of peak 1 [32]. and Pb(II) ions to metal amalgam and that of the Eu(III) and V(III) ions to the divalent form. even though O2 can penetrate these films. The inhibition of the E(III)/Eu(II) and V(III)/V(II) electrode reaction indicates that no electron tunneling can occur across the lipid film. This indicates that the phase transition responsible for peak 1 increases the permeability of the monolayer. In view of their R and C values.3. denoting exclusive control by the penetration of the ion across the film [32]. and the diffuse-layer region. the polar heads. at least over the potential range of its stability.1. At potentials approaching peak 1 the current decreases in time.2 which the permeable areas in the defective lipid film are regarded as forming an array of regularly distributed microelectrodes [21].1.2. to the glycerol backbone. In this model the potential difference φ across the metal–solution interface consists of the sum of the potential differences across the hydrocarbon tail region. in the order. On the other hand. which depends upon the sum of σM and of the charge density σin of any charged .3 SAMs on Hg Electrodes and Si 113 middle of the flat capacity minimum [31]. the contributions follow each other in the order of decreasing relaxation times. The plot is fitted to a series of four RC meshes. whose contributions are represented by the four dashed curves in the figure.2. they can be ascribed.2. of thickness β and dielectric constant εβ ∼ 2. polarizable anions such as bromide and iodide facilitate Cd(II) reduction and Cd(Hg) oxidation to the extent with which they penetrate the monolayer at more positive potentials. The current for Cu(II) reduction along the foot of the wave inhibited by the lipid monolayer is independent of time. σtot ) − with : σtot ≡ σM + σin + σex (2) Here the first term is the potential difference across the hydrocarbon tail region. whose incorporation makes the lipid film permeable to hydrogen ions.2. Cu(II). Starting from the origin. the polar head region.3. The second term is the potential difference across the polar head region.

this term also includes any contribution to the dipole potential from the orientation of the water molecules in direct contact with the polar heads. 1 + Kj [H + ] 1 . Differentiation of Eq. the sum of σM .114 1 Preparation of Monolayer Modified Electrodes sM sin g(sM + sin) e0eg sex Nmdip − e e 0 g fd Mercury b s e0eb M g 0 Distance b d Fig. σM assumes values from −0. 1 + Kj [H + ] [H + ] = e−F φj /(RT ) for j = in . groups buried well inside the polar head region. σin and the charge density σex of any ionized groups directly exposed to the aqueous phase. φj = φd (4) 1+ max is the charge density correHere σj sponding to the fully ionized j th group.5 µC cm−2 under usual experimental conditions. (2) with respect to σM yields the following expression for the reciprocal of the differential capacity: d φ 1 = = C dσM + dφd dσtot β γ + ε0 εβ ε0 εγ dσex dσin + dσM dσM + γ dσin ε0 εγ dσM (3) under the reasonable assumption that µdip is practically insensitive to the small changes in σM . where µdip is the dipole-moment normal component of the polar heads and N is their number per unit surface. Finally. φj = φx=β for j = ex . The dashed curve represents the profile of the average potential against the distance from the mercury surface. 3 Schematic diagram of the model for a lipid monolayer deposited on mercury. with the major changes in σtot being due to σin end σex as a consequence of a change in pH. (4) and negative in the second. In fact. φd is the potential difference across the diffuse layer. The diffuse-layer thickness has been compressed with respect to the monolayer thickness. for ease of representation [34]. which is positive in the first expression of Eq. which according to the Gouy–Chapman (GC) theory is a function of the electrolyte concentration c and of the whole charge density σtot experienced by the diffuse-layer ions.2 to −0. dφd /dσtot is expressed by the GC theory. namely. . The third term is the dipole potential due to the polar heads. The charges σin and σex of the ionizable groups are considered to depend on the corresponding protonation constants Kin and Kex according to Langmuir isotherms: max σj = σj max σj = σj Kj [H + ] .

the possibility of increasing their initial area A by over 3 times by expanding the supporting mercury drop completely immersed in the aqueous electrolyte. σtot ) can be calculated from the GC theory. φd (c. while φ differs from E by an unknown constant that depends exclusively on the choice of the reference electrode. the differential capacity takes the simple form: 1 1 dφd = + C Cm dσtot with : Cm = 1+ dσex dσM −1 β γ + ε0 εβ ε0 εγ (5) Here Cm is the capacity of the lipid monolayer. the latter measurement was carried out by the procedure based on the contraction of the lipid-coated mercury drop [12]. To estimate the whole surface dipole potential χ. yields a pKa value of 0. since its phosphate group is buried somewhere inside the polar head region.8 for that of DOPC [35].7 µF cm−2 . The more general expression of Eq. Denoting by θ the angle formed by the axis of the tilted lipid molecules with the normal .1valent electrolyte KCl at different pH values to Eq. while the carboxyl and ammonium groups are more exposed to the aqueous phase. The fitting to Eq. σin . namely. Analogously. (2) allows the surface dipole potential χ ≡ −N µdip /ε0 εγ to be estimated as a function of σtot . exhibits a sigmoidal shape. (3) was therefore adopted. σex of DOPS and DOPA are determined at different pH values and at a constant applied potential E. (4). requires not only the measurement of C as a function of the KCl concentration and of pH but also that of σM as a function of pH. the overall charge density of a dioleoylphosphatidic acid (DOPA) monolayer passes from negative to positive values as the pH is varied from 4 to 1.5 for the phosphate group of DOPE and of 0. shown in Fig. which for dioleoylphospholipids can be accurately estimated at 1. this strongly suggests that the change in χ with varying the overall charge density of the DOPS and DOPA monolayers is mainly to be ascribed to the reorientation of the water molecules in contact with the polar heads. 4. Fitting the small changes in C with varying the concentration of the 1. a property of phospholipid monolayers in the liquid-crystalline state at room temperature was exploited. (3). It was concluded that the overall charge density. σin + σex . so as to continue covering the whole drop surface. The behavior of DOPS is more involved. The plot of (χ + constant) versus (σin + σex ) for DOPS and DOPA. Once the charge densities σM . (4). the lipid molecules must progressively increase their tilt and decrease their number N per unit surface. with σin and σex expressed by Eq. without incorporation of water into the monolayer [15]. with σin equated to the charge density of the phosphate group. with σex expressed by Eq. In fact. apart from an additive constant. of a DOPS monolayer varies from slightly negative to slightly positive values as the bulk pH of the bathing solution is varied from 7 to 4 [34]. with the maximum slope lying at (σin + σex ) = 0. This plot is reminiscent of the surface dipole potential χw because of the gradual alignment of the water molecules adjacent to the surface of a bare metal along the direction of the electric field created by the charge density on the metal [36]. (5).3 SAMs on Hg Electrodes and Si 115 For lipids with no ionizable groups buried inside the hydrocarbon tail region (σin = 0).5. During the gradual drop expansion. Eq.1. σex depends upon σM only through the diffuse-layer potential difference φd .

the dashed line is a curve of χw against the charge density σM calculated by Damaskin and Frumkin [36] for a metal–water interface.1 M KCl [24].1 0. σtot cos θ) N µdip or. of the initial unexpanded area A of the film to the final expanded one.3 0.6 0. after drop expansion will all be equal to their initial values times cos θ.116 1 Preparation of Monolayer Modified Electrodes 0. to the plane of the lipid monolayer. 4 Plots of (χ + constant) versus (σin + σex ) for DOPS ( ) and DOPA ( ) self-assembled monolayers at −0. its cosine is just equal to the ratio.7 0. A(θ). the dipole-moment normal component µdip of their polar heads.1 0.2 0.50 V/SCE in buffered solutions of 0.2 (c + constant) [V] 0.5 0 0. σtot cos θ) Cm N µdip γ − σin cos2 θ − = ε0 εγ ε0 εγ The charge density σM (θ) on the metal as a function of θ in Eq.2 −20 −15 −10 −5 0 5 10 15 −0. Moreover. A/A(θ).3 −0.4 −0. after rearrangement: σM (θ) cos θ + φd (c. For comparison.8 0.3 20 (sin + sex) or sM [µC cm−2] Fig. the charge densities σin and σex due to the ionized groups of the polar heads. (6) can be estimated by noting that the charge Q(θ) following cw [V] φ (6) . and the thickness β and γ of the hydrocarbon tail and polar head regions. Recalling that the potential difference φ across the whole interface before the expansion has the form of Eq. (2) and considering how the various parameters in this equation change following the expansion. the potential difference after the expansion will take the form: φ= − γ σM (θ) cos θ + σin cos2 θ Cm ε0 εγ ε0 εγ cos2 θ + φd (c. the number N of lipid molecules per unit surface.

allows an extrathermodynamic estimation of the absolute potential difference. φ. the whole left-hand side of Eq. 4 by setting χ = 0 for (σin + σex ) = 0.3 SAMs on Hg Electrodes and Si 117 the drop expansion is clearly equal to: Q(θ) = σM (θ)A(θ) − σM A (7) Q(θ) is obtained by measuring the charge that follows the expansion of a lipid-coated mercury drop with the drop completely immersed in the aqueous electrolyte. and yield a dipole potential of +140–+150 mV. which does not contain ionizable groups inside the hydrocarbon tail region (σin = 0). By plotting this quantity against cos2 θ at a constant applied potential φ. Conversely. Eq. however. positive toward the interior of the film. At the higher pH values at which the polar heads of DOPS and DOPA become progressively more negative. (2) to a DOPC SAM. a straight line is obtained. across the whole mercury–aqueous solution interphase [37]. can be regarded as constant in view of its small rate of change with a change in the charge φ= . The slopes of the plots for DOPC and DOPS at those pH values at which these monolayers are neutral are similar. (6) become progressively more positive. which amounts to about +150 mV and is positive toward the interior. φd . the dipole potential for DOPA is much smaller. whereas the charge density σM on the unexpanded film is obtained as already described. (5). but rather to a group common to these two lipids and buried deeper inside the polar head region. we obtain values close to those directly calculated from the neutral DOPS and DOPA monolayers. exposed to the aqueous phase and effectively screened by the water molecules. by measuring the charge following the contraction of a lipid-coated mercury drop while keeping its neck in contact with the lipid film spread on the surface of the aqueous electrolyte [12]. which. therefore. (2) can be written as follows: N µdip σM + χm with : χm = − Cm ε0 εγ (8) where χm is the surface dipole potential of the polar heads and the capacity Cm of the lipid SAM is given by Eq. φ includes the dipole potential due to the electron spillover. their surface dipole potential values estimated from Eq.1. Upon ignoring the small potential difference. and a further contribution from the orientation of the adsorbed water molecules. The DOPS and DOPC monolayers having very similar surface dipole potentials indicate that this potential is not to be ascribed to the serine or choline group of their polar heads. whose slope is equal to the surface dipole potential minus the potential difference across the polar head region created by any charged groups buried in this region. Application of Eq. which is small on a neutral lipid monolayer and becomes progressively more positive with an increase in the negative charge on the polar heads of the lipid. as estimated from Fig. across the diffuse layer. whose polar head consists of the sole phosphate group and whose glycerol backbone is. This can be reasonably identified with the glycerol backbone. This indicates that the dipole potential in phospholipids consists of two main contributions: a contribution from the glycerol backbone. If we subtract from these values the contribution from water reorientation. By estimating the potential difference φd across the diffuse layer as a function of θ by the use of the GC theory. +30 mV [15]. This also explains the low value of the dipole potential of DOPA. (6) can be measured as a function of θ.

positive toward the hydrocarbon tails. Moreover. The adsorption isotherm of lipids monolayers and the reorientation peaks Leermakers and Nelson [38] determined the adsorption isotherm of lipid monolayers on a metal substrate by an approximate statistical treatment of a lattice model in which apolar water monomers and segments of heads and tails of the lipid molecules interact with each other and with the substrate. Upon ascribing to χm an average value of +200 mV. (8) can be written: σM φ(−0.1. to a minor extent. According to the authors [38]. 1.1 and Ref. 16). the interactions of the water monomers and of the lipid head segments with the substrate are considered to become progressively more attractive with an increase in the absolute value of the interfacial electric field. The model predicts the tails in contact with the metal and the heads exposed to the aqueous phase along the flat capacity minimum.8 µF cm−2 + (0. This gives rise to a inhomogeneous layer of two phases consisting of a thin lipid bilayer and of a thin lipid monolayer. of the water monomers) with the tails for the substrate causes a displacement of tail segments by head segments at potentials at which the tail segments still have a higher affinity for the substrate compared to water.200 ± 0.450 V/SCE) = + χm Cm = −0.1 µC cm−2 at −0. in view of their polarizability. Competition of the heads (and. At still more negative potentials the affinity of the tails for the substrate is overtaken by that of the water molecules. If the affinity of the tail segments for the substrate is not particularly high. Eq. under the reasonable assumption that an increase in the hydrocarbon chain length and the presence of .80 µC cm−2 1.118 1 Preparation of Monolayer Modified Electrodes density σM on the metal. this may explain the merging of peaks 1 and 2 into a single peak and a decrease in the potential range of the flat capacity minimum in passing from dioleoyl phosphatidylcholine to dipalmitoyl phosphatidylcholine and to dimyristoyl phosphatidylcholine. This further transition is regarded as responsible for peak 2. as estimated by different procedures both on BLMs and on a mercury electrode [15.450 V/SCE (see Sect.2. the dipole potential χm due to the oriented polar heads of a DOPC monolayer.8 µF cm−2 . In view of the constant amount of lipid molecules on the surface of the mercury drop. Cm on DOPC-mercury equals 1. while σM equals −0.050)V (9) ∼ −(250 ± 50)mV = It follows that the absolute potential difference φ between mercury and the aqueous phase can be obtained by increasing the applied potential E measured versus the SCE by about 250 mV. (8) are experimentally accessible and thermodynamically significant.8 ± 0. Both σM and Cm in Eq. giving rise to a single peak due to a direct passage from a lipid monolayer to patches of lipid bilayer and of water covered areas. 20]. has been reported to assume values ranging from +150 and +250 mV. This transition is regarded as responsible for peak 1. Thus. A negative shift in the applied potential causes an increasing attraction of the heads for the substrate. both incorporating some water molecules: in the thin bilayer the tails of the lipid molecules are directed toward each other. this leads to one-half of the drop surface almost exclusively covered by water and the other half covered by a lipid bilayer.2. at sufficiently negative potentials head segments and water monomers displace the tail segments from the surface in a single transition.3.

this should more than compensate for the expected increase in capacity stemming . 0. polychlorinated biphenyls. The slight decrease in the flat capacity minimum. In the latter case the mole fraction of the compound in the film is known.3. the adsorption isotherm of the given compound can be obtained. Both the above chlorinated biphenyls are more effective than biphenyl because of their greater molecular polarizability. thus. such as polynuclear aromatic hydrocarbons [39]. In fact. Thus. and phenothiazine [40] into DOPC monolayers on Hg causes a negative shift and a depression of peaks 1 and 2. say.1. and hence their affinity for mercury. is probably to be ascribed to a thickening of the film following their incorporation in the lipid monolayer.1 Electroinactive Compounds As a Electroinactive neutral compounds rule. which is often accompanied by a slight decrease in the differential capacity minimum. four or five aromatic rings [41]. while the effect of benzene and naphthalene is negligible. as measured. which is often observed with an increase in the bulk concentration of these compounds. even assuming that the lipid molecules tend to form a lipid bilayer along peak 2. even though the lipid material required for the formation of a lipid bilayer covering the whole drop surface is now available [12]. Planar polyaromatic molecules intercalate more easily between the lipid tails than the nonplanar. The current transients obtained by stepping the potential across the potential range of peak 2 show a minimum followed by a maximum and by an exponential decay to zero [21].1. At any rate.3. The negative shift in the capacity peaks increases with the bulk concentration of the compound first linearly.3 SAMs on Hg Electrodes and Si 119 C=C double bonds enhance the hydrophobicity of the tails.3 Incorporation of Lipophilic Molecules in Phospholipid SAMs on Hg 1. 4-monochlorobiphenyl is more effective than 2-monochlorobiphenyl. by keeping the neck of the lipid-coated mercury drop in contact with a lipid film spread on the surface of an aqueous electrolyte at potentials slightly negative of peak 2. The hydrophobic compounds may be adsorbed in the film from very dilute aqueous solutions or else by spreading a mixed solution of the compound and of the lipid in pentane on the surface of the electrolyte and by transferring the mixture to an HMDE. is not sufficient to explain this effect. twisted ones. undecane and dodecane have a high partition coefficient but no observable effect on lipid monolayers. the time dependence of the current satisfies the expression for an instantaneous nucleation and growth process. by the octanol/water partition coefficient. incorporation of neutral hydrophobic organic compounds. but then tends to attain a limiting value. Hydrophobicity alone.1. This effect becomes more pronounced with an increase in the aromaticity and hydrophobicity of the compound. and was ascribed to the growth and coalescence of the preexisting defects formed along peak 1. whose structure is distorted by the steric hindrance of the ortho-chloro substituent [40]. it becomes appreciable with hydrocarbons with three. and hence are more effective in shifting the peak potentials in the negative direction.2. and by comparing the response of the film so obtained with that obtained by slow equilibration of a lipidcoated electrode with an aqueous solution of the compound.7–0. such a bilayer must be somewhat disorganized and permeable to water. 1. expected for a compact lipid bilayer.3. the differential capacity remains much higher than the value.8 µF cm−2 . Thus.2.

7 µF cm−2 is the capacity of the DOPC monolayer (see Eq. of the lipid tails. Hence χ = − (N µdip /ε0 εγ ) is practically equal to − σM /Cm . was reported to form pores inside a mercury-supported DOPC SAM by a mechanism of nucleation and growth similar to that of a number of channel-forming peptides [43]. an effect that can explain −2 why compounds with such different structures may act as powerful inducers of terminal differentiation of various types of tumors. the differential capacity of a DOPC SAM containing 33 mol% KC is as low as 1. a steroid that differs from cholesterol mainly by the presence of a carbonyl group. ≈2.250 V/SCE. Under these conditions. At potentials positive of −0. whose sigmoidal shape reveals two consecutive two-dimensional phase transitions. the DOPC and KC molecules are expected to be randomly distributed within the monolayer. Adsorption of neutral molecules in the polar head region may appreciably alter its surface dipole potential. σtot ) that accompany the small changes in σM are negligibly small. 8). and the changes in φd (c.750 V on a mercury electrode coated with a lipid 100 monolayer consisting of 67 mol% DOPC + 33 mol% KC and immersed in aqueous 0. The resulting change χ in χ can be determined from Eqs (2) and (5) by measuring the change σM in σM that accompanies this adsorption at constant applied potential E = φ + constant. These transitions are characterized by an increased flow of negative capacitive charge and by a concomitant increased separation between consecutive charge versus time curves in Fig. 5. The potential steps responsible for pore formation by KC molecules give rise to the potentiostatic charge versus time curves shown in Fig. where Cm = 1. 5 Charge versus time curves following a series of potential steps from a fixed initial potential Ei = −0. With DOPC monolayers. 0 50 t [ms] . and KC has the same effect as cholesterol in increasing the rigidity of the film and decreasing its differential Q [µC cm−2] −1 Fig. 5. It was thus shown that the so-called hybrid polar compounds produce a positive shift in the surface dipole potential of phospholipid monolayers [42].250 to −0.250 V to final potentials E varying by −10 mV increments from −0. 6-Ketocholestanol (KC). The concomitant decrease in the height of the reorientation peaks 1 and 2 and their broadening are due to a decrease in the cooperativity of the reorientation of the lipid molecules.120 1 Preparation of Monolayer Modified Electrodes from the higher dielectric constant of aromatic compounds compared to that. caused by the intercalation of the foreign molecules.2 µF cm−2 .1 M KCl [43]. σin equals zero.

On the other hand. causing an increase in differential capacity. the fraction θ of the electrode surface covered by the compound will have a capacity Cc higher than that.2 to 6. whose capacity Ct is much lower than that of the head region and close to that. In general. the compound may also determine a condensation and an increase in the alignment of the lipid monolayer. The decrease in differential capacity from 6. causes a progressive increase in the differential capacity and a resulting narrowing of the region of the flat capacity minimum.c. this shift is compensated for by a flow of electrons to the mercury surface along the external circuit. as measured from the metal toward the solution. Cc . of the pure lipid domains. While remaining merely adsorbed in the polar head region. The increase in differential capacity from 1. Cm . Lipophilic ions As a rule. it may also be partly due to a certain destabilization of the lipid film and to a resulting increase in its permeability. it will not affect the tail region. The first phase transition is ascribed to an increase in the alignment of the KC dipoles along the direction of the interfacial electric field. Cm . The cationic phenothiazine . of the whole lipid monolayer. with the oxygen of the carbonyl group more fully turned toward the aqueous solution. because the polarizability of the compound (and hence its Cc value) is higher than that of the lipid tails.5 µF cm−2 observed over the potential range between the two phase transitions is ascribed to the first phase transition giving rise to bundles of KC molecules. causing a decrease in −1 the overall capacity C ∼ (Ct−1 + Cc )−1 . the overall capacity is given by C = θCc + (1 – θ)Cm and is. Such a permeation. This charge movement causes a positive shift in the potential difference across the lipid monolayer. As a rough approximation and disregarding any edge effects at the boundary between the two different domains.5 to 1. This causes the increase in negative charge that characterizes the first two-dimensional phase transition. if the compound ‘‘penetrates’’ the tail region. The increase in capacity is ascribable to the charge displacement resulting from ion translocation from the polar heads to the mercury surface and backward across the hydrocarbon tail region. of the film of the compound will be in series with Ct .1. lipophilic ions tend to permeate the lipid monolayer on the negative side of the region of the capacity minimum if cationic. and on the positive side if anionic. with the oxygens turned toward the interior of the bundles. The permeability of the lipid film to Tl+ ions induced by the first phase transition. higher than that of the pure lipid film. In this case the capacity. support the formation and subsequent disruption of pores across the lipid monolayer. If the compound is simply ‘‘adsorbed’’ on top of the lipid film or intercalated between the polar heads. which is due to electrostatic attraction for the charged electrode surface.8 µF cm−2 after the second phase transition suggests that this transition involves the disruption of the pores and a return to a random distribution of DOPC and KC molecules within the mixed monolayer. therefore. At constant applied potential. this decrease will be low. signal superimposed on the bias potential. following the a. resulting in its thickening and in a decrease in capacity. In these hydrophilic pores the inorganic ions can move back and forth following the ac signal. The effect of lipophilic ions on the capacity minimum is analogous to that of other lipophilic compounds and may be summarized as follows.3 SAMs on Hg Electrodes and Si 121 capacity. and its abrupt decrease induced by the second phase transition.

At more negative potentials this is followed by a rounded pseudocapacity peak due to the reduction of the chargetransfer complex.5 V versus Ag/AgCl.1. 44]. 3) and in direct contact with the electrode surface (x ≈ 0) rather than in the much less polarizable intermediate hydrocarbon tail region. once decreased by the charge involved in the same potential step in the absence of the incorporated ion. All these ions depress and broaden peaks 1 and 2. The cysteine resulting from such a reduction tends to desorb (see Sect.3. This cleavage also yields two other molecular fractions of prothrombin. We can therefore envisage two potential energy wells for these ions at x = 0 and x = β. before penetrating the tail region at higher concentrations. The anionic diuretic furosemide causes an initial slight decrease in the capacity minimum at low bulk concentrations [33] and then an increase at higher concentrations [33. The charge involved in a potential step from a potential negative (positive) enough for the anion (the cation) to be entirely located at x = β to a potential positive (negative) enough to induce a complete translocation of the ion to x = 0. Peptides and proteins The cationic antibiotic polymyxin narrows the minimum capacity region on the negative side and decreases the capacity minimum by ∼0. just as neutral compounds. results from the cleavage of the plasma protein prothrombin under the catalytic action of the prothrombinase complex in the presence of Ca2+ ions. namely. 44]. that appreciable adsorption is also obtained in the absence of Ca2+ .3. in addition to electrostatic interactions. fragment I and fragment II. This indicates that this peptide does not penetrate the hydrocarbon tail region. (RS)2 Hg or (RS)2 Hg2 . when the capacity minimum. Thrombin. C. Thus. This indicates that hydrophobic interactions are also operative.2). not all the prothrombin incorporated in a PS monolayer is displaced from the surface [5]. however. It is generally assumed that prothrombin adheres to negatively charged membrane surfaces by Ca2+ bridges between the negative charges of PS and the γ -carboxyglutamic acid residues of fragment I of prothrombin.2. discretenessof-charge effects were considered. for instance. Lecompte and Miller [6. yields directly the opposite of the charge density of the ion in the lipid film. This may indicate that these anions start interacting with the polar heads at low concentrations. In the presence of prothrombin.35 µF cm−2 [46]. attains the limiting value of 7 µF cm−2 . This value is attained at higher prothrombin bulk concentrations if Ca2+ is absent or if the pure PS .122 1 Preparation of Monolayer Modified Electrodes derivatives cause a moderate increase in the capacity minimum [40. By adsorbing prothrombin on PS monolayers supported by mercury. which the cystine residues form with the mercury surface atoms at the most positive potentials. 1. This procedure allowed the determination of the adsorption isotherms of the TPhP+ and TPhB− ions in DOPC and DOPS monolayers [45]. which stimulates blood coagulation. with a potential energy barrier in between [45]. In interpreting these isotherms. Small lipophilic ions such as tetraphenylphosphonium (TPhP+ ) and tetraphenylborate (TPhB− ) prefer to be located in the polar head region (x ≈ β in Fig. the quadrature component of the electrode admittance shows a flat capacitive minimum at about −0. Both the capacity minimum and the pseudocapacity peak increase with the prothrombin concentration until about 3 µg cm−3 . 47] found. by complexing Ca2+ with EDTA.

Ion channels are responsible for the flow of hydrophilic ions across biomembranes along their electrochemical potential gradient.3 SAMs on Hg Electrodes and Si 123 monolayer is replaced by a mixed monolayer of 75% PC and 25% PS. through its hydrophilic amino acids. two helical monomers of gramicidin form a helical dimer. The monomer of gramicidin incorporated in a mercury-supported phospholipid monolayer has been reported by Nelson to act as an ion channel toward Tl+ . while 25 mol% suppresses both steps. across the membrane. The adsorption of prothrombin on PC monolayers is negligible. and thrombin. These C versus cA−I steps correspond to two consecutive penetration steps into the hydrocarbon tail region. fragment II. with a plateau at ∼4 µF cm−2 . The charge under the voltammetric peak for the reduction of (RS)2 Hg at a PS monolayer points to a maximum value of 4 out of the 12 cysteine residues present in a prothrombin molecule. in this case the effect of Ca2+ may be due to a decrease in the charge and in the resulting electrostatic repulsion between adsorbed prothrombin molecules.4 is obtained for the surface coverage θ by the protein domain. Expressing C by the equation C = θCp + (1 − θ)Cm . about one-half the thickness of a biomembrane. probably associated with two different conformational changes of apoA-I. possibly electrostatic. such as alkali metal ions. indicating that not all its electroactive groups have access to the electrode surface. This may be explained by the cholesterol molecules rigidifying the lipid monolayer.1. are insensitive to the presence of Ca2+ and determine an increase in the capacity minimum only at higher bulk concentrations. coated with a monolayer of phospholipids in which special proteins (apolipoproteins) and cholesterol are embedded. To span a biomembrane. which is then followed by a further sigmoidal step. For cA−I ≤ 4 µg cm−3 the differential capacity minimum C is not affected. where Cm is the capacity of the pure lipid monolayer and Cp ∼ 14 µF cm−2 is that of a pure protein monolayer. thereby preventing it from associating with some penetrating domains of apoA-I. which do not contain γ -carboxyglutamic acid residues and cannot attach to the negatively charged monolayers by Ca2+ bridges.5 µF cm−2 . with a plateau at ∼7. namely. The interaction of apolipoprotein A-I with PC-coated mercury proceeds in steps when increasing progressively its bulk concentration. but the concomitant decrease in the orientation peaks of PC points to an interaction of apoA-I with the polar heads of the lipid. Ten mole percent cholesterol in the PC monolayer suppresses the second penetration step. While the separate fragment I exhibits a behavior similar to that of prothrombin. from the membrane side where the electrochemical potential of the ion is higher to that where it is lower (passive transport). cA−I [48]. A widely investigated ion channel is gramicidin. with the N -terminals of the dimer interacting in the center of the membrane. but it is appreciably increased in the presence of Ca2+ [5]. The resulting hydrophilic pore allows the transport of monovalent cations. The ˚ length of a gramicidin channel is of 13 A. a limiting value of 0. With a further increase in cA−I the plot of C versus cA−I shows a first sigmoidal step. Lipoproteins are molecular aggregates that transport water-insoluble lipids in the blood plasma: they contain a core of neutral lipids. a linear pentadecapeptide with helical structure that turns its hydrophobic groups toward the exterior of the helix and its hydrophilic carboxyl groups toward the interior.

in which the rate-determining step is a preceding homogeneous chemical step associated with Tl+ entry into the channel prior to Tl+ electroreduction [51. The chemical step preceding the electrochemical step was again treated as homogeneous. If gramicidin is incorporated in the lipid monolayer. with a resulting influence on their local concentration. while no interpretation was provided for the following chemical step. [55] by the potential-step chronocoulometric technique. . thus allowing its penetration across the monolayer and its electroreduction to thallium amalgam [49–54]. such as Mg2+ and Dy3+ . If the mercury electrode is coated with a phospholipid monolayer. Nelson proposed a CE mechanism. but the plateau is lower because it is controlled not only by diffusion but also by the rate of penetration of the thallous ions into the ion channel. 6). Its rising section exhibits a Nernstian behavior and its plateau is exclusively controlled by diffusion. while incorporation of the aromatic pesticide dichlorodiphenyl trichloroethane (DDT) slows it down [51]. E) at constant t = 100 ms versus the final potential E. have an opposite effect [52]. On a bare mercury electrode. and hence its potential dependence is of the Nernstian type. This is ascribed to the electrostatic interaction of this charge with Tl+ ions in the immediate vicinity of the lipid film. The potential. the thallous ion is electroreduced to a thallium amalgam. Thus. Rueda and Nelson et al. Incorporation of retinol in a gramicidin-modified DOPC monolayer accelerates Tl+ transport. This is ascribed to the effect of these neutral compounds within the monolayer on the energy barrier to the translocation of the ion within the channel. From a cyclic voltammetric and a chronoamperometric investigation of Tl+ ion electroreduction through the gramicidin channel. The further step involving the surmounting of a potential energy barrier located somewhere in the middle of the channel is considered to be in quasiequilibrium. The rising section still exhibits a Nernstian behavior. The same system was investigated by Becucci et al. the thallous ion cannot permeate the film and hence no reduction current is observed. Since the CE mechanism previously proposed by Nelson [51. solution composition. This electrode process at a mercury-supported phospholipid monolayer incorporating gramicidin was employed by Nelson as a model system to probe the effect of lipid charge. curve a. while polyvalent cations. [53] investigated Tl+ electroreduction in gramicidin-modified DOPC monolayers on mercury by electrochemical impedance spectroscopy. and incorporation of biologically active compounds on ion channel transport. as shown in Fig. 52]. of the minimum in the curve of the Warburg coefficient against potential was found to shift by 13 mV toward positive values with respect to the reversible half-wave potential for Tl+ electroreduction at a bare mercury electrode. which provides a satisfactory fit to the impedance spectroscopic data. the sigmoidal charge versus potential curve for thallous reduction reappears (solid curve b in Fig. it was shown that a negatively charged DOPS monolayer increases the rate of Tl+ transport with respect to a neutral DOPC monolayer. 6. giving rise to a sigmoidal curve of the chronocoulometric charge Q(t. This behavior can be explained quantitatively by a mechanism that includes the diffusion of the thallous ions toward the lipid film and a potential-independent ‘‘heterogeneous’’ step consisting in the dehydration of the ion and its binding to a site located at the mouth of the ion channel. 52] predicts a negative shift in Emin . Emin .124 1 Preparation of Monolayer Modified Electrodes ion. a CEC mechanism was postulated.

which creates a dipole potential positive toward the interior. of the thallous ion/thallium amalgam couple by an amount equal to (RT/F) ln(Qd /Ql ). where Qd is the diffusion limiting charge and Ql is the limiting charge in the presence of the gramicidin-modified DOPC film.5 × 10−7 M gramicidin by stepping from a fixed initial potential Ei = −0.1 M KCl aqueous solution containing 4 × 10−4 M Tl+ + 1. because of the presence of a carbonyl . postulated an additional homogeneous chemical step mimicking the deactivation and release of a Tl+ -gramicidin intermediate from the electrode surface. obtained from a 0. Since the transfer of the thallous ion in direct contact with the metal surface to the mercury with amalgam formation is expected to be Nernstian. 6. Two lipophilic neutral molecules are commonly incorporated into membranes with the aim of altering their dipole potential. (b) on mercury coated with a DOPC monolayer upon stirring to allow gramicidin incorporation. More recently. it also predicts a positive shift in the half-wave potential with respect to the formal potential. which was calculated on the basis of the above mechanism.4 0. This prediction agrees with experiment. The dashed curves were calculated on the basis of the mechanism outlined in the text [55]. E 0 . in competition with the surmounting of the potential energy barrier located within the channel.8 b 0. as shown by the dashed curve b in Fig.250 V/SCE to progressively more negative potentials: (a) on bare mercury. Rueda and coworkers [56]. phloretin. the dependence of the faradaic charge upon the overall applied potential E is also Nernstian. and KC. (c) on mercury coated with a DOPC monolayer containing 23 mol% 6-ketocholestanol upon stirring. 6 Plots of the ratio of the chronocoulometric charge Q (t = 100 ms) to its diffusion limiting value Qd against (E − E0 ).6 c 125 Q /Qd 0. by investigating this system by electrochemical impedance spectroscopy.3 SAMs on Hg Electrodes and Si 1 a 0.1. which creates a dipole potential negative toward the interior of the lipid film. The mechanism predicts a plateau that is controlled partially by diffusion toward the film and partially by the binding step at the mouth of the channel.2 0 150 100 50 0 –50 –100 –150 –200 –250 E– [mV] E0 Fig. namely.

3. Incorporation in a DOPC monolayer yields a single irreversible voltammetric peak that shifts by 62 mV toward more negative potentials per each unitary increment in pH and is tentatively ascribed to reduction to the corresponding alcohol. owing to the flow of the capacitive current that is required to charge the interphase. In fact. in view of its pKa value of about 8. The solid curve c in Fig. the rate .2. the aldehydic form of vitamin A. The charge Q(t) following each potential step was recorded versus the time t elapsed from the instant of the step for 50 ms. At the less negative potentials at which UQ is still electroinactive. At more negative final potentials Q(t) increases in time first abruptly. the favorable dipole potential created by phloretin. 58]. the unfavorable dipole potential.3. because of the gradual electroreduction of UQ in time. Figure 7 shows a series of curves of the charge Q(t) as a function of time for progressively more negative final potentials. This leads to a decrease in the rate constant for the surmounting of the barrier. positive toward the interior of the film. which has the typical Butler–Volmer dependence upon the applied potential. where ubiquinol is completely reoxidized to UQ. the charge Q(t) increases abruptly in less than 1 ms. slows down this intermediate step by increasing the height of the potential energy barrier within the ion channel. The mechanism of its reduction inside a phospholipid monolayer supported by mercury was investigated by carrying out a series of consecutive potential steps from a fixed initial value Ei . As expected. Conversely. and then more slowly. incorporation of phloretin in the lipid monolayer containing gramicidin has no effect on the charge versus potential curve for thallous ion reduction [55].1. created by incorporating 23 mol% KC in the DOPC monolayer. The more positive peak depends weakly on pH at pH values < 8 and is tentatively ascribed to the reduction of a Schiff base formed between retinal and the amino group of DOPS or DOPE. A cyclic voltammetric investigation of retinal incorporated in mercury-supported phospholipid monolayers was carried out by Nelson [59]. as provided by a DOPC monolayer containing 1 mol% UQ. With a further negative shift of the final potential. to progressively more negative potentials [60]. 6 is the experimental Q(t = 100 ms) versus (E − E 0 ) curve. whereas the corresponding dashed curve was calculated on the basis of the pertinent mechanism. Ubiquinone-10 (UQ) is an important.126 1 Preparation of Monolayer Modified Electrodes group [57. This causes a drawing out of the charge versus potential curve for Tl+ reduction. retinol. is the light-absorbing molecule of the visual system of all organisms that possess image-producing eyes.2 Electroactive Compounds Retinal. where UQ is still electroinactive. ubiquitous biomolecule that is present in many membranes and acts as a proton and electron carrier in the respiratory chain of the mitochondrial membrane. after which the potential was stepped back to the initial value. 1. negative toward the interior of the film. owing to the capacitive contribution. Incorporation of retinal in DOPS or DOPE monolayers causes the reduction peak to split into two. In fact. the Schiff base is known to be reduced at potentials more positive than the corresponding aldehyde and is expected to be mainly in the protonated form at pH values < 8. cannot accelerate the overcoming of the potential energy barrier more than predicted by a Nernstian-type behavior. and then remains constant in time.

and their common slope is a measure of the differential capacity of the lipid monolayer. for UQ concentrations in the lipid film < 1 mol%. Plotting the charge Q(t) at a constant electrolysis time.d. UQ−• .4 V –0. UQH• : −− UQ + e ←− − −→ UQ−• [UQ]/[UQ−• ] = exp r.6 V 127 –1. The faradaic contribution. after which Q(t) becomes again independent of time. until ultimately the UQ incorporated in the lipid monolayer is completely reduced in less than 1 ms. The charge versus time curves at different potentials and pH values allow the mechanism of UQ reduction to be clarified on the basis of a general approach. 7.max –0. say 50 ms. followed by the ratedetermining protonation of this radical anion yielding the corresponding neutral radical.max attained by Qf (t) measures the charge involved in the complete reduction of the UQ incorporated in the film and agrees with a two-electron reduction of UQ to UQH2 .s.075 M borate buffer of pH 9.2 −0. The maximum limiting value Qf . against the applied potential yields a sigmoidal curve.3 SAMs on Hg Electrodes and Si –0.1. Qf (t).700 V in 25 mV increments.3 V 0 25 50 −0.7 V –0. UQ reduction takes place via the reversible uptake of one electron yielding the UQ radical anion.200 V/SCE to final values E varying from −0. of UQ electroreduction increases progressively.5 V Q [µC cm–2] –0. to Q(t) due to the reduction of UQ is readily estimated by measuring the charge from the straight line obtained by extrapolation of the foot of the charge versus potential curve.45 −0.225 to −0. The right-hand side shows the corresponding Q(t = 50 mV) versus E curves [60].0 Q f. Equilibrium F (E − E 0 ) RT −→ UQ−• + H+ − − UQH• Rate = k[H+ ][UQ−• ] (10) . The foot and the plateau run practically parallel.7 t [ms] The left-hand side of the figure shows Q(t) versus t curves for 1 mol% UQ reduction in a 0. 7 E (SCE) [V] Ei = −0.5 –0. as obtained by stepping the potential from a fixed initial value Fig. as shown in Fig. with a rising portion preceded by a sloping foot and followed by a sloping plateau.4.

is kept constant.3 RT) versus log t at constant pH and Qf yields a roughly straight line of unit slope. The chronocoulometric procedure employed for UQ was also adopted to study rds . the quantity F Ep /(2.3 RT) was plotted against the logarithm of the scan rate. therefore. or else as a function of pH at constant t: F E = log t + constant 2.3 RT) versus – pH at constant v. at constant pH as well as against – pH at constant v.3 RT for constant t and [UQ] (12) The UQ concentration at a given time t is kept constant if the faradaic charge Qf (t) that consumes the initial UQ concentration. is kept constant. (12) and. via the Nernst equation as applied to the first electron-transfer step in quasiequilibrium. log v.128 1 Preparation of Monolayer Modified Electrodes This rate-determining step is followed by the rapid uptake of a further electron and a further proton yielding the final product. then the integral in Eq. when [UQ] = [UQ]in . in agreement with Eq. The resulting differential equation can be integrated by separation of variables between time t = 0. upon noting that the potential Ep of the voltammetric peak for UQH2 oxidation practically corresponds to a constant faradaic charge Qf . [UQ](t). The oxidation of ubiquinol-10. Keeping the right-hand side constant allows one to write it in such a way as to express the applied potential E as a function of electrolysis time t at constant pH. Plotting FE/(2. 10). and the same result is obtained by plotting FE/(2. (11) is also constant. F − d[UQ] + = −kt[H ] e RT [UQ] (E−E 0 ) [UQ]in (11) If the UQ concentration at the given time t. as in the case of UQ reduction (see Eq. ubiquinol. on the basis of cyclic voltammograms yielding a unit slope for the plot of FE p /(2.3 RT) versus – pH at constant t and Qf . and a given time t: F − d[U Q] + = −k[H ][UQ]e RT dt [UQ](t) (E−E 0 ) . and the same is true for the corresponding right-hand side. Thus. UQH+• 2 2 + OH− − − UQH• + H2 O. −→ UQH• + OH− − e− ←−→ UQ + H2 O (13) A reversible uptake of the first transferring electron followed by a ratedetermining protonation step. [UQ]in . The rate of consumption of UQ is therefore proportional to the hydrogen ion concentration of the buffer solution adjacent to the lipid monolayer times the concentration of the UQ−• radical anion. this can be expressed as a function of the UQ concentration. incorporated in a DOPC monolayer was investigated by cyclic voltammetry using an approach perfectly analogous to that adopted for the above chronocoulometric measurements [61].3 RT for constant [H+ ] and [UQ] F E = −pH + constant 2. UQH2 . with the mechanism of Eq. was also reported for the reduction of oxidized glutathione [62] and of diphenyl disulfide [63] incorporated in DOPC-coated mercury. [UQ]. (10). The unit slope of both these plots points to the mechanism: UQH2 − e− ←−→ UQH+• .

the lefthand side of Eq.3 SAMs on Hg Electrodes and Si 129 the electrochemical behavior of vitamin K1 . K1 H2 . The chronocoulometric procedure was also employed to study the electroreduction of the polyaromatic cation safranine [65] and that of the azocrown ether L16 to the corresponding hydrazo form [66]. By integrat[V 2 ing this equation after separation of variables we obtain: [V2+ ]∗ 0 d[V2+ ]/[V2+ ]2 = 2k exp[f (2E1 [V2+ ](t) 0 + E2 )] exp[−3f E]t (16) where [V2+ ]* is the initial viologen concentration. The data analysis. V2+ → V+ and V+ → V0 . as obtained from the Q(t. the main proton acceptor involved in the rate-determining deprotonation of the K1 H+• cation radical is H2 O. carried out by the same potential-step procedure adopted for UQ (see. points to a reversible electron-transfer step followed by a rate-determining protonation step. carried out on the basis of Eq. Viologens are electroreduced in two pH-independent electron-transfer steps. E) versus t curves at different potentials E by keeping the faradaic charge constant at a value corresponding to the first Q versus E wave. to a constant value of the concentration [V2+ ](t) of the still unreduced V2+ species). both incorporated in a Hg-supported DOPC monolayer. The mechanism of K1 reduction and that of oxidation of the corresponding quinol. The plot of ln t versus FE/(RT). e. The only difference is represented by the fact that. Consequently. − − −→ 2 V+ + V0 − − V+ rds.g. Chronocoulometric measurements on the lipophilic dioctadecylviologen (C18 )2 V2+ (henceforth briefly denoted by V2+ ) incorporated in a DOPC monolayer. (16) is kept constant and. This slope can be rationalized on the basis of the mechanism: V2+ + e ← → V+ . 7). V+ + e ← → V0 . in K1 H2 oxidation.1. the kinetics of K1 H2 oxidation is independent of pH. k 0 E1 0 E2 (14) where the first two elementary chargetransfer steps are in quasiequilibrium and the third one is a chemical ratedetermining step. This equation shows that. rather 2 than OH− . Fig. if we extract from the Q(t. upon incorporating this physiological quinone in a self-assembled DOPC monolayer supported by mercury [64]. as in the case of UQ reduction. At V2+ concentrations less than 1 mol% the overall height of the two waves corresponds to the uptake of two electrons per V2+ molecule in the lipid monolayer. are analogous to those for the UQ/UQH2 couple. E) against the applied potential E at constant electrolysis time t = 100 ms: the first chronocoulometric wave is three times higher than the second [67]. is linear and exhibits a slope of 3. hence. . In this case the rate v of the process is given by: v= d[V+ ] 1 d[V2+ ] 2 =− = k[V+ ][V0 ] dt 2 dt F RT 0 0 = k exp[f (2E1 + E2 )][V2+ ]2 exp(−3f E) with : f ≡ (15) where the concentrations [V+ ] and [V0 ] are expressed as a function of [V2+ ] through the corresponding Nernst equa0 tions: [V2+ ]/[V+ ] = exp[f (E − E1 )] and + ]/[V0 ] = exp[f (E − E 0 )]. an essential constituent for blood coagulation. yield two sigmoidal waves in the plot of the charge Q(t. (12). E) versus t curves the pairs of values of t and E corresponding to a constant value of Q (and.

The slope of the linear Q(E. E) versus E waves.5 along the plateau of the first wave and of 2 along the second one. The main difference is represented by the fact that (C7 )2 V2+ is incorporated in the lipid monolayer from its aqueous solution. Only after the extensive studies of self-assembled alkanethiols and their derivatives on gold. All the main features of the dependence of Q(E. many of these investigations were focused on electroanalytical detection of thiols by stripping [70–72] or square-wave voltammetry [73–75] under conditions in which the amount of the thiol deposit on Hg is proportional to its bulk concentration. (14). the same is true for the righthand side. respectively. t) upon t and E are quantitatively accounted for on the basis of the above mechanism [67]. The mechanism of Eq. (14) is consistent with the presence of two Q(t = 100 ms. in agreement with the mechanism of Eqs (15) and (17). Thus.3 . that is. The processes responsible for the two waves are therefore: −→ 2 −→ 2V2+ + 3e − − V+ . The mechanism of formation of these SAMs on mercury was barely investigated [76–79]. where n is the number of Faradays exchanged per mole of the reactant and D is the diffusion coefficient of the latter. which have provided a route to wellordered. V2+ acts as an electron-transfer mediator from Fe(CN)6 3− dissolved in the aqueous solution to the mercury surface across the DOPC monolayer. Since the overall height of the two waves corresponds to the uptake of 2 F mol−1 of V2+ . the two consecutive waves involve the uptake of 3/2 and 1/2 of 1 F. However. 69] in studies of the cysteine/cystine system by dc polarography. Qd (t) = 2nF (Dt/π)1/2 [(C7 )2 V2+ ]*. where it is sparingly soluble. the first of which is three times higher than the second. oriented monolayer films [80. for instance. a faradaic contribution Qf due to the amount of viologen incorporated under equilibrium conditions at the initial potential Ei where it is still electroinactive. V+ + e − − 2V0 2 (17) the first of which agrees with the mechanism of Eq. Consequently. t) versus t curves along the plateau of the two waves consist of a capacitive contribution Qc . the increasing separation between the two waves with an increase in [V2+ ]* is explained by the increasing stability of the V2 + dimer with respect to the two V2+ and V0 monomers. 81]. Thiol SAMs on Hg The formation of thiol monolayers on Hg was first reported by Kolthoff and coworkers [3. The incorporation step is diffusion controlled. These initial findings started a series of investigations on the formation of films of water-soluble thiols on Hg from their aqueous solutions.3. While the first two contributions flow almost instantaneously. 1.1. This explains the slope of 3 for the ln t versus FE/(RT) plot. at submonolayer levels. An analogous mechanism is operative in the reduction of the diheptylviologen dication (C7 )2 V2+ incorporated in a DOPC monolayer [68]. which is impermeable to Fe(CN)6 3− in the absence of V2+ . These authors demonstrated that thiol films form spontaneously on Hg in solutions containing cysteine. plus a further faradaic contribution Qd due to (C7 )2 V2+ diffusion from the bulk solution during the electrolysis time t at the final potential E. t) versus t 1/2 plots is indeed proportional to the viologen bulk concentration and yields an n value of 1. the chronocoulometric Q(E. Qd increases progressively in time and its time dependence is expressed by the Cottrell equation.130 1 Preparation of Monolayer Modified Electrodes therefore.

1. according to the general reaction: Hg + RSH ⇐ ⇒ Hg − SH1−α R+λ−α + λe + αH+ (18) Here λ is the partial charge-transfer coefficient. with oxygen reduction to water in its presence. a SAM of mercaptopropionic acid in a thiol-free solution is disrupted on a Hg support. but detectable. featureless. tendency of Hg-thiol adducts such as Hg(SR)2 to dissolve [73]. under conditions of total charge transfer (α = λ = 1). no definite evidence for the formation of these monolayers can be gained. transfer of SAMs of rather soluble thiols from the thiol solution in which they have been formed to a thiol-free solution in the same solvent causes a partial dissolution of the SAM. SAMs of water-insoluble thiols. α and λ are expected to assume close values. No such dissolution of gold by thiols has ever been reported. and α is the degree of dissociation of the sulfhydryl group. self-assemble spontaneously on mercury from their aqueous solutions. and has no stoichiometric implications. these electrons can only be removed through the flow of an oxidation current along a closed electric circuit. namely. mercury electrodes are readily renewable and there is no need to condition them prior to use. Moreover. This may be due to the lower Hg−S binding energy (∼200 kJ mol−1 ) with respect to the Au−S binding energy (∼400 kJ mol−1 ). In this case.1 Preparation Methodology and Water-soluble thiols. 79] thiolate monolayers has been postulated. but not on a Au support. However. Hg has a homogeneous.1. As distinct from phospholipids. much more easily. As a matter of fact.3. Thus. In the absence of oxygen. formation of mercurous [3. the fraction of electron charge transferred from a sulfur atom to the mercury upon adsorption. 1. Hg has a high affinity for thiols. or also to a slight. The Hg notation is merely used to denote chemisorption of the RSH thiol on Hg. because the passage from mercurous to mercuric thiolate does not involve a flow of electrons along the external circuit. proceeds to full electrode coverage because it occurs simultaneously with oxygen reduction. such as long-chain alkanethiols. which removes electrons from the Hg electrode.3. 82–87] has attracted much interest because of the unique properties of this liquid metal. As a rule. Like Au. the reaction of Eq. with λ = 1. referring to mercurous or mercuric thiolate monolayers becomes meaningless in the case of partial charge transfer. Moreover. Thus. (18). while Au exhibits surface steps and kinks that play a significant role in establishing defects in the deposited films. at an appropriate applied potential.3 SAMs on Hg Electrodes and Si 131 the use of liquid mercury in place of gold [16. However. the selfassembly is accompanied by partial or total electron transfer from the sulfhydryl group to the metal and by concomitant sulfhydryl deprotonation. Self-assembly of thiols on Hg also takes place under open-circuit conditions. 69] or both mercurous and mercuric [77. at the Hg–water interface are usually obtained by immersing a mercury drop in a 20% (by volume) . with hydrogen evolution in the absence of oxygen or. such Procedures as cysteine. defect-free surface. full SAMs of 6-thioguanine and 6thioguanosine were reported to form on an HMDE under open-circuit conditions only in the presence of oxygen [88]. Since partial electron transfer from the sulfhydryl groups and their deprotonation are strictly correlated events.

or to Langmuir monolayers on aqueous or organic subphases. The atomic surface layering of bare mercury persists in the thiol-covered surface. the strong Au−S bonds prevail over interchain interactions.3. imposing a well-defined long-range order.2. On a solid support such as Au(111). Figure 8 shows this normalized profile for bare Hg (dashed line) and for n-octadecanethiol and n-dodecanethiol monolayers.5 M NaOH aqueous solutions. In Langmuir monolayers the order is induced by interchain interactions. which is sensitive to the molecular structure within the surface plane [89].132 1 Preparation of Monolayer Modified Electrodes solution of the thiol in ethanol or hexadecane from 10 seconds to 2 minutes [82. Naturally. pentane or hexane). This difference in behavior is explained by a competition between interchain van der Waals interactions within the monolayer and interactions of the monolayer with its support. does not affect the SAM properties. which exceed the strength of the hydrogen bonds between the monolayer and the subphase. The thiol-coated mercury drop obtained by this ‘‘soaking procedure’’ is then rinsed with the solvent to remove unadsorbed alkanethiol and immersed into the aqueous solution.3. or stirring the solution with a stir bar. The main result was the observation that these SAMs have no in-plane long-range order. Another procedure (spreading procedure) consists in spreading an amount of thiol corresponding to six to nine monolayers. the small mismatch between this support and alkane spacings is compensated by a molecular tilt of ∼30◦ . where they are soluble under the form of alkanethiolates [74.1 Surface-sensitive Techniques Owing to the difficulty of applying surfacesensitive techniques to a liquid surface such as mercury. as opposed to analogous SAMs on solid supports such as Au. 86]. Same considerations apply to alkanethiols with up to eight carbon atoms in 0.1.2–0. Alkanethiol SAMs on Hg were also investigated by X-ray reflectivity [89]. with the sulfur atoms firmly bound to the surface of the mercury drop and the alkyl chains exposed to the solution. mounting in a cell. After one or two immersions and subsequent emersions. which probes the electronic density profile along the surface normal. an alkanethiol monolayer is formed. long-chain alkanethiols insoluble in water are soluble in organic polar solvents such as ethanol [16. on the surface of an aqueous solution.3. Normal handling of an HMDE coated with these SAMs.3. at least for alkanethiols with nc > 10–15. only very few structural investigations by these techniques are available in the literature. indicating that the .g. The structure of SAMs of n-alkanethiols with a number nc of carbon atoms from 8 to 30 on mercury was investigated by grazing-incidence X-ray diffraction (GIXD). such as rinsing. 87].1. On liquid mercury the strong Hg−S interactions prevail over interchain interactions. allowing the solvent to evaporate and immersing the mercury electrode into the solution through the thiol film at a well-defined velocity [86].2 Structure and Physical Properties of Thiol SAMs on Mercury 1. there is no underlying corrugation potential to order the thiol SAM. 1. but since the liquid mercury surface has no intrinsic long-range order. These SAMs are stable for a long time in thiol-free aqueous solutions. dissolved in a suitable solvent (e. 85] and acetonitrile [84]: in electrolytic solutions of these solvents they can self-assemble on Hg and be investigated by electrochemical techniques. This was obtained by fitting the reflectivity data to a density-dependent model reflectivity calculated from the Born approximation.

pointing to a vertical orientation of these molecules within the SAM. The upper and lower figures are aligned with each other. The high SAM elec˚ tron density (0.2 0 –30 –20 –10 0 10 z [Å] thiol monolayer induces no major changes in the liquid/(metal surface) structure. exhibit standing-up phases at high coverage and lying-down phases at low coverage [92]. only lying-down phases on mercury are found [91]. [93]. The length of this step matches that of the fully extended alkanethiol molecules. An attempt to obtain scanning tunneling microscopy (STM) images of alkanethiol SAMs on mercury was made by BrucknerLea et al. where an in-plane order is observed [90]. 1.6 0. the surface roughness. which is close to that in crystalline alkanes. while fatty acids. A vertical orientation appears only when strong headgroup–mercury interactions exist. The only differences with respect to bare mercury are a shoulder in the density profile at the position of the sulfur atoms. .0 0. estimated from the width of the density profile of the outermost mercury layer. whose volume was regulated by a syringe. Using the constant height mode.2 1. For alkanes. and a step at the position of the alkyl chain. These y-directed oscillations.02 e A−3 ). due to slow waving of the mercury surface.1.3 SAMs on Hg Electrodes and Si Fig. is about ˚ 1 A.34 ± 0. the STM images of bare mercury show broad oscillations along the slow-scan (y) axis.23 A2 . points to a densely packed monolayer. a slight decrease in the amplitude of the first mercury layers. were avoided by resetting the height baseline at every x scan. estimated from the in-plane peaks of the GIXD patterns of thiol multilayers on Hg.4 0. but not along the fastscan (x) one. 8 133 <r(z)>/r∞ Schematic real-space model and normalized electron density profiles < ρ(z)>/ρ∞ (where ρ∞ is the bulk electron density of mercury) obtained from the fits of reflectivity data to a density-dependent model for n-octadecanethiol (bold line) and n-dodecanethiol (thin line). A mercury sessile drop. STM images of bare mercury appear smooth. with the origin of z coinciding with the first mercury layer [89].8 0. In this way. Vertical lines in the model mark the position of the three outermost surface layers of mercury. In both cases. lacking such headgroups. was partially coated with n-octanethiol by exposing it to the thiol vapor for less than 2 minutes. This agrees with a cross-sectional area ˚ per molecule of 19. which interact with Hg more weakly than thiols.

69.85 m2/3 t 2/3 in view of the volume of the spherical drop being proportional to the time t elapsed from drop birth. 1. 77.3. where m is the maximum surface concentration of the thiol. the STM image shows reproducible islands of similar tunneling current on a background of lower tunneling current. This indicates that in the present case charge transfer is total. noting that A(t) equals 0. and 2-mercaptopyridine N-oxide [78]. thus suggesting that the thiol film is in the liquid-like region of the surface pressure–area curve. such as benzyl mercaptan. 75]. being insoluble in water. in practice. Any arguments in favor of the formation of a mercurous or mercuric cysteine thiolate monolayer are purely hypothetical [3. 69]. In the case of cysteine. where m is the mercury flow rate. Unfortunately. At an HMDE cysteine yields a dc adsorption polarographic prewave over a pH range from 2 to 9 [3. At more positive potentials. total charge transfer can be safely assumed for all soluble thiols. Under these conditions. and the mean limiting current attains a maximum value that does not increase with a further increase in the thiol bulk concentration.2 Electrochemical Properties Soluble thiols The electrochemical behavior of water-soluble thiols is exemplified by cysteine. no STM images of single thiol molecules have been obtained so far on Hg. the sessile drop maintains its spherical shape.2 M NaOH [74]. This suggests that the thiol film is now in an ordered two-dimensional solid state. For 2-mercaptopyridine N-oxide the formation of the corresponding disulfide was postulated [78]. 79]. A(t). it is usually assumed that the product is a Hg(I) thiolate [69. 77] which.2. Since Hg(II) thiolate is also sparingly soluble in water. by decreasing the drop volume slightly.134 1 Preparation of Monolayer Modified Electrodes while those of thiol-coated mercury show large surface features. At very low cysteine concentration the limiting current of this prewave is diffusion controlled.3. As the volume of the sessile drop is decreased further. according to Eq. Hence. Linear sweep voltammograms of cysteine at an HMDE yield an oxidation peak that . There is no general consensus on the nature of the resulting oxidation product. cysteine and other water-soluble thiols [74] yield a dc polarographic wave (the so-called main wave) that starts developing as soon as the prewave has attained its maximum limiting height and whose limiting current is diffusion controlled. At concentrations >∼ 2 × 10−4 M the growing area. of the drop is instantaneously covered by a compact thiol monolayer as soon as it protrudes from the capillary orifice. (18). disproportionates into the corresponding Hg(II) thiolate and Hg [74]. 74. This value corresponds to a compact cysteine SAM for λ = 1. This equation allows λF m to be estimated at ∼70 µC cm−2 . 1-butanethiol and 1-decanethiol in 0.85λF m m2/3 t −1/3 . Under these conditions the charge Q(t) transferred to the mercury upon adsorption is equal to m A(t). This is due to cysteine adsorption with partial charge transfer. Similar dc oxidation prewaves are observed with many thiols. which is one of the most extensively investigated. the drop assumes a flattened shape owing to an increase in the surface area-tovolume ratio. it is expected to ultimately deposit and form a multilayer on the mercury surface [74. The resulting STM images show small parallel n-octanethiol ridges of higher current density (1–10 nA high).1. the maximum mean limiting current is given by im (t) = Q(t)/t = 0. In particular.

therefore. the reductive desorption peak of cysteine and of other thiols [74. the disulfide resulting from the chemical oxidation of cysteine. The fact that the additional peak appears at a less negative potential than the single peak present before the splitting as soon as the bulk concentration becomes higher than that required for the formation of a compact monolayer under diffusion control strongly suggests that it is due to dissolution of a mercury thiolate multilayer on top of the monolayer in direct contact with the mercury surface [75]. Thus. Differently stated. The dc polarographic main wave has often been ascribed to a faradaic process inhibited by the film formed during the prewave and which may proceed only after a breakdown of this film [69. This seems to be the case with cysteine. 75]. and is then subjected to a negative linear potential scan. in fairly good agreement with the charge estimated from the corresponding dc adsorption prewave. as in the case of mercury cysteine thiolate. it is quite probable that the prewave is due to a process facilitated by adsorption of the product of the electrode reaction of Eq. (18). with the less negative peak being due to the Hg(I) compound [79]. 79. 95]. The resulting film is. during the pretreatment [74. with λ = α = 1. a voltammetric reduction peak is observed. (18). or to the result of ‘‘compacting’’ of the mercuric cysteine thiolate film [76]. 74]. 75. at least partially. As a matter of fact. and the product must diffuse away from the electrode. 78] has been reported to split into two.3 SAMs on Hg Electrodes and Si 135 levels off when the charge under the peak attains a maximum limiting value of about 80 µF cm−2 [76]. with respect to the case in which the mercury thiolate is not adsorbed. analogous to that resulting from cysteine chemisorption. it may also deposit on the drop surface. the free energy involved in the formation of the prewave is decreased by an amount corresponding to the free energy of adsorption of the mercury thiolate. Thus. usually at relatively high concentrations. chemisorbes on Hg with cleavage of the −S−S−bond and formation of two Hg−S bonds [3. However. The first dc polarographic reduction wave [77] (or the first voltammetric reduction peak [76]) of a cystine solution has the character of a desorption wave resulting from the . The latter monolayer is expected to be more difficult to reduce than the overhanging multilayer if the Hg−S bond is stronger than the interaction forces within the multilayer.1. Cystine. If the product is sparingly soluble. of the oxidative adsorption dc prewave [69]. the charge under this reductive desorption peak has often been found to be greater than that of the corresponding oxidative adsorption peak or. equivalently. it was attributed to the presence of both mercuric and mercurous cysteine thiolates in the film. This excess charge may be ascribed to reduction of a mercury thiolate multilayer formed on top of the thiol chemisorbed monolayer in direct contact with mercury. if a stationary mercury electrode is pretreated in a cysteine solution at a potential positive of the rising portion of the dc polarographic main wave. The main wave starts to develop at bulk thiol concentrations at which there is no longer room for adsorbed product molecules on the drop surface. Quite often. This is ascribed to the release of electrons from the mercury to the sulfur atoms of adsorbed cysteine according to the backward reaction of Eq. and therefore the prewave is developed at a less positive potential than in the absence of mercury thiolate adsorption [94]. 77. with release of cysteine molecules to the aqueous solution. Different tentative explanations have been provided for this splitting.

The irreversible character of the latter wave may possibly be due to a slow cleavage of the −S−S−bond [79].6 –0. this desorption wave is followed by an irreversible diffusion-controlled wave [77]. For nc ≥ 6 no peak III is observed. This is ascribed to a reversible partial electron transfer from S to mercury [77]. The foot of this adsorption wave is characterized by a positive pseudocapacitive current. E1/2 = (Epa + Epc )/2. The midpoint between the reduction peak potential and the corresponding oxidation one. Reversal of the voltage scan yields two cyclic voltammetric reduction peaks corresponding to the oxidation peaks I and II (see Fig. this decreases linearly with nc according to the relation Gads = A − Bnc [87]. Bottom: cyclic voltammogram recorded at a higher current sensitivity over a narrower potential range. as shown in Fig. the latter value corresponds to a practically close-packed monolayer in the case of total charge transfer (λ = 1). n-Alkanethiolates with a number nc of carbon atoms from two to eight yield two voltammetric oxidation peaks in aqueous 0. as distinct from the negative purely capacitive current exhibited by the supporting electrolyte alone.4 E vs Ag/AgCl [V] Fig. 9 [87].0 –0.5 M NaOH.8 –0. 9 Top: cyclic voltammogram of Hg in aqueous 0. As distinct from a cysteine solution. III 10 µA II I II I 4 µA The more negative (peak I) is ascribed to a rapid and reversible oxidative adsorption of a submonolayer quantity of Cnc H2nc+1 S− . 9. .5 M NaOH solution containing 5 mM C5 H11 S− .136 1 Preparation of Monolayer Modified Electrodes transfer of negative charge from the mercury to the sulfur atom of the adsorbed monolayer and release of cysteine to the solution. which becomes impermeable to the thiolate molecules. bottom). owing to the deposition of a bulk film of mercurous or mercuric thiolate. yields the Gibbs adsorption free enthalpy for the oxidative/reductive adsorption process via the relation Gads = −F E1/2 . The nc -dependent term is considered to measure the energetic contribution resulting from the transfer of the amphiphilic n-alkanethiolate from bulk water onto the –1. while the second. so as to avoid recording peak III [87]. considerably sharper peak (peak II) results from further deposition of Cnc H2nc+1 S− to yield an essentially compact monolayer. because of the electroreduction to cysteine of bulk cystine diffusing toward the electrode. The charge under the two peaks increases from 80 to 95 µC cm−2 with an increase in chain length. probably because of an increased compactness of the SAM. which is ascribed to an irreversible electron transfer from the S atoms to mercury [77]. Aqueous solutions of cystine also yield a dc polarographic oxidative adsorption wave. n-Alkanethiolates with nc < 6 also show a further more positive oxidation peak (peak III). scan rate = 100 mV s−1 .

during the positive potential scan. At potentials negative of the adsorption–desorption peaks.3 SAMs on Hg Electrodes and Si 137 metal surface. (18) with λ = α = 1. Thus. these consisted in adsorbing the thiol on an HMDE from a thiol solution at a potential negative of the adsorption–desorption peaks. Cyclic voltammograms of soluble thiols are often characterized by an oxidative adsorption peak. This procedure was also used to measure the adsorption isotherms of two ω-mercaptoalkanoic acids.35 to −0. attaining a maximum limiting value corresponding to a full monolayer coverage (83 µC cm−2 ). during the negative potential scan (see Fig. and by a reductive desorption peak. 10a [100b].1 .2 (a) 0. the reductive desorption peak may undergo splitting [96. The charge under the resulting reductive desorption peak increases with an increase in the thiol concentration used for the adsorption.6 –0. Clear evidence for such a physisorption was provided in the case of ω-mercaptoalkanoic acids [98] by ex situ measurements. which were found to satisfy the Frumkin model with attractive lateral interactions.l M acetic acid containing 1 × 10−4 M 6-thioguanine.0 E [V] Fig. while the A term is regarded as the constant contribution associated with the Hg−S interaction.1. At higher bulk thiol concentrations. 10 (a) Cyclic voltammogram of mercury in a pH 4 aqueous solution of 0. If the ex situ procedure is modified by immersing the thiol-coated mercury drop in a thiolfree solution at a potential negative of 40 i [µA cm−2] 0 –40 –0. but remain physisorbed on the mercury surface. rinsing it with water. immersing it in a thiol-free solution under a potential positive of the adsorption–desorption peaks. and scanning the potential in the negative direction.4 –0. (b) Current versus time curve obtained by stepping the potential from −0. removing the electrode from the solution under the same applied potential. 97]. this peak sharpens and shifts to more negative potentials with an increase in thiol length and a decrease in the size of its headgroup. 10a). The nature of the functional group affects the sharpness and potential of the reduction peak. i (b) 0 t [s] 0. due to the corresponding backward reaction. thiols are generally not desorbed.025 V/SCE across the oxidative adsorption peak of Fig. due to the forward electrode reaction of Eq.

which is typical of a two-dimensional phase transition [100b]. Keeping an HMDE in a 20 µM mercaptohexanol solution in 0. such as Ru(NH3 )6 3− reduction [99]. A somewhat different behavior was reported for mercaptohexanol [96]. thanks to strong attractive intermolecular interactions. while the charge under the current–time curve remains constant. 101] form particularly compact SAMs on Hg. the appearance of a second sharper and less negative reductive desorption peak is ascribed to a passage of the thiol molecules from a flat to a vertical orientation. and no multilayers are formed. the film is not blocking toward Ru(NH3 )6 3− electroreduction. at longer times this is accompanied by a less negative reductive desorption peak. in agreement with the general reaction of Eq. When a single desorption peak is observed. well-organized phase to a two-dimensional condensed SAM. the latter inhibits multilayer formation and oxygen electroreduction. the charge under the peak increases progressively with the rest time.138 1 Preparation of Monolayer Modified Electrodes the desorption peak. The condensed SAM is formed by a mechanism of nucleation and growth. because films of ω-mercaptoalkanoic acids with eight or less carbon atoms do not sufficiently block the electron transfer. a single reductive desorption peak is first observed. which is sharp and symmetrically shaped. at potentials positive of the peak. and then by recording the desorption peak in the thiol-free solution. while the physisorbed phase gradually dissolves. 100a] and 6-thioguanine [100b. only a modest decrease in the rate of Ru(NH3 )6 3− electroreduction is observed. being practically equal to . the charge under the peaks decreases with an increase in the rest time. Ex situ experiments indicate that the condensed SAM is stable in thiol-free solutions. while it becomes blocking when the further less negative desorption peak develops at longer times. while it has no effect on the rate of outer-sphere electrontransfer processes. specifically ring–ring stacking interactions. if the ex situ procedure is modified by adsorbing the thiol from the thiol solution for a given rest time at a potential positive of the adsorption peak. c. which becomes progressively sharper. as clearly demonstrated by the shape of the current–time curves obtained by stepping the potential from the region of the physisorbed phase to that of the two-dimensional condensed one. 10b). Mercapto derivatives of nucleobases such as 6-thiopurine [99. Scanning the potential in the positive direction gives rise to an oxidative adsorption peak that marks the passage from a physisorbed. which is close to that corresponding to a full thiol monolayer. On the other hand. These curves show a minimum followed by a maximum. This behavior denotes a gradual dissolution of the physisorbed thiol in the thiol-free solution. for λ = α = 1. A similar evolution of the reductive desorption peak in time is observed with a pH 4 solution of 30 µM 4-mercaptophenol [97]. across the oxidative adsorption peak (see Fig. The current maximum increases and becomes narrower with an increase in the width of the potential jump. shifts by 60 mV toward more negative potentials per each unitary increment in pH.5 M NaOH at a potential positive of the adsorption–desorption peaks for progressively increasing times. The adsorption peak. keeping the drop at this potential for a given rest time and then recording the adsorption and desorption peaks. This is due to the formation of a progressively thicker film of the thiol during the rest time. (18). At potentials positive of the final compact SAM of vertically oriented molecules. In this case. The charge under both desorption peaks attains a limiting value of 73 µC cm−2 .

4 V [82]. this is prevented by a sufficiently high scan rate. the charge under the reduction peak of C18 decreases with an increase in scan rate. the charge under the reduction peak attains an almost constant maximum value [84.1. a closepacked SAM with exactly the same properties is often restored [16. are characterized by a broad potential range over which they form stable SAMs with a low and practically constant differential capacity. In the case of 6-thioguanine. yields an oxidation readsorption peak. The charge under the peak depends to some extent on the nature of the solvent. attaining a constant minimum value of ∼70 µC cm−2 for scan rates ≥ 100 mV s−1 [16]. the mercury electrode is kept for 2–4 minutes at a potential corresponding to the flat capacity minimum. in which the aqueous solution is saturated with the thiol that is spread on its surface. just after the negative-going scan that causes reductive desorption. while in water it varies . Thus. 1. where n-alkanethiols are moderately soluble and are directly adsorbed from the solvent. while oxidation of bare mercury in 0. The peak may also split into two at high pH values [16]. it amounts to ∼115 µC cm−2 for n-octadecanethiol from ethanol [16] and ∼80 µC cm−2 for n-hexadecanethiol from acetonitrile [84]. under saturating conditions.1 M NaF takes place at about 0. owing to the increased hydrophobic interactions resulting from the lower solubility of thiols in water. which remain in the proximity of the electrode and can spread back onto the electrode surface without any loss of material. Henceforth. If.1. This restoration can be explained by postulating that the desorption gives rise to thiol micelles or similar organizations. Thus. For n-alkanethiols with a number of carbon atoms higher than about five. Thus.3. a mercury electrode coated with a SAM of nhexadecanethiol is not oxidized until about 1.3 SAMs on Hg Electrodes and Si 139 that involved in the voltammetric adsorption peak.3. It is usually higher in organic solvents. Moreover. This indicates that charge transfer from the sulfhydryl group to the metal is accompanied or preceded by deprotonation. This occurs more frequently by using the ‘‘spreading’’ procedure (see Sect. In aqueous solution. it is usually higher in organic solvents than in water. A negative linear voltage scan yields a desorption peak due to the backward electrode reaction of Eq. whose peak potential shifts in the negative direction by about 60 mV per each unitary increment in pH [16]. This phenomenon is ascribed to a slow hydrogen evolution resulting from the penetration of water molecules into the partially disordered C18 SAM and their electroreduction by the catalytic action of the sulfur atoms. n-alkanethiols with a number nc of carbon atoms will be briefly denoted by Cn .3.4 V/SCE. (18). This is due to the highly impermeable and defect-free SAM. This range extends in both directions with an increase in chain length. and can be interpreted quantitatively by including an additional contribution from double-layer charging and one from slow adsorption of disordered thiol molecules [100c]. which protects Hg against oxidation.1). The flat capacity minimum of n-alkanethiols extends over a broader potential region in water than in organic solvents such as ethanol. Reverting the potential scan. the flat capacity minimum in acetonitrile varies from 3 to 6 µF cm−2 on passing from C18 to C6 [84]. after reductive desorption of the thiol. the current transients are close to those predicted for a two-dimensional instantaneous nucleation. such as long-chain n-alkanethiols. Insoluble thiols Water-insoluble thiols. 86]. 85].

the plot of log |Z| versus log f (Bode plot) has a slope of −1 (Fig. This occurs at higher frequencies the lower is R . With well-behaved n-alkanethiol SAMs. where f is the frequency of the ac signal.140 1 Preparation of Monolayer Modified Electrodes from 0. namely. Strictly speaking.1. Rt is of the order of 20 M cm2 . Over a broad frequency range. because of the high polarizability of the peptide bonds. While the impedance of the capacitor Ct is given by – j/(2πf Ct ). the modulus. q. and ultimately greater than Rt . experienced by the diffuse-layer ions to be estimated at −3 µC cm−2 . and starts controlling Z for f < 10−1 Hz. Hence. the aqueous electrolyte is represented as a resistor R is series with the thiol monolayer (see inset 1 of Fig. 11). and the Bode plot tends again to become horizontal.1. but a capacity of the order of 10 µF cm−2 . A different situation is encountered with thiolpeptides.0 [85]. this has often been identified with the charge under the reductive desorption peak. 2. The mercury–thiol solution interface can be satisfactorily simulated with an equivalent circuit in which the thiol monolayer is represented as a capacitor Ct with a parallel resistor Rt . the impedance of the resistors Rt and R is equal to their resistance. Therefore. On the other hand.2. and is therefore frequency independent. 11 allows Cd to be measured as a function of c. 104] correction for the 1. 11). of the impedance is controlled by the capacitor Ct . A closer insight into the electrical properties of thiol-coated mercury can be gained by using electrochemical impedance spectroscopy. as shown in inset 3 of Figure 11. at very low frequencies.70 to 0. allows the charge density. C = ε0 ε/d. with [103] or without [87. the capacity Ct of nalkanethiols is so low that the contribution of Cd is entirely negligible.3. by setting the dielectric constant ε equal to the value. The values in water are in fairly good agreement with the differential capacities calculated from the Helmholtz formula for a parallel-plate capacitor.3 . and the Bode plot tends to become horizontal.95 µF cm−2 on passing from C18 to C14 [86].3. the use of the equivalent circuit in inset 2 of Fig. the equivalent circuit should also include the capacity Cd of the diffuse layer adjacent to the thiol SAM. and hence the higher is the electrolyte concentration. |Z|. Total and Free Charge Density on Mercury Coated with Thiol SAMs One important parameter of alkanethiol monolayers is the charge involved in their self-assembly on electrodes. 11). These relatively hydrophilic molecules form SAMs that exhibit a high resistance comparable with that of n-alkanethiols. due to the presence of any traces of impurities capable of penetrating the film. C values of n-alkanethiol SAMs with nc from 8 to 18 also satisfy the Helmholtz formula with ε = 2. Fitting this dependence to the GC theory. In practice. the control of the impedance tends to pass to Rt . In this case the diffuse-layer capacity Cd can be estimated by making it comparable with Ct by the use of KCl concentrations c as low as 5 × 10−3 M. By covering a KCl concentration range from 5 × 10−3 to 0. of decane and the thickness d of the thiol film equal to the length of a space-filling model of the thiols in the most extended configuration. At very high frequencies the impedance of the capacitor becomes so low that the control of the impedance passes to the series resistor R . −j/(2πf Ct ) tends to become comparable to.1 M and regarding Ct as independent of the electrolyte concentration. in series with the Rt Ct mesh (inset 2 of Fig. oligopeptide molecules that terminate with a sulfhydryl group for anchoring to the metal [102].

11 layer. and 0. in the presence of adsorption with charge transfer.6 × 10−2 M (c). namely.27 (c). due to the surface excess of free electrons. 1/Cd .02 0. This quantity is called ‘‘total charge’’ by Frumkin [105] and will be denoted here by σM (E). and 0.1 to 105 Hz.3 SAMs on Hg Electrodes and Si Ct (2) 141 Cd RΩ 5 Rt Ct Rd 80 4 (1) RΩ Rt Log |Z| [Ω cm2] a b c d 3 0. At frequencies < 102 Hz all Bode plots coincide.14 M cm2 .1. as obtained at −1.04 Cd (σM = 0)–1 [cm2µF−1] 0. It should be distinguished from the ‘‘free charge’’ q(E).06 d 0 2 4 Log (f ) [Hz] Plots of log |Z| and of the phase angle versus log f for a thiolpeptide-coated mercury drop immersed in 5 × 10−3 M (a). the latter quantity can only be estimated on the basis of extrathermodynamic assumptions. 1. as calculated on the basis of the Gouy–Chapman (GC) theory. only the experimental points for the lower KCl concentration were reported. Rt = 0.1 M (d) KCl. which is actually experienced by the diffuse-layer ions. the charge density on the metal side of the interphase.87 K cm2 (d).000 V/SCE over the frequency range from 0. Inset 3 shows the reciprocal. 80 (c) and 84 µF cm−2 (d). 3. The solid curves are 1/Cd (σM ) versus 1/Cd (σM = 0) plots calculated from the GC theory for different charge densities σM on the metal.01 1 0 0 0. hence. 1. in series with an Rt Ct mesh representing the self-assembled thiol and a further Rd Cd mesh representing the diffuse Fig. Rd = 4.53 (a). In this connection it should be pointed out that the only thermodynamically significant charge in adsorption processes involving partial or total charge transfer between the adsorbate and the electrode is the charge to be supplied to the electrode to keep the applied potential E constant when the electrode surface is increased by unity and the composition of the bulk phases is kept constant. The solid curves are least-squares fits to the simple equivalent circuit of inset 2.17 (b).02 a b c 20 0. whose values are reported on each curve [102].03 [cm2 µF−1] 40 (3) –1 –2 –3 2 C −1 d 0. The method of choice to measure σM both on solid and liquid electrodes consists in starting with an uncoated electrode –Phase angle (°) 60 . Ct = 11 µF cm−2 . which consists of the electrolyte resistance R . of the experimental diffuse-layer capacitance versus the 1/Cd (σM = 0) value corresponding to the same KCl concentration. Cd = 68 (a). capacitive contribution.3 × 10−2 M (b). 61 (b). 4.

85 V/SCE. This is possible only on the basis of extrathermodynamic assumptions. thus allowing the estimation of the total charge density σM (E) at E. the changes in σM over this potential range lie within the limits of experimental accuracy. while the σM value on bare mercury at a potential just negative of the peak equals −16 µC cm−2 [16]. This yields a total charge density of +54 µC cm−2 over the range of stability of the C18 SAM. While the latter capacitive charge is very small. it can be identified with the charge density σM at E2 on a bare mercury electrode.2.3. which yields a σM value of ∼70 µC cm−2 . From a thermodynamic point of view.142 1 Preparation of Monolayer Modified Electrodes immersed in a solution of the supporting electrolyte alone and in stepping the applied potential from the pzc to a final potential Ef negative enough to exclude the adsorption of the adsorbate under investigation. yields a σM value of ∼ +56 µC cm−2 over the whole broad potential range of stability of the monolayer [16]. the former is not negligible. where they are sufficiently soluble. such as the oxidation adsorption prewave of cysteine (see Sect. An alternative procedure applicable to liquid electrodes consists in recording the charge accompanying the expansion of an HMDE immersed in a solution of the adsorbing surfactant at constant applied potential E. since it includes the difference between the capacitive charge at a potential E2 just negative of the desorption peak and that at a potential E1 just positive of it. where this SAM is completely desorbed at Ef = −1.2). This procedure is substantially identical with that based on the measurement of the maximum limiting height of dc polarographic adsorption waves. because of the very low differential capacity of the C18 monolayer. provided such a potential is experimentally accessible: the charge Q accompanying the potential step pzc → Ef is then just the common value. The charge accompanying a further potential step from any given initial potential E to Ef at an adsorbatecoated electrode in the same supporting electrolyte will be equal to σM (Ef ) − σM (E).1 M tetramethylammonium chloride. In the following. it will be shown that the capacitive contribution can be approximately identified with the free charge density q(E). In fact. . at potentials just negative of the desorption peak. thiol desorption is not complete. Application of this procedure to a C18 SAM on a mercury electrode immersed in aqueous 0. which is very small over the potential range of stability of n-alkanethiol SAMs.1 M tetramethylammonium chloride. The charge under the reductive desorption peak of n-alkanethiols is not a precise measure of σM . 1. of the total charge density both in the presence and in the absence of the adsorbate. In the case of a C18 SAM on a mercury electrode immersed in aqueous 0. As a first approximation. The resulting σM values range from 70 ± 10 to 80 ± 10 µC cm−2 . σM (Ef ). It can be applied only in the presence of surfactant concentrations high enough to ensure an almost instantaneous adsorption equilibrium during drop expansion. even though.3. This procedure was adopted to measure σM for monolayers of n-alkanethiols with 8 ≤ nc ≤ 18 [85]. These thiols were self-assembled on mercury from methanolic NaClO4 solutions.1. in excellent agreement with the value obtained by the more accurate potential-step chronocoulometric procedure (vide supra). it is impossible to separate σM into a capacitive and a faradaic contribution [106]. the charge under the desorption peak amounts to −70 µC cm−2 .

If this can be reasonably considered to be of the order of 15–20 µC cm−2 . A more significant estimate of the partial charge-transfer coefficient λ requires the absence of equilibrium between the surface compound due to charge transfer from the adsorbate to the metal. 84]. Since such dissolution involves total charge transfer. a total charge density of ∼ +80 µC cm−2 is obtained.20 nm2 [85]. and χt is the surface dipole potential of the thiol. Both charge values were not corrected for the capacitive contribution. In this case. experimental σM values close to ∼ +80 µC cm−2 point to a close-packed monolayer of perpendicularly oriented n-alkanethiol molecules resulting from total charge transfer from the sulfhydryl group to mercury.3. Thus. or for thiolates dissolved in strongly alkaline aqueous solutions [87]. and can be reduced only in acidic media [73. β is the distance of the center of charge of the sulfur atoms from the metal surface. σi is the charge density of the −S− groups of a hypothetical close-packed monolayer of thiolate ions.1. (18). 1.3 SAMs on Hg Electrodes and Si 143 The charge under the oxidation adsorption peaks of long-chain alkanethiolates from aqueous 0. Strongly alkaline aqueous solutions may also favor a modest solubility of mercury adducts. d is the whole length of the thiol molecule.1. Therefore. which is given . In these solutions the solubility of mercury adducts is not entirely negligible. The cross-sectional area of a linear hydrocarbon chain in close-packed monolayers of aliphatic compounds is estimated at ∼0. ε∞ is a dielectric constant accounting for distortional polarization.1). in both cases σM is close to 80 µC cm−2 . where the C18 coating shifts the onset of mercury oxidation to potentials positive of those observed on bare mercury in the same electrolyte.6 V versus a Ag/AgCl reference electrode [87]. This requirement is fulfilled. This value agrees with that estimated from GIXD and X-ray reflectivity measurements on n-alkanethiol SAMs on Hg [89] (see Sect. taking into account both the partial charge-transfer coefficient λ and the degree of dissociation α of the sulfhydryl groups as expressed by Eq. instead of favoring such an oxidation. as indicated by the formation of a massive deposit of mercury alkanethiolates from aqueous 0. for the transfer of one electron per n-alkanethiol molecule in the monolayer.5 M NaOH at potentials as negative as −0.3. such as methanol [85] and acetonitrile [84]. for example. the dissolution of mercury in organic solutions of thiols is significant. The (d/ε0 ε∞ )(σM + λσi ) term is the potential difference across the whole length of the thiol molecule created by the ‘‘free charge’’ on the metal. σM values close to +80 µC cm−2 are not surprising. These values are normally reported for monolayers that are directly self-assembled from thiol solutions in organic solvents. by C18 SAMs in aqueous solutions of pH less than the pKa = 12 of this thiol. and that under the reductive desorption peak of C10 from acetonitrile was found to be equal to ∼ −98 µC cm−2 [84]. the potential difference across the interphase can be approximately expressed as follows [16]: φ= d −β d (σM +λσi ) + [(1 − λ)σi ε0 ε∞ ε0 ε∞ d − (1 − α)σi ] + χt = (σM + ασi ) ε0 ε∞ β (α − λ)σi + χt (19) − ε0 ε∞ Here. and the corresponding compound in the bulk solution.2.5 M NaOH was reported to amount to ∼ +95 µC cm−2 [87].

(21). of the C18 SAM. as distinct from the C18 alkanethiol.7 to a good approximation. of length (d − β). Moreover.7 µFcm−2 . its dipole potential χt cannot be regarded as negligible.144 1 Preparation of Monolayer Modified Electrodes by the negative charge λσi transferred from the sulfur atoms to the metal.2. created by the charge density on the sulfhydryl groups. In the opposite limiting case of a unitary degree of dissociation. the charge density (σM + ασi ) is small. Thus. In this case the partial charge-transfer coefficient λ ≈ (q – σM )/σi is. After rearranging terms. In the limiting case of a zero degree of dissociation α. this charge density is negative and equal to (1 − λ)σi . In view of the considerations made in connection with Eq. In practice. therefore. 1. on the −S− groups of a hypothetical close-packed monolayer of C18 anions is about −80 µC cm−2 . Differentiating Eq. 11. since the absolute values of σM and ασi are much greater than their algebraic sum. the transfer of a negative charge density λσi to the metal leaves an equal and opposite positive charge density −λσi on the sulfur atoms. (9).3. thus allowing the free charge density q = σM + λσi experienced by the diffuse-layer ions to be estimated at −3 µC cm−2 from the GC theory [102] (see Sect. (19) with respect to σM under the assumption that the dipole potential χt and the partial charge-transfer coefficient λ ≈ α are not appreciably affected by a change in σM . |σM + ασi | turns out to be about 2 orders of magnitude smaller than |σi | [16]. we can set α ≈ −σM /σi = 0. plus the thermodynamically significant and experimentally accessible charge density σM .3. φ. In the case of the water-soluble thiolpeptide of Fig. since partial charge transfer and deprotonation of the sulfhydryl group are strictly correlated events. φ is more positive than the applied potential E measured versus the SCE by ∼ 250 mV. this is also an approximate estimate of the partial charge-transfer coefficient λ for C18 . while the total charge density σM measured at −1. The knowledge of q also allows an estimation of the dipole potential χt of the thiolpeptide through Eq. approximately equal to unity. Moreover.000 . Ct = 0. the charge density σi estimated on the assumption of a close-packed hexagonal array of thiolpeptide molecules is approximately equal to −20 µC cm−2 . However. the capacity C of thiolpeptide-coated Hg is high enough not to obliterate diffuse-layer effects. we can neglect the (β/ε0 ε∞ ) (α − λ)σi term with respect to the other. The [(d − β)/ε0 ε∞ ][(α − λ)σi ] term is the potential difference across the chain of the thiol. yields the following expression for the reciprocal of the differential capacity of the thiol monolayer: 1 d φ d = = dσM C ε0 ε∞ σM + ασi + χt C (20) Combining Eqs (19) and (20) yields: φ= (21) If we apply this equation to the C18 alkanethiol. (9)) and from the differential capacity.1. Taking into account that σM and |σi | are both much greater than |σM + ασi |. At −1.2). (see Eq. from the approximate extrathermodynamic estimate of the absolute potential difference across the mercury–aqueous solution interphase. (d/ε0 ε∞ ) (σM + ασi ).000 V/SCE by the potential-step procedure equals +17 µC cm−2 . the dipole potential χt of the n-alkyl chain can be regarded as negligible to a good approximation. σM equals +56 µC cm−2 (vide supra) and the charge density. σi . both because β is d and because α and λ are expected to assume close values.

(21).1). it is exclusively controlled by slow electron tunneling kinetics and depends upon the overpotential η according to the well-known relation i = F kap c∗. shows a reduction current across a C16 SAM.4 108. Substituting these numbers in Eq. Thus. φ is therefore equal to −0. another relatively hydrophilic thiol. Pb2+ . Even the electroinactive lipophilic ions TPhB− and TPhP+ are prevented from translocating across a C18 monolayer on Hg [86]. values of σM .5 M KCl was thoroughly investigated by Majda and coworkers [85. a χt value of about −470 mV is obtained. respectively. The β value amounts to 1. say with nc = 2. 110].14 ± 0. From Eq. here β is the decay constant per methylene group and i0 is regarded as the current density in the absence of the thiol monolayer.785 V/SCE [107]. and dielectric properties through a gradual tilting of the thiol chains. longchain thiols inhibit electron transfer the more the longer is their chain [82. Thus. the Ru(NH3 )6 3+ reduction current continues to be limited by slow electron tunneling kinetics.2. Electron Transfer across Thiol While short-chain SAMs on Mercury n-alkanethiol and ω-thiocarboxylic acid monolayers. 11 µF cm−2 and −3. density. which may reach up to 4% of that on bare mercury [82].3. thanks to their liquid-crystalline state at room temperature. nalkanethiols with nc > 14 fracture easily upon mercury drop expansion in excess of ∼5% [85. where c∗ is the bulk reactant concentration and α is the charge-transfer coefficient. affect the rate of electron transfer of redox couples such as Ru(NH3 )6 3+/2+ only slightly. a typical example of a metal ion/metal amalgam couple. This denotes a constancy in the dielectric constant of the SAM. C and q equal to +13 µC cm−2 . with o kap = kap exp(−αηF /RT ).1. n-alkanethiols whose transition temperature to the liquid-crystalline state is higher than room temperature block almost completely not only inorganic redox couples such as Ru(NH3 )6 3+/2+ and Fe(CN)6 3−/4− but also lipophilic couples such as UQ/ubiquinol-10 or viologens. 1. It is apparent that the current upon drop expansion increases with a decrease in film thickness much less than . were measured at −0. Moreover.1. Monolayers of n-alkanethiols with nc from 9 to 14 maintain their impermeability and dielectric properties upon slow stepwise expansion of the HMDE up to 30%. However.2. 86]. a partial charge-transfer coefficient λ of 0. where C equals 11 µF cm−2 [102]. which maintains its volume.3.09 [85].1.5 µC cm−2 . 1. Conversely. Thus. by keeping the drop expansion within the above limits. The reduction current density i of Ru(NH3 )6 3+ across SAMs of nalkanethiols with 8 ≤ nc ≤ 18 from aqueous 0. The current density measured at constant applied potential decreases exponentially with the length of the hydrocarbon chain. according to the relation i = i0 exp(−βnc ).2. Upon estimating σi at −70 µC cm−2 from a space-filling model of this thiol. This current density is much lower than its diffusion limiting value. (21) it follows that χt amounts to ∼ −200 mV [37].750 V. the differential capacity C per unit surface increases proportionally to the drop area during drop expansion. Using the same approach for an SAM of triethyleneoxythiol. as in the case of phospholipidcoated mercury (see Sect. 109].24 was determined.3. 84.3 SAMs on Hg Electrodes and Si 145 V/SCE. Figure 12 shows plots of ln i versus the film thickness at constant E both for different n-alkanethiols on an unexpanded drop and for C12 on a progressively expanded drop.

0 0 5 10 15 20 q [°] 25 30 35 40 –14 –15 –16 14 15 16 17 18 19 20 21 Monolayer thickness [Å] Fig. 12 Plots of the logarithm of the tunneling current density i versus the geometric monolayer thickness. the current i is therefore given by: i = i0 exp(−βtb d) + i0 nc exp[−βtb (d − dcc tan θ)] exp(−βts dcc ) (22) where βtb and βts are the throughbond and through-space decay constants. a pathway that does not change in length during monolayer expansion. For simplicity. predicted under the assumption that the monolayer behaves as an isotropic dielectric barrier in which electron tunneling efficiency is independent of its molecular structure [85]. the tunneling current i is regarded as consisting of a main contribution due to a whole ‘‘through σ -bonds’’ pathway along a single alkyl chain of length d. i0 exp(−βtb d).146 1 Preparation of Monolayer Modified Electrodes –10 A i [µA cm–2] 2. The modest current increase observed as the film thickness decreases following drop expansion is ascribed to lateral ‘‘hops’’ between adjacent alkyl chains. (22) to the data [85].8 1.65 V/SCE on an unexpanded HMDE coated with n-alkanethiol monolayers of different chain length (A) and on a progressively expanded HMDE coated with a C12 monolayer (B).6 1. where dcc is the contact distance between adjacent alkyl chains modeled as cylinders. . The solid curve is a least-squares fit of Eq. By ascribing to the latter pathway a probability equal to the number nc of carbon atoms in the n-alkanethiol chain. Data recorded at −0. From Figure 13(a) it is apparent that this lateral ‘‘through-space’’ hop decreases the length of the whole ‘‘through σ -bonds’’ pathway by an amount x = dcc tan θ. The inset refers to the data of curve B and shows a plot of i versus the tilt angle θ of the C12 chains.4 –11 –12 1. This provides the first direct evidence that electron tunneling proceeds primarily through the alkyl chains. and θ is the tilt angle. plus a minor contribution in which this pathway is modified by the inclusion of a single lateral ‘‘chain-to-chain’’ hop.0 1.2 Ln (i ) [A cm–2] –13 B 1.

13(b). On an unexpanded C16 -coated HMDE the reduction current i for both probes. To exclude the possibility that the small increase in the tunneling current following drop expansion might be ascribed to partial penetration of the redox probe into the n-alkanethiol monolayer. recorded at a scan rate high enough (>5 V s−1 ) to exclude partial diffusion control. increases with a negative shift in the overpotential η first exponentially. it should also cause a decrease in λ. 14 for the case of IrCl2− ). the reorganization energies λ of the IrCl6 2−/3− redox probe and of the more hydrophobic ferrocene derivative. A redox probe can partially permeate the alkane region of the monolayer [85. the chain-to-chain coupling is significantly weaker than the throughbonds coupling. which dominates in perpendicularly oriented monolayers. In addition to the through-bonds pathway. and Hd 2 (ε) is the electronic coupling. The attainment of a plateau 6 in the i versus −η plots requires extremely negative overpotentials (−eη > 2λ) and corresponds to Marcus’ inverted region for homogeneous electron-transfer reactions. while the plots of dkap /dη. where kap = i(η)/F c∗ is the apparent rate constant. As expected.05 A in excellent agreement with an estimate obtained by ab initio calculations [85]. . where ρ(metal) = {exp[(ε − εF )/kT ] + 1}−1 is the Fermi distribution density of electronic states in the metal.01 A−1 and ˚ −1 . ρ(ox) = (4πλkT )−1/2 exp[−(λ− eη)2 /4λkT ] is the distribution density in the redox probe according to Marcus. The chains exhibit a tilt adopted in response to monolayer expansion.91 ± 0.31 ± 0. Thus. no decrease in the electron-transfer rate can be observed with an increase in driving force. the i versus −η plots show an inflection point. q x q dcc dcc S S S Hg S (a) S S S S Hg (b) S S S Hg S Fitting this equation to the experimental i versus θ plot for the C12 SAM (inset of ˚ Fig. an additional pathway (marked by the densely dashed line) involves a chain-to-chain coupling. as shown schematically in Fig. 109]. because tunneling from the continuum of electronic states below the Fermi level εF is still possible for −eη > λ. (a) The monolayer is essentially pinhole free. 13 147 Schematic representation of two possible different structures adopted by an alkanethiol monolayer upon expansion of an HMDE. 12) yields βtb = 0. In fact.3 SAMs on Hg Electrodes and Si Fig. An expression for kap is obtained by integrating the expression ρ(metal)Hd 2 (ε)ρ(ox) over the electron energy levels ε. if partial penetration of a redox probe into an expanded monolayer causes a certain increase in tunneling current as a result of a shorter tunneling distance. (b) Hg drop expansion results in the formation of pinhole defects. A redox probe is located outside the monolayer/solution interface. are bell-shaped (see Fig. The latter value is βts = 1. FeCH2 N−(CH3 )3 2+/+ . but then tends to a plateau. were determined on both unexpanded and expanded mercury drops [109].1. When the role of electron donor is played by a metal.

0 i [A] 4 Overpotential 2 A 0 0. Assuming that the Fermi distribution is a step function and that Hd 2 (ε) is independent of η.148 1 Preparation of Monolayer Modified Electrodes × 10−7 × 10 –4 B 6 5 8 dkap/dh –1 –1 [cm s V ] 4 3 2 1 0 −0. Therefore. electrode surface area = 0. 14) yields λ values close to 1 eV for both redox probes [109]. in the case of the hydrophobic ferrocene probe. When carrying out analogous measurements on differently expanded C16 SAMs.2 −0. in good agreement with the predictions of the Marcus dielectric continuum model for an aqueous environment. due to mercury oxidation.0 −1. The inset Fig.5 [A] −1. which depends upon η only via the Gaussian function ρ(ox).8 E (SCE) [V] Current versus potential curve of C16 -coated mercury in aqueous 0.5 6 0.5 M KCl in the absence (A) and in the presence (B) of 1.4 −0.0 −0. dkap /dη takes the form (4π 2 / h)ρ(metal)Hd 2 ρ(ox).0246 cm2 .4 0. a chlorophyll molecule lacking the phytyl .12 V s−1 . 14 shows a plot of dkap /dη versus η for the reduction of IrCl6 2− under the same experimental conditions. This indicates that the λ value is invariant with the monolayer expansion and that no penetration of IrCl6 2− into the alkyl chains of the SAM takes place. Fitting this expression to the experimental dkap /dη versus η plots (inset of Fig. The solid curve corresponds to the Gaussian fit through the data [109].2 0. Conversely. the access of IrCl6 2− and FeCH2 N – (CH3 )3 2+ to the electrode surface is restricted to a plane outside the C16 unexpanded monolayer. even a small expansion (2%) of the C16 SAM results in a very large increase in current and a destruction of the monolayer. the maxima of the Gaussian dkap /dη versus η plots for the IrCl2− probe 6 lie at the same overpotential up to a maximum tilt of the alkyl chains of ∼20◦ . scan rate = 5.0 × 10−3 M IrCl6 2− . A film of chlorophyllide (Chlide).6 −0.

positioned vertically and coaxially one above the other. Junction experiments .5 V decreases exponentially with the length of the hydrocarbon chain.3 SAMs on Hg Electrodes and Si 149 chain.3 [113]. The potential of the Gaussian maximum was used to determine the reorganization energy λ for the Chlide electroreduction process. the photocurrent increases much less than observed by decreasing the alkanethiol chain length on a nonexpanded drop. Increasing the thickness of the alkanethiol SAM by increasing its chain length causes the photocurrent.1. while the use of two contacting thiol-coated HMDEs. the junction area can be estimated with sufficient accuracy.3 [114]. Illumination of Chlide causes the photoexcited molecule to take one electron from the metal. with n and m ≥ 9. When using two volumes of mercury in a glass tube.89 ± 0. to decay exponentially ˚ with a decay constant β as low as 0. the plot of the reciprocal of the differential capacity C of the film against its thickness d. according to the relation i = i0 exp(−βnc ). satisfies the Helmholtz formula. corrected for the reorganization energy. If the thickness of an alkanethiol monolayer is decreased by expanding the drop surface. in the bilayer junction results in an increase in the tunneling current. λ was found to decrease regularly with an increase in the thiol chain length.17 A−1 .1 [114]. where λ is greater for C14 than for C12 [112]. 114]. the dielectric constant ε of the junction was found to be 2. yielded an ε value of 2. Differentiating these photocurrents with respect to the applied potential and plotting the resulting derivatives against potential yields bell-shaped curves that can be fitted to a Gaussian.7 ± 0. Thus. they do not coalesce. Thanks to the liquid nature of mercury. they form a Hg−Hg junction consisting of two alkanethiol monolayers anchored to the surface of the two contacting mercury phases.0 ± 0. C = ε0 ε/d [113. the double dash denotes van der Waals interactions at the interface between terminal groups of the two SAMs. The decrease in the reorganization energy λ for Chlide electroreduction with an increase in the thiol chain length is tentatively explained by a concomitant decrease in the amount of water molecules incorporated in the thiol SAM [111]. in place of a methylene group. with formation of the Chlide− radical anion. was adsorbed on top of mercurysupported SAMs of n-alkanethiols of chain length from C12 to C18 [111]. This trend is opposite to that observed with chlorophyll molecules adsorbed on mercury-supported thiol SAMs [112]. thus confirming that electron transfer takes place primarily along a ‘‘through σ -bonds’’ pathway. equated to the sum of the lengths of two fully extended alkanethiol molecules in a perpendicular orientation with respect to the mercury surfaces. The reduction photocurrents following illumination of the Chlide film were measured over the potential range in which this photoexcitable molecule is electroinactive in the dark. here and in the following. with the decay constant β per methylene group equal to 0. 114]. which has no macroscopic surface roughness. As in the case of thiol-coated Hg electrodes. the tunneling current density measured at a voltage bias V = −1. The latter device allows the formation of both symmetric and asymmetric Hg−Cn //Cm −Hg bilayer junctions. When two volumes of mercury are separated by an alkanethiol film. This low β value is explained by a concomitant energy transfer. Insertion of an amide group −CONH−. with no chain intercalation at the resulting bilayer midplane [113. and hence in the electronic coupling. as distinct from solid electrodes. rather. and their action spectra were determined.

The potentials of the two electrodes are controlled independently with respect to a common reference electrode immersed in the solution. The lifetime of these Hg−SAM(1)//SAM(2)−Hg junctions is of the order of 100 s. the two metal electrodes) and unoccupied orbitals of the organic material separating them.5 V. This determines a potential drop through the TCNQ site. and their benzylic homologs. This situation is encountered when the Fermi level of the metal electrodes and the lowest unoccupied molecular orbital (LUMO) of the ‘‘molecular bridge’’ interposed between them are separated by a large energy gap. separating the electrodes.Hg ). in that the current flowing from Hg to Ag is about nine times higher than that flowing in the opposite direction.150 1 Preparation of Monolayer Modified Electrodes can be carried out over a wide range of voltages. When the SAM(2) tethered to the silver electrode is formed from a dialkyl disulfide with a covalently linked tetracyanoquinodimethane (TCNQ) group. 2. at 1 V magnitude bias [117]. with β approximately independent of the bias voltage V over the range from 0. immersing an HMDE into this solution so as to form a Hg−C16 SAM. ultimately leading to junction breakdown. the tunneling decay constant β decreases only slightly with an increase in voltage V . the through σ -bonds mode of electron tunneling is only scarcely affected by the external electric field. It consists of two HMDEs. HSCH2 (Ph)k H. Under certain . as shown by impedance spectroscopy measurements.1 to 1 V. An ‘‘electrochemical inclusion junction’’ has also been described [118. or greater. follows the relation i = i0 exp(−βdAg. tunneling mediated by interactions between donor and acceptor (in the present case. which is asymmetric with respect to bias. intercalation seems to proceed more rapidly for thicker junctions. thus. This time evolution involves chain disorder and chain–chain intercalation. SAM(2) was formed with alkanethiols from C8 to C16 . The current increases linearly with V at low V values. Apparently. and exponentially at high V values. HS(CH2 )10 CONHCH2 pyRu(NH3 )5 . while it is only in van der Waals contact with SAM(1). the Hg−C16 //SAM(2)−Ag rectifies current. namely. Hg−SAM(1)//SAM(2)−Ag junctions have also been prepared by forming a SAM on the surface of an evaporated film of silver. and are brought into contact in an aqueous solution. 3). dAg. Hg−C16 //C16 −Hg junctions are stable under voltages as large as ±2. it is covalently linked to the rest of SAM(2). This behavior is typical of electron transport by ‘‘superexchange tunneling’’. and bringing it into contact with the silver electrode with a micromanipulator [116]. 119]. This behavior is explained by the single TCNQ functional group having an energy different from the rest of the sites of the molecular bridge and a different site-coupling energy to its neighbors. thus. their structure evolves with time. HS(Ph)k H (k = 1. Owing to the van der Waals and coulombic forces squeezing the junctions. oligophenylene thiols. both of which support a SAM of the ruthenium pentamine pyridine-terminated thiol. The decrease in current density with increasing length of the molecules forming SAM(2). covering it with a solution of hexadecane containing C16 .Hg . and therefore with the distance. only with alkanethiols longer than C8 . and increases with their chain length [115]. However. by using a bipotentiostat. much less than predicted by the theory of electron tunneling between two metal plates across a square potential energy barrier.

the resulting RuII releases its electron to RuIII of the adjacent SAM. without the disturbing presence of stray currents due to defects. In fact. Tethered Bilayer Lipid Membranes on Hg The possibility of self-assembling bilayers covalently on metals with the formation of rugged functionalized electrodes has stimulated research aiming at exploiting self-assembly for the realization of biomembrane models capable of incorporating integral proteins in a functionally active state. integral proteins have a hydrophobic section buried inside the lipid leaflet of the biomembrane. so as to move both Fermi energies from above to below the electronic states of the RuII /RuIII couple. or a twostep hopping mechanism. and both potentials were shifted upwards.3 SAMs on Hg Electrodes and Si 151 conditions. with the maximum lying in the proximity of the RuII /RuIII redox potential. biomembrane models consisting of lipid bilayers (often referred to as tethered bilayer lipid membranes. This electron transfer takes place only when the electronic states of the RuII /RuIII couple fall between the Fermi energies of the two mercury electrodes. tBLMs) should meet a number of requirements: (1) they should be robust enough 1. To achieve this goal. via ion channels or ionophores. Moreover. which must therefore be sufficiently flexible to accommodate this section. Often. The mechanism responsible for this current is considered to be resonant tunneling. To avoid their denaturation and to promote their function. This has potential not only for fundamental research on protein functions but also for biosensor applications. an alkanethiol monolayer is first obtained by immersing the mercury drop for 1 or 2 minutes in a thiol solution in ethanol. Requirements (2) and (3) are necessary for the incorporation of integral proteins into the lipid bilayer in a functionally active state.1.1 V. the more negative electrode (the cathode) transfers an electron to RuIII of its own SAM. the plot of the resulting current against the potential of the anode is bell-shaped. The phospholipid monolayer on . Thanks to the high affinity of mercury for sulfur. with electrons actually populating the molecular bridge. the incorporation of integral proteins into biomembranes must ensure that their protruding hydrophilic sections are accommodated in a hydrophilic medium on both sides of the lipid bilayer.1. (2) they should be as flexible and fluid as lipid films in the liquidcrystalline state. is possible only if an aqueous layer is interposed between the bilayer and the electrode surface. Mixed alkanethiol–phospholipid bilayers on an HMDE are readily prepared by exploiting the hydrophobic interactions between the hydrocarbon tails of the alkanethiol and those of the phospholipid [64].4 for long-term stability. Requirement (4) is needed to make the biomembrane model sufficiently blocking as to characterize ion channel activity by electrochemical means. more positive electrode (the anode). In one experiment. and (4) they should be sufficiently free from pinholes and other defects that might provide preferential pathways for electron and ion transport across the lipid bilayer [120]. and be easily and reproducibly prepared. they also have hydrophilic sections protruding by over ˚ 60 A outside the lipid bilayer. which transfers it to the corresponding. (3) they should have water on both sides of the lipid bilayer. the potential difference between the two electrodes was kept constant at 0.3. the transport of hydrophilic ions across the lipid bilayer. with electrons localized somewhere in the molecular bridge for an appreciable time during electron transport.

107] and the channel-forming peptide melittin [107] decreases the resistance of the film. 121]. (21) it is apparent that. This disposition allows a free exchange of material between the thiolspacer-coated drop and the lipid reservoir on the surface of the aqueous electrolyte. incorporation of ionophores such as the ion carrier valinomycin [102. In these tBLMs. Subsequently. The differential capacity of the mixed bilayer so obtained agrees with the value calculated from the equation C = Ct Cp /(Ct + Cp ). In fact. under these conditions the charge density q = σM + ασi experienced by the diffuse-layer ions is zero. φ ≈ (E/SCE + 0. such as UQ and vitamin K1 [64]. thus denoting a very low number of pinholes and other surface defects. the transmembrane potential) can be estimated by noting that its zero value is practically attained at the applied potential E at which the absolute potential difference across the whole interphase. where Ct and Cp are the experimental values of the capacities of the thiol and phospholipid SAMs on mercury. with formation of a floating lipid bilayer on top of the hydrophilic thiolspacer. from Eq. the drop is brought into contact with a lipid film that has been previously spread on the surface of an aqueous electrolyte. The applied potential at which the transmembrane potential equals zero can also be approximately estimated by incorporating valinomycin in the lipid bilayer [37. Moreover. 9). this mercury-supported thiolspacer/(lipid bilayer) system exhibits a differential capacity close to that of solvent-free black lipid membranes. no hydrophilic layer is interposed between the bilayer and the electrode surface. Thus. The potential difference across the floating lipid bilayer on top of the thiolspacer SAM (i.152 1 Preparation of Monolayer Modified Electrodes top of the alkanethiol monolayer is then obtained by immersing the thiol-coated mercury drop in an aqueous solution on whose surface a phospholipid monolayer has been previously spread. it determines a typical minimum in the plot of the phase angle of the electrochemical impedance against the frequency over the frequency range that would be exclusively controlled by the capacity of the biomimetic membrane if the ionophore were absent. just as the electric field across the floating lipid bilayer. because the relative solubility of the thiolspacer in water causes the gradual dissolution of the film. Thanks to the defect-free surface of liquid mercury. taking care to keep the drop neck in contact with the lipid reservoir.e. Valinomycin is a K+ -selective ion carrier that may shuttle K+ ions across . allowing the ethanol to evaporate. The thiolspacer is self-assembled on an HMDE by keeping the mercury drop immersed in its ethanol solution for 30 minutes. In a first attempt to overcome these limitations. Complete immersion of the drop into the solution is to be avoided. the alkanethiol monolayer was replaced by a SAM of a hydrophilic ‘‘thiolspacer’’ consisting of a polyethyleneoxy [107] or an oligopeptide [102] chain terminated with a sulfhydryl group for anchoring to the mercury surface. thus excluding the space and water required for the proper folding of the extramembrane parts of integral proteins. The flexibility and fluidity of the chemisorbed alkanethiol monolayer in direct contact with the electrode is much less than that of BLMs. this makes these Hg-supported mixed bilayers unsuitable for ion transport mediated by ionophores and practically impermeable to lipophilic molecules of biological importance.250 V) (see Eq. is equal to the calculated value of χt . The thiolspacer-coated mercury drop is then extracted from the solution.

This consists of a hydrophylic spacer terminated with a sulfhydryl or disulfide group at one end. their use is rather uncomfortable. both in the absence and in the presence of the ion carrier valinomycin [30]. of the capacity of the RC mesh. thus increasing its conductivity. since the drop neck must be kept in contact with the lipid reservoir on the surface of the aqueous electrolyte during measurements. A particularly convenient thiolipid named DPTL consists of a tetraethyleneoxy chain covalently linked to a lipoic acid residue for anchoring to the metal at one end. Immersing the thiolipid-coated mercury drop into an aqueous electrolyte. The voltage-gated channel of melittin. the conductance decreases owing to saturation of the thiolspacer. and the conductance of the tBLM increases up to a limiting value. with the hydrocarbon tails turned toward the aqueous solution. This plot shows four partially fused semicircles (see Fig. while the ω value at the maximum of the semicircle measures the reciprocal of its time constant. which mimics the aqueous phase on the metal side of the bilayer. especially when reported in a ωZ versus ωZ plot (see Sect.1 M KCl are particularly rich in characteristic features. Each semicircle corresponds to a RC mesh.1). When q is positive. which can be straightforwardly fitted to an equivalent circuit consisting of four RC meshes in series. 15). The impedance spectra obtained upon incorporating valinomycin in this tBLM from its 1. incorporated in a tBLM prepared with a triethyleneoxythiol thiolspacer [107]. and covalently linked to the polar head of a phospholipid at the other end. and bound via ether linkages to two phytanyl chains at the other end (see its structure in Fig. 1. 121–123]. [124] for the preparation and characterization of tBLMs on gold. More convenient tBLMs are obtained if the HMDE is coated with a monolayer of a ‘‘thiolipid’’ [30. for anchoring to the mercury surface.2. on whose surface a lipid film has been previously spread. with the hydrocarbon tails of the two monolayers turned toward each other. causes a lipid monolayer to self-assemble on top of the thiolipid monolayer. the K+ ions are electrostatically repelled from the thiolspacer. 1/C.8 V. . A tBLM obtained by self-assembling a diphytanoylphosphatidylcholine monolayer on top of a DPTL-coated mercury electrode was investigated by impedance spectroscopy over a frequency range from 1 × 10−2 to 1 × 105 Hz and over a potential range of 0.1.2. the diameter of the semicircle measures the reciprocal. In spite of some satisfactory results obtained with lipid bilayers self-assembled on top of mercury-supported hydrophilic thiolspacers. K+ ions start penetrating into the thiolspacer. ultimately.3 SAMs on Hg Electrodes and Si 153 the bilayer. it can be demonstrated that the inflection point of the curve of the conductance against the applied potential E corresponds to a zero value of the transmembrane potential [37]. This procedure yields a lipid bilayer anchored to the mercury surface through the hydrophilic portion of the thiolipid. Under the simplifying assumption that the short-range interactions of K+ with the thiolspacer medium are comparable with those with the aqueous phase. 37. τ = RC. Tethering the thiolipid to the metal surface yields half a lipid bilayer. was found to open at a calculated transmembrane potential practically equal to that reported on a BLM. Shifting the applied potential to more negative values.3. 15). at still more negative potentials. The frequency increases in the direction of increasing ωZ . it has been used by Naumann et al.5 × 10−7 M solution in aqueous 0.

J. which provides a means of detecting and characterizing these dielectric slabs. J. which is interpreted by a model of the electrified interface [30]. This tBLM was also used to incorporate the channel-forming protein OmpF porin from its aqueous dispersion in detergent [123]. R. and the aqueous solution adjacent to the tBLM. 2. 29.154 1 Preparation of Monolayer Modified Electrodes o Hg s s o o o o o o o o o o o o o P o o + N 10 ωZ’ × 107 [Hz Ω] 6 2 2 4 6 ωZ’’ × 107 [Hz Ω] 8 Fig. M. on the basis of the potential dependence of their R and C values.41 V/SCE. 3. M. 45. Lecompte. 3439–3446. R. References 1. 19. I. Rev. The four RC meshes are ascribed to different portions of the tBLM. R. Soc. I. 15 are ascribed to the lipoic acid residue. Bach. M. Pagano.5 × 10−7 M valinomycin. Bottom: plot of ωZ versus ωZ for a tBLM in aqueous solution of 0. Biophys. 123. 4. 259–266. Miller. 6. Solution . 1973. Barnum. the tBLM is a heterogeneous system with a substructure in which the dielectric and conductance properties of the substructural elements are different. When proceeding in the direction of increasing ωZ . E. Colloid Interface Sci. 1976. Kolthoff. The analysis of the impedance spectra indicates that OmpF porin increases the conductivity of the tBLM over a narrow potential range straddling the zero value of the potential difference across the lipid bilayer moiety. recorded at −0. D. Miller. I. Miller. Bioeng. M. the lipid bilayer. Miller. Biochemistry 1980. 15 Top: structure of the DPTL thiolipid in contact with a diphytanoylphosphatidylcholine molecule. J. 3061–3065. 62. Montal. 119–175. 1969. 1940. R. the tetraethyleneoxy moiety. due to interfacial polarization at the substructural-element interfaces. 5. 126–137. I. C. the RC meshes in Fig. 250–260. Chem.1 M KCl and 1. I. Annu. F. In fact. Colloid Interface Sci. F. J. Colloid Interface Sci. 1988. The arrows relate the semicircles of the ωZ versus ωZ plot to the different substructural elements of the tBLM [30]. Am. 5. R. this gives rise to a dispersion of the impedance with frequency. Lecompte.

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and chemical stability. (b) Bridging hydrocarbon fixed by two C−Si bonds. Application for biochemical analysis has also been extensively pursued. such as Si(111)-(7 × 7) reserved in vacuum. Si surfaces covered with grafted organic moieties have been frequently reported to be robust against the practical environment and even in powerful reagents [6–9]. The single line composed of adsorbed molecules can be easily imagined as a material of molecular wires [11. This attempt is probably the leading edge in the development of intelligent biochips with integrated electronics for signal detection and processing.158 1 Preparation of Monolayer Modified Electrodes C H Si C-Si bond (a) (b) Fig. Hamers et al. as the C−Si bonds on the single-crystalline planes are electronically localized. The passivation and modification of electronic properties were conducted by Buriak on porous Si surfaces. Actually CH3 species on Si(111) remains undecomposed at 600 K in vacuum [5]. first found a chain reaction of styrene adsorption on a (2 × 1)-hydrogenterminated Si(100) wafer [17]. The dissociation energy of C−Si bond has been estimated to be >300 kJ mol−1 [4]. the covalently bonded species are anticipated to be immovable along the surface. It is certainly amazing that just one monolayer of organic fragments can nullify the harsh reactivity of the clean Si surface. Lopinski et al. on which the organic adsorbate was utilized for photolithography and photoluminescence [10]. Related to this. Figure 2 shows scanning tunneling spectroscopy (STM) images of a . More practically. reported fixation of single strand DNA by covalent linkage on Si and other semiconductors. notably larger than the adsorption heat of molecules on noble metals. 16]. 1 Schematic view of hydrocarbon adsorbates covalently bonded on Si(111) surface. Modification of electronic properties was frequently attempted [10–14]. and performed electrochemical detection of DNA hybridization [15. (a) Single-chain alkyl fixed by one C−Si bond. bond on the surface is important because it brings about advantageous properties such as thermal stability. Another category of prospective application is electronics by molecular chains. and the electronic properties of this ‘‘nanowire’’ were examined [19]. The robustness of organic-modified Si(111) frequently attracts interest application. 18]. into inertness in the atmosphere. low mobility along the surface.

Nature 2005. which directly influence the quality of surface. but the molecules nearest to the dangling bond remain prominent. (Figure 1 of P.6 V. have not been always well recognized. (b) At an intermediate bias of −1. On Si(111). molecules appear darker. presented a highly ordered adlayer terminating all Si atoms just by exposing clean Si(100)-(2 × 1) to gaseous cyclopentene (C5 H8 ) in UHV environment [22]. increasingly so at greater distances from DB1. DiLabio. the details of structure and composition of the organic adlayer.4 V. The dangling bonds on surfaces of Si and Ge are reactive with O2 and other components of air and would result in the deterioration of the whole surface. 2 Visualization of the electrostatic potential emanating from a point source for a styrene chain on H:Si(100). G. styrene chain formed on H:Si(100)-(2 × 1). L. it was demonstrated that even CH3− . that in which the stoichiometric full coverage is attained. complete rejection of dangling bonds should be achieved by appropriate reaction and handling conditions.. There are some typical cases in which every surface Si atom is actually terminated by one C−Si bond. At increased sample bias of −2. This phenomenon was explained on the basis of molecular-orbital calculation. in which the electronic orbitals in each styrene adsorbate are modified by the existence of a dangling bond located at one end of the chain. This sort of full-coverage adlayer can be expected only when the adsorbate is small enough to be contained within one (2 × 1) supercell. 658 [19]).1. (a) With negatively charged dangling bonds labeled DB1 and DB2. The discovery of H:Si(111)-(1 × 1). G. J. was an epoch-making event to open up the field of organic chemistry on semiconductors handled out of ultrahigh vacuum (UHV).8 V. causing molecules to appear bright (topographically elevated) and of nearly constant height across the line. Pitters et al. (c) In the absence of a negative dangling bond all molecules would appear dark at −1.3 SAMs on Hg Electrodes and Si 159 (a) (b) (c) Fig. Piva. on which every surface Si is monohydride terminated [20]. fills . Hamers et al. 435. namely. The prominent white bar is a line of surface-bound molecules. If the surface is supposed to be handled in air or in liquid. molecular p-states are ‘‘turned on’’. (2 × 1) adlattices can be formed by cycloaddition of cyclic olefins onto surface Si−Si dimers [21]. A. the smallest alkyl moiety. On clean Si(100). Figure 3 shows STM images of cyclopentene molecules bonded in parallel to the dimer rows of Si(100)-(2 × 1) terraces. The practical criterion that characterizes covalent adsorbates on semiconductor surfaces is that every dangling bond generated by the truncation of a single crystal should be terminated by an adsorbate. Despite those prospects of practical applications.

Long-chain alkyls and aromatics cannot be accommodated without such spacing species [25]. The structure of the anchoring part depends on the method of forming the C−Si bond. Even a C2 H5− group is slightly too bulky to be accommodated within Si(111)(1 × 1) unit cell. This sort of monolayer usually exhibits a good robustness and is as useful as fully terminated surfaces. R. 27]. This is a difficulty in obtaining ordered adlayers due to the lack of mobility along the surface. Attempts to make an adlayer with species bulkier than those typical adsorbates inevitably lead to formation of a mixed adlayer with small adsorbates that fill the spacing areas. One exceptional case. most of the organic moieties cannot make one-by-one termination of Si(111) in a macroscopic area [12]. Attachment of olefins modified with functional groups is more complicated as the functional groups may be more reactive with hydrogen-terminated Si . Phys. most of the space over a single-crystalline Si(111) surface when every surface Si is terminated by one CH3 group [24]. S553 [23]). light) or by catalysis. Appl. reported by Allongue et al. 66. Because steric hindrance is anticipated between adsorbates. Hovis. showing retention of molecular orientation across step edges. In such treatment. the adsorbates are arranged randomly [26]. one should consider not only the formation of isomeric adsorbates but also the reactions at unexpected portions in the reactant molecule. compared with the cases of small admolecules on noble-metal surfaces. Liu. S. On the basis of fundamental surface science on single crystals. (a) Cyclopentene adsorbed on ‘‘on-axis’’ Si(001). Hamers. such as terminating H. is a series of para-substituted phenyl groups grafted by electrolysis of precursor diazonium cations on hydrogen-terminated Si(111). n: integer). [7. The most frequently used method of organic deposition is called hydrosilylation.160 1 Preparation of Monolayer Modified Electrodes (a) Fig. which can be put in order by thermalization. OH. heat. On real adlayers. 3 (b) (c) High-resolution STM images of cyclopentene. such as designated (m × n) periodicity (m. Another microscopic structural issue to be tackled is the detailed bonding arrangement near the anchoring part. J. H. or silicon oxide. it is preferable to arrange organic adsorbates and spacing adsorbates in a well-ordered manner. (b) Clean surface of 4◦ -miscut Si(001) showing double-height steps. (Figure 3 of J. A 1998. (c) Cyclopentene adsorbed on 4◦ -miscut Si(001). Their STM images were explained to represent a (2 × 1) adlattice composed of phenyls and terminating hydrogen atoms arranged alternately. in which hydrogen-terminated Si surfaces are treated in terminally double-bonded olefins with a proper source of excitation (radical initiator.

we should assess the byproducts and contamination during the process of deposition as well as during the procedure of surface analysis. Most surface-sensitive analytical tools can usually present adequate information on contaminants with high fidelity. 1. 34]. Then. H:Si(100)-(2 × 1) is composed of surface Si−Si dimers with each Si terminated by one hydrogen atom. which often obscure the target adsorbates and bother surface analysis. Photoadsorption of 1amino-3-cyclopentene in liquid phase onto H:Si(100) seemed to deposit molecules linked to Si by C=C and those by NH2 [28]. For Si(111). Sulfuric acid-Peroxide Mixture. The technique of protected derivatives commonly used in organic synthesis was applied on Si(100) surface to deposit amino-terminated hydrocarbons [29]. Then the wafers are subjected to extensive oxidation in reagent mixtures such as H2 SO4 + H2 O2 (3:1. 90 ◦ C).2. We also have to be careful of the hydrocarbon contaminants in atmosphere. the wafers are sometimes pretreated in HF (a few percent) to remove irregular precovering oxide layer. and Buriak [35] are excellent. Wolkow [32].3 SAMs on Hg Electrodes and Si 161 than terminal C=C. The surface is strongly hydrophobic. HCl + H2 O2 (90 ◦ C. Oxidative reagents should be avoided in solutions. and microscopic perfection of H:Si(111)-(1 × 1) was well studied by various methods [36. etching in dilute HF or 40% aqueous solution of NH4 F at room temperature effectively removes the oxide layer to form ideal H:Si(111)-(1 × 1) [20]. To learn more about the development of this field. [33. and so on. It is a good idea to use two kinds of solvents. Spectroscopically useful D:Si(111)-(1 × 1) can be prepared by fluoride solution in D2 O [38. The signs of impurities should be carefully watched and quantified by proper methods of calibration under cross-checking with different techniques. In general. Oxidation of Si substrate cannot be avoided completely in treating H:Si(111) in aqueous/nonaqueous solvents in conventional sealed glassware. NH4 OH + H2 O2 (AmmoniumPeroxide Mixture. These surfaces can be prepared by atomic H treatment of clean Si(100)-(2 × 1) or heating in high-pressure hydrogen gas [42]. some topics on hydrogen-terminated Si(111) and chlorineterminated Si(111) that emerged in the last few years are introduced. [31]. HPM). 39]. The surface usually contains unterminated dangling bonds (neutral Si surface monoradicals).1.2 Handling of Si Specimens for Adsorbate Preparation and Surface Analysis Surface treatment of Si wafers as purchased usually starts with degreasing by sonication or rinsing in organic solvents. Bent et al. The produced surface can be kept clean in air for at least a few minutes. [30]. Due . Hydrochloric acid-Peroxide Mixture. which can hardly be eliminated by extensive hydrogen treatment [43]. For hydrogen-terminated Si(100). the procedures to handle Si wafer surfaces are briefly discussed in terms of deposition reaction and surface analysis. the review articles by Yates et al. which dissolve different kinds of organic debris. such as trichloroethylene and acetone. H:Si(100)(2 × 1) and H:Si(100)-(3 × 1) are well known [40]. The H:Si(100) (3 × 1) surface is composed of alternate rows of monohydride dimers and dihydride silicon atoms [41]. Wayner et al. diluted HNO3 + H2 O (1:1. SPM or ‘‘piranha’’ solution). The sacrifice oxide layer after treatment in such solutions is approximately 10-nm thick. 100 ◦ C.3. To obtain a homogeneous thickness of the oxide layer. 37]. In this article. APM).

2.3. The residual gas in the vacuum generated by oil rotary pump is water and oil. first hypothesized that the spacing species to accommodate alkyl chains on Si(111) is OH species according to X-ray photoelectron spectroscopy (XPS) observation [6]. clean evacuation from the atmospheric pressure to ∼10−4 Torr. By this procedure. Operation of a B–A gauge placed on a line of sight from the specimen should be avoided. Immersion of H:Si(111) in water without deaeration promotes oxidation of the surface [9]. It is difficult to perform liquid-phase reactions on H:Si(111) for an extended period of time in aqueous solutions unless some reducing reagents are added. electron sources sometimes deliver hydrocarbon contamination on Si.162 1 Preparation of Monolayer Modified Electrodes to such dangling bonds. H:Si(111) and organic-modified Si surfaces are resistive to air and can be passed between vacuum or purged containers through air. for evacuation from atmospheric pressure. just a short period of exposure to the atmosphere does not usually oxidize the surface to any detectable extent and the laboratory procedures can be done conveniently. or by using Lewis-acid catalysis. Introduction of the Si specimens into a vacuum chamber should be done carefully. However. Reactions in organic solvents are successfully performed in airtight glassware or glove boxes purged with inert gas. The origin of OH might be the peroxide radical initiator or O2 dissolved in the reaction fluid. contamination by hydrocarbons and oxidation can be reduced below the limit of spectroscopic detection. In UHV. After quick. 1. the surface cannot survive in the atmosphere [44]. Use of diluted olefins in an inert solvent (such as saturated alkanes) improves the quality of the alkyl adlayer [49]. such as liquid-nitrogen cooled sorption pump or helium cooled cryopump. Etching of Si(100) in fluoride solutions results in an inhomogeneous surface composed of partially (100)-(2 × 1) and (111) facets [45] and the surface is much less defined than H:Si(111)(1 × 1). UHV chambers and tubings are convenient for most heating and gas exposure treatments. The adlayer of long alkyl chains is robust and convenient to stabilize Si surfaces and to make modifications over the adsorbates. It is necessary to use an oil-free pump. Most . The process of adsorbate deposition should be carried out in a well-controlled environment.3. The largest chance of contamination is when the surface is in the stage of initial vacuum pumping. and the latter causes severe hydrocarbon contamination. first reported the fabrication methods of long alkyl chains (>10 carbons) [6].3. H:Si(111) and organic-modified Si are not positively contaminated within a short period. the vacuum container can be switched to a turbomolecular pump running at top speed. such as N2 or Ar. The deposition reaction was activated by the coexistence of a radical initiator in liquid phase [6]. The specimens should be rinsed and dried under a dry atmosphere after the reaction. UHV is ideal in storing the surfaces and is indispensable for handling clean Si surfaces of Si.1 Adsorption of Terminal Olefins on H:Si(111) Since 1995 when Linford et al.2. When the specimen is in the atmosphere. the reaction between H:Si(111) and terminally double-bonded olefins (1-alkenes) has been accepted as a practical method of organic deposition. Linford et al. by light irradiation [46–48]. by heating [6].3 Summary of the Latest Researches 1.

which is supposed to be oxygen attached to the adsorbates. [17]. [15] deposited amino-terminated decyl by a similar protection/deprotection method. Sieval reported aminoterminated alkyl grafted on hydrogenterminated Si(100) by a rather sophisticated amine protection/deprotection process to avoid direct reaction of NH2 and Si surface [50]. A complete alkyl adsorbate is then formed. Small portions of SiO2 deposited during the adsorption process are considered to be the nuclei of SiO2 island enlargement [7]. summarized the extent of substrate oxidation depending on the method of reaction activation [13]. Oxygen not incorporated in SiO2 at Si surface is often detected by XPS [25] or Auger electron spectroscopy (AES) [9]. The adsorbates are bulky and the substrate–adsorbate interface did not perhaps affect the function of DNA. A small extent of radical initiator. well-defined adlayer. (1) (2) (3) This process is actually visualized by Lopinski et al. In some cases the attachment of functional groups to Si surface can be avoided by the difference of reaction rates between the terminating double bond and the functional group [39. and furthermore grafted DNA on the amino group.) R−CH=CH2 + ·Si(surface) − − R−(CH·)−CH2 −Si(surface) −→ − − − − − − −→ R−(CH·)−CH2 −Si(surface) + H:Si(111)(surface) − − − − − − − − R−CH2 −CH2 −Si(surface) + ·Si(surface) functional groups. immediately picks up a neighborhood surface-terminating H. or hν H:Si(111)(surface) − − − − − − − − → −−−−−−−− · Si(surface) + ·H(This · H dissipates away. They could discern isolated dangling bonds (vacancies of hydrogen termination) and styrene . Strother et al.1. in which the best quality was attained by Grignard reaction on chlorinated Si substrate discussed in the next chapter. and the wetting and chemical properties of the whole adlayer usually seem not to be affected by the existence of oxygen adsorbate. This category of methods has been most utilized to form adsorbates including substrate oxidation was not inevitable. probably due to the treatment in aqueous solution for hydrolysis. 51].3 SAMs on Hg Electrodes and Si 163 of the succeeding researches using longchain alkenes lack in assessment of oxygen directly bonded on the Si surface. and the residual amount of surface oxygen is an index of the reproducible. The dangling bond (·Si) plays the role of chain carrier for the whole process. The long-chain alkyls may screen the adsorbates nearest the surface Si atoms. leaving one Si dangling bond. The C radical. who revealed the chain growth of styrene along the dimer row of H:Si(100)-(2 × 1) by STM. The mechanism of hydrosilylation has been elucidated as the ejection of a terminating hydrogen atom to form a Si dangling bond followed by an attack of the terminal double bond in olefin to form C−Si bond [6]. Adsorption of O can be due to accidental oxidation from the environment. or just H2 O molecules entangled in the adlayer. which is formulated as: . The leftover dangling bond again captures olefin. Webb et al. generated in the preadsorbate as a result of C−Si bond formation.

Yamada et al. and one end of the styrene chain is always accompanied by a dangling bond. and incorporation of surface-terminating D into alkyl adsorbate was evidenced by vibrational analysis [39]. [52] Recently. This causes the formation of bridge type adsorbates. presented a vibrational evidence that sec-type and n-type adsorbates from gaseous allylamine appear sequentially according to the increase of total coverage [39]. which the sec-type adsorbates nominally contain. Adsorption of styrene takes place on a site nearest to a dangling bond. Another possibility for future in-depth consideration is whether the alkyl chains.164 1 Preparation of Monolayer Modified Electrodes admolecules in UHV. was explained to proceed by the generation of surface Si cationic radical [13. such as shown in Fig. The adsorbates of sec-type were characterized by the vibrational modes of −CH3 group. the photoadsorption of allylamine (CH2 =CH−CH2 NH2 ) on D:Si(111)-(1 × 1) was performed. (a) Primary (n-type) adsorbate. The H N C Si (a) Fig. Recently. The primary type (n-type) is simple and usually accepted. while there had been no reason presented to reject the secondary type (sec-type). Figure 4 shows these two types of adsorbates for allylamine precursor. may be excited and subjected to bond formation with Si besides the reaction of double-bond end. which seems to be taken over immediately by adsorbate bonding. such as C2 H5 AlCl2 . which is ideal for impurity rejection and the succeeding surface analysis. The photoreaction was performed in an UHV setup. Lopinski et al. (b) secondary (sec-type) adsorbate. which are considered to be indifferent of H-terminated Si surface. Strictly speaking. the anchoring C−Si part of olefin-originated alkyls can be either of primary carbon or of secondary carbon. 53]. 4 (b) Schematic view of allylamine adsorbates anticipated on Si(111) surface. 1b. proposed a similar reaction mechanism on H:Si(111)(1 × 1). . The activation by Lewis-acid catalyst.

4 V.5 nm. −1 V (sample bias). and Si(111) was also subjected to Grignard reaction in the early stage. L89 [57]).5 × 6. The existence of a bridge type adsorbate on Si(111) has not been recognized widely so far but it will be interesting to find a concrete method of preparation and to exploit its characteristic macroscopic properties. 40 pA. which are commercially available.3. this work was pioneering in the use of alkylating reagents on Si surfaces. Surf. 57] reported well-ordered monolayers of Cl:Si(111)-(1 × 1) and Br:Si(111)-(1 × 1) examined by STM and high-resolution electron energy loss spectroscopy (HREELS) formed by (photo-)reaction in gaseous Cl2 or Br2 on H:Si(111).3. 50 pA. G. Sci. . Br.5 nm. Eves. 5 STM constant current images of halogenated Si(111) prepared by gas phase reactions at room temperature. the formation (a) (b) (c) Fig.2. The mechanism is simply formulated as: RMgX + Cl:Si(111) − − −→ R:Si(111) + MgXCl (4) Grignard reagents are delivered as solutions in diethylether or tetrahydrofuran (THF). 579. 1. Recently Rivillon et al. (b) Cl/Si(111)-6. 59] applied an outstanding method of surface infrared spectroscopy and detected Cl−Si vibration signals. Despite imperfect impurity rejection and surface analysis. The precursor halogenated Si surfaces had not been put into detailed investigation until recently. [56. [54. indicating that the original methyl end in 1-butene was destroyed [39]. 2005.1.5 × 6. P.2 Grignard Reaction on Halogenated Si(111) The formation of C−Si bond by Grignard reagents (Cm Hn MgX. As one of the most attractive topics in the field of Si surface science. 400 pA. Lopinski. X=Cl. J. Bansal et al. [58. The surface was composed almost solely of monohalide Si atoms. even better than hydrogen-terminated Si(111) (Fig.3 SAMs on Hg Electrodes and Si 165 photoadsorption of 1-butene on H:Si(111) did not yield CH3 vibrational signals. The halogenated surfaces were atomically flat with low defect density. Cl:Si(111) and Br:Si(111) slowly react with components of air and should be handled in vacuum or in inert gas. 55] chlorinated H:Si(111) in a benzene solution of PCl5 under coexistence of radical initiator and then immersed the chlorinated surface in alkyl–Li solution or alkyl–MgX solution. I) has been widely used in organosilicon synthesis. Removal of surface Si atoms as gaseous Si halides is considered to be involved in flattening the modified surfaces. −0. (a) Cl/Si(111)-50 × 50 nm. 5). Lopinski et al.5 V. (Figure 2 of B. (c) Br/Si(111)-6. −0.

sensitively detected by HREELS. 19. [24. gap voltage = −1. [55] listed the results for CH3 and longer alkyls and assumed that CH3 can terminate every surface Si atom on Si(111) on the basis of geometrical consideration. 10660 [24]).48 V. the rotation about the C−Si axis vertical to the surface is attractive. Figure 6 shows the flatness of the methylated surface viewed in a wide zone. The features actually represent the electron orbitals. The amount of SiO2 impurity. Bansal et al. (a) (b) (c) (a) A wide-range STM image of methylated Si(111). indicating all the characteristic vibration modes including the C−Si stretching motion. Kawai. A concrete evidence for methyl (1 × 1) termination was presented by Yamada et al. 6 high-resolution STM image. Chem. Scan size = 500 nm × 500 nm. examined a methylterminated Si(111) from Cl:Si(111) and CH3 Li by X-ray photoelectron diffraction and spectroscopy aided by synchrotron radiation [60].38 nA. and it is difficult to extrude the geometric arrangement of H atoms in CH3 just by viewing the images. preset tunneling current = 2. However. Yu et al. 61] as high-resolution STM images. J.. performed STM imaging of CH3 :Si(111)-(1 × 1) at the low temperature of 4. They concluded that the length of C−Si bond vertical to the surface is 0. A.5 cm−1 . Phys. . Yamada. [13] also extensively compared the perfection of alkyl adlayers prepared by various methods. 10 nm × 10 nm. The energy barrier of rotation excitation may be analogous to that of torsion of C−Si bond in an isolated CH3 −SiH3 molecule. (b) A Fig. (c) 4 nm × 4 nm.166 1 Preparation of Monolayer Modified Electrodes and structure of methyl-terminated Si(111) by Grignard reaction has been studied in detail. (Figures 3 and 4 of T.1%.51 V. −1. 2.7 K [62].65 nA.21 V (sample negative). 7). was controlled below 0. HREELS of CH3 :Si(111)-(1 × 1) was also presented (Fig. as well as the lattice of methyl moieties arranged in (1 × 1) periodicity. In terms of the movement of adsorbed CH3 group. M. which corresponds to a frequency of 590. Terry et al.186 nm.58 nA. 2004. −1. Webb et al. The features representing methyl groups changed according to the STM gap voltage. 121. They claimed that the rotation of every CH3 group was locked at a position of C−H bonds rotated by (7 ± 3)◦ away from the center of the neighboring −CH3 group. Wawro et al. so far no methods have been found to observe this rotation collectively. The CH3− group is probably the only hydrocarbon species that can terminate Si(111) in (1 × 1) periodicity with practical stability.

Niwa et al. 507 cm−1 : C−Si bending. the space filling of adsorbates does not geometrically allow every Si atom to be terminated. 121. This peak corresponds to the electronic state that contributes to electronic conduction through the surface. A. CH3 :Si(111)(1 × 1) was also applied as the ultrathin channel medium of field-effect transistor [14]. J. This conducting property is also materialized in an electrolytic phenomenon. M. 10660 [24]). 7 HREELS of the methylated Si(111). Kawai. Chem. It is interesting to address the electronic property of CH3 :Si(111)-(1 × 1) not only for the purpose of application as the lithography resist layer but also as the basis of nanoelectronic devices. 1099 cm−1 : Si−O stretching in SiO2 .3 SAMs on Hg Electrodes and Si 106 167 683 Counts [cps] 507 789 1268 1099 1423 2944 x2000 0 0 500 1000 x50 1500 2000 2500 3000 3500 4000 Wavenumber [cm−1] Fig. The I–V characteristic curve of STM reached a peak at −1.84 eV. 1423 cm−1 : CH3 umbrella motion. Phys. Yamada. 789 cm−1 : CH3 rocking.. incident angle = exit angle = 60◦ from the surface normal. (Figure 2 of T. and a certain part of terminating Cl atoms must be left over in the space between alkyl adsorbates. As for Grignard reagents containing alkyl groups larger than methyl. 2944 cm−1 : C−H stretching.5 eV in the occupied levels additionally to the I–V curve of H:Si(111). 2004.6 meV.1. 1268 cm−1 : CH3 asymmetric bending. Such Cl atoms are considered to be replaced by oxygen-containing species during rinsing or by exposure . Wawro et al. The full width at half maximum of inelastic peak = 7. HREELS incident electron energy 2. [61] demonstrated that CH3 :Si(111)(1 × 1) as an electrode in an aqueous redox solution exclusively lowers the peak potential of redox reaction. 683 cm−1 : C−Si stretching.

68]. On flat H:Si(111). The robust properties of this surface were found to be the same as those formed by alkene photoadsorption or by Lewis-acid catalysis. The formation of Si−R and Si−MgX was assumed. The H−Si stretching signal at 2090 cm−1 became invisible to IR as the coverage of organic increased [26].3. This issue is discussed in the next chapter. Boukherroub et al. concluded that a new mechanism of Grignard reagent should be proposed to replace terminating H [64]. that 100% methylated surfaces were obtained [67. Infrared spectroscopy seems to be more affected by adsorbate screening effects than HREELS. which was advantageous in the detection of surface products. the H−Si signal was apparently detected on surfaces prepared under the same condition.3. Replacement of terminating H with decyl groups was recognized. incorporation of Siterminating D species was detected. rinsing in a THF solution of CF3 COOD did not introduce D−Si [65]. However with HREELS. The possible terminating species was anticipated to be hydrogen. Grignard Reagents and H:Si(111) H:Si(111) is less likely than Cl:Si(111) to react with alkylmagnesium reagents according to the classic formulation of Grignard reaction. Careful use of D:Si(111) and HREEL showed C−Si stretching signal at 678 cm−1 [5].168 1 Preparation of Monolayer Modified Electrodes to air. . However. [5]. This interpretation fitted with a rather rough surface of porous Si. The formation of C−Si bond in methyl Grignard reaction on H:Si(111) was first evidenced by Yamada et al.3 of pit formation related to the backbond breakage.2. many cases of adsorbate formation on hydrogenterminated Si surfaces have been reported. indicating that Grignard reaction cannot completely remove original terminating hydrogen atoms. Kim et al. explained this process by dissociative insertion of R−MgX into Si−Si bonds just below the surface (called backbonds). and the Si−MgX species was considered to be quenched in Si−D by the presence of deutrated acetic acid. Formation of decyl (C10 H21− ) adsorbates by decyl Grignard reagent on H:Si(111) was first performed by Boukherroub et al. At the same time. It is certainly easier to replace a part of the terminating hydrogen atoms on H:Si(111) by alkyl groups. reported that highresolution XPS did not detect Cl after deposition of C2 H5− or C6 H5− CH2− on Cl:Si(111) rinsed in methanol [25]. Webb et al. The replacement of residual Cl species is probably uncontrollable and introduces more chances of contamination. so far.[5] This fact influences the interpretation of spectra of CH3 :Si(111) formed by electrochemical anodization in a Grignard reagent solution. By using CH3 COOD. [63] first reported derivatization of hydrogen-terminated porous silicon by Grignard reagents. The STM images of CH3 MgBr-treated H:Si(111) showed that methyl groups just formed small lattice patches and adsorbates were randomly placed with a significant open area [66]. They included a quenching procedure with acetic acid after the Grignard reaction. [64] The atomic force microscope (AFM) images of alkyl-terminated Si(111) show a flat Si surface without any sign 1. Kim et al. The HREEL spectra always contain H(D)–Si stretching signal. a limitation was recognized in detecting organic adsorbates and terminating hydrogen by infrared spectroscopy.

1997. by using n-type and p-type silicon. Piva. indicating that the adsorbate-wise areal density is constant. L. D. Niwa. 2003.1. 19. W. G. Eisenberger et al. B14. Phys. J. Homma et al. Yamada et al. Strother. K. and Si. Demirel. M. Decyl bromide intentionally added in a diethylether solution of decyl magnesium bromide significantly accelerated deposition of decyl groups. D. B 2003. T. Lett. 658. Yamada et al. Y. Nakagiri et al. K. 2000.. G. 106. J. G. A.. van der Weide et al. 123. Lett. S. Electroanal. Yamada. DiLabio. P. Kawai. Sugimura. N. The mechanism of H:Si(111) replacement by Grignard reagent has not been elucidated on the basis of concrete experimental evidences. Kato. 1995. The chance of unwanted substrate oxidation during the fabrication process can be minimized. J. 1990. Sieval. Phys. 129. T. 125. Lopinski. or even in a Cu-plating solution containing F− for a short period [9]. J. Homma et al. N.3 SAMs on Hg Electrodes and Si 169 The Grignard reaction on H:Si(111) is probably the most useful method to obtain robust Si surfaces for practical purposes. G. The alkylhydrogen mixed adlayers are strongly hydrophobic and resistive toward dissolved oxygen in water [9]. Fedorov. 65]. Chem. P. J. Technol. 16. J. Chem. RMgX. Yamada. Appl. T. 4085. W. More varieties of hydrocarbons. P. Lewis. Huisman. J. Z. M. W. B101. Biosens. G. 2004. K. Whelan. Webb.. can be deposited with adequate stability. de Villeneuve. 9. Soc. the hydrocarbon groups are transferred to the Si surfaces within the precursor Grignard reagents without isomerization and component detachment. 2. B. A. J. G. Fenter. A. 127. 2001. M. we can expect the application of alkyl halides as the alkylation reagent to open a new route to organic deposition on Si. J. H. such as branched or unsaturated hydrocarbon moieties [26.. M. B 2004.. Nature 2005. Chem. Sci. 12. 3535. J. Soc. Hirao. 48. 2005. 1996. B. M. Y. 4. Technol. Hofer. 2002. C. and by considering the electronic and thermodynamic energy levels of RX. Acid Res. 11. H. P.. J. M. J. In nearly all the cases. 532. A. Takano. 15. Buriak. . Phys. Pinson.. Soc. 2005. 117. M. 520. W. Phys. Chem. 2415. Smith.. Lopinski et al. Chem. 6. 7057. Am. 15030. Phys. 8039. G. J. 34. Treatment of H:Si(111) in pure tetradecyl bromide yielded a finite amount of alkyl adsorbate and a significant amount of SiO2 . Chem. Nucl. 1013. Chem. 107. B 2003. 108. Lett. 3240. Fisher. The adlayers formed are constantly a mixture of alkyl and H regardless of the chain length. Craighead et al. 39. 19. Chabal G. C. 14. A. Inoue. 7. D. 435. L. Sieval. Recently Fellah et al. 4140. D. J. References 1.. H. J. alkali solutions [64].. 5. 6846. 365. Bernard et al. It was difficult to compare the reaction kinetics with the Grignard reagent. 2002. J. 5404. T. Stewart. A. Lercel. K. T. Lie. W. 56.. Wolkow. 107. 656. Phys. Vac. Wayner. 1996. C. H. Higashi. Sci. S. Pitters et al. Langmuir 1998. 8.. D. Chem. Sch¨ 1necker o et al.. The C signals of AES [26] and XPS [55] indicating the saturation coverages are proportional to the chain length. 20. Okiguchi. J. M. Cai. D. compared to the case for Cl:Si(111). Chem. 10. L. L. N. proposed a mechanism involving a trace amount of alkyl halide residue contained in the Grignard reagent solution [69]. Chem. M. Am. Am. 28. M. Hossain. S. 7821. Although this analysis was not completed. 1759. B14. Yamada. 17. J. Linford. S. Fukunaga.. Vac. 13. R. Niwa. The effects of alkyl halide were scrutinized by voltammetric electrolysis of Grignard reagent. A 2002. J. R. Chem. 406. R. C. regardless of the chain length. Peck. Soc. H. Trucks et al. L. Nissink et al. 3145. T. 18. W. J. Bioelectron. 247. P. 3. J. Nature 2000. Hamers. A. J. P. R. Phys. Chem. 14. Am.

Heij et al. Yamada et al. A. Chem. Surf. Prog. 2583. T. I. 2002. 454–456. Fid´ lis. R. Yu. Rev. J. Electrochim.. Doak. Appl. Lauermann et al. Feltz et al. 2004. C. H. Lett. L. Asanuma. Niwa. Sakurai. 1996. 305. B. Soc. 444. Filler. X. Appl. Kim. L7. R. 18. Bent. Terry. Phys. 109. J. Yamada. Y. Bent. Phys. Jpn. J. B 2006. 6740. J. G. 22. 40. 45. S. Surf. 52. 16. 1998. Takano. de Smet. R.. S. R. Annu. Zuilhof et al. Chem. M. Am. Lett. 4845. Linke. Chem. 7357. 2002. B. Ozanam. Phys. 37. E. 2002. J. Phys. Jpn. 177. L. J. Baluch. 788. Soc. Sci. L. J. J. Lee et al.. 26. Phys. Lin. E.. F. 46. M. 120. 38. Hovis. Hessel. Li. 41. 2003. 109. 56.-H. Liu. R. 67. S. Lett. P. Lopinski et al. 1589. J. 57. T. H. Cai et al. Chem. J. Chem. R. 1339. 2000. 1990.. Li. 29. Sieval. F. Surf. 8288. S. I. 1991. J. Webb. 55. M. Morin. 2001. Heike et al. 1999. K. Chem. 69. Sieval. Lopinski.-N. 4516. S. 110.. Hamers. Int. Hashizume. 63. J. Rev. Chabal. Higashi. M. Soc. 40. Linford.. Lopinski. Electron Spectrosc. 1489. 1997. R. Higashi et al. Hamers. T. Langmuir 1999. 66. Appl. A. L. Jpn.. C. 30. Phys. Surf. Phys. R. 1997. Z. Appl. L. L361. de Smet. G. T. Allen. S. 203. 31. P. Langmuir 2004. Langmuir 2002. R. C. 3930.. 1998. M.-P. Yi et al. and 28. 73. Chazalviel. 2000. J. 33. S. G. K. Noto. J. J.. Sieval.. L. J. Chabal et al. A 1998. R. 34. J. Am.. Phys.. Hul’ko et al. 50. Acta 2000. Phys. Angew. 879. R. 58. S. Strother. 2004. Chabal. Sci. 1998. L1350. Sun. 125308. 2003. Sci. Cicero. B 1997. Yamada et al. A. M. B 105. R. Chabal. Chem. Sci. M. C. J. F... T. N. Heij et al.. G. Rev. 49. H. Hitosugi et al. 17. A. J. S. F.. Sci. 42. M. Eves. S. van Lagen et al. 53. R. B 2006. 18. Hamers. C. 67. T. Acc. 23. H. Soc. 66. 15. A. Bansal. C. Chidsey. R. H. 1271. J. van Lagen et al. 64. T. 62. T. 7225. J. 526. E. B. V. P. A 23. G. D. Surf. 284. 33.-Y.. 2001. 45. H. Rivillon Y. Allongue. Wayner. R. S. B. Appl. 1056. Langmuir 2002. S. J. Phenom. Inoue. U. 110. 3. Commun. Langmuir 2001. Boukherroub. 68. F. Yates Jr. 1352.. Rivillon. 413. J. Chen.-S. A. S. Y. Sci. J. Sci. 5013. M. 58. 48.-Z. J. 50. B. A. Chidsey. Technol. Soc. 2005. A 2004. S. K. Linke. Chem. L8. Chem. N. A. Surf. Y. B 71.. 2000. Takano. D. J.. Shimada. Buriak. Q. Appl. Am. Ed. Shirasaka. 95. 121. P. Chem. 85. Bensebaa et al. Wawro et al. M. Q. J. J. Sun. Sci. 2. 500. Wolkow. C. Thirstrup. S. Miyadera. Ozanam et al. Boukherroub. 61. P. Nakayama et al. P.. Buriak. 1993. J. 17.-Y. 127. S. Coulter.. 617. Fukunaga et al. Yamada. 35. O. 291. 411. Chem. e Sci. Chem. Phys. 2004. E. Heike. Hovis. H. M. Surf. 1. 2005. Lin. 71. 36. 39. Vac. . Pinson. Lett. R. X. 22. 7554. G.. Ellison et al. 33. F. G. 3831. S. Phys. Technol. 32. Hitosugi. P. 65. 60. 24. M. de Villeneuve. R. N. 1997. 2005. Electrochem. T. 37. 1656. Phys. G. H. K. Biteen et al. Webb et al. Phys. Kawai. E. 47. Phys. Wolkow. B. P. Amy. S. N. B 2005.. T. Appl. L. Chidsey. A. A. Rev. 27. J. 25. A. 15. 671. 102. L89. A. 579. C. Phys. Guisinger. 2005.. 54. 2514.. Chem. Phys. Bansal. B. 10266. Langmuir 2001. J. 44. 20. J. Yamada. Chem. 23. J.. T. Yamada.. N. J. D. 1998. A. D. Luo. Phys. Neuwald.. D. J. Yamada. 5688. 2001. Eves. J. 101. Y. 21. Fellah. H. Koma. Basu et al. H.. D. Chem. R. Waltenburg. W. 10660. 72. Langmuir 2005. 196. Cicero. J. Langmuir 1999. 43. 118. Laibinis. 54. E. 3241. Yu. J. Surf. Linford. M. Res. 59. D. D. Perkin Trans. Chem. T. Chem. Vac. L1. 1995.. Sci. 2004. 6359.170 1 Preparation of Monolayer Modified Electrodes 21. Lopinski. P. Webb. T. Nemanick. 296. B. J. K. Noto et al. Am. M. Ries et al. Wigren et al.. Becker. H. J. 7554–7559. J. S553. Shirasaka et al. Lett. S. 477. 120. T. Langmuir 2000. Appl. Chem.. B 2005. Vleeming. 43. J. 36. 1100. Relat. Kajiyama. 51.

One is a linear alkyl chain terminating one surface Si atom. The existence of the C−Si bond on the surface is important because it brings about advantageous properties such as thermal stability.1 practically. and industrial technology [1–3]. Modification of electronic properties was frequently attempted [10–14]. chemistry. Another category of prospective application is electronics by molecular chains.Edited by A. Stratmann Vol. such as Si(111)-(7 × 7) reserved in vacuum. Si surfaces covered with grafted organic moieties have been frequently reported to be robust against the practical environment and even in powerful reagents [6–9].2 Modification of Silicon Wafer Surfaces with Small Organic Moieties Taro Yamada RIKEN. 16]. The other is a hydrocarbon moiety fixed by two C−Si bonds. I. and performed electrochemical detection of DNA hybridization [15.F. The passivation and modification of electronic properties were conducted by Buriak on porous Si surfaces. Bard and M.Rubinstein. Actually CH3 species on Si(111) remains undecomposed at 600 K in vacuum [5]. Lopinski et al.J. first found a chain reaction of styrene adsorption on a (2 × 1)-hydrogenterminated Si(100) wafer [17]. notably larger than the adsorption heat of molecules on noble metals. This article deals with a category of organic adsorbates that is attached to the outermost surface Si by the C−Si covalent bond.1. Figure 1 illustrates two typical examples of hydrocarbon moieties attached directly to surface Si. The dissociation energy of C−Si bond has been estimated to be >300 kJ mol−1 [4]. Related to this.2. This phenomenon was Encyclopedia of Electrochemistry. The robustness of organic-modified Si(111) frequently attracts interest application.Rusling Copyright  2007 Wiley-VCH Verlag GmbH & Co.3. The single line composed of adsorbed molecules can be easily imagined as a material of molecular wires [11. More 1. low mobility along the surface. Application for biochemical analysis has also been extensively pursued. on which the organic adsorbate was utilized for photolithography and photoluminescence [10].3 SAMs on Hg Electrodes and Si 157 1. Edited by M. and chemical stability. The covalent linkage in organic adsorbates can mediate the connection of a variety of molecular groups with surface Si atoms. biology. Figure 2 shows scanning tunneling spectroscopy (STM) images of a styrene chain formed on H:Si(100)-(2 × 1). The diversity of organic species can guarantee almost limitless possibilities for molecules and moieties attached to Si surface. 10 Modified Electrodes.3. KGaA. into inertness in the atmosphere. 2-1 Hirosawa. and J. Saitama 351-0198. as the C−Si bonds on the single-crystalline planes are electronically localized. Weinheim. Wako-shi. 18]. Japan Introduction Monolayers of organic adsorbates bonded on silicon wafer surfaces have properties for prospective applications in nanometerscale physical science. and the electronic properties of this ‘‘nanowire’’ were examined [19]. the covalently bonded species are anticipated to be immovable along the surface.ISBN: 978-3-527-30402-8 . reported fixation of single strand DNA by covalent linkage on Si and other semiconductors. Hamers et al. in which the electronic orbitals in each styrene adsorbate are modified by the existence of a dangling bond located at one end of the chain. This attempt is probably the leading edge in the development of intelligent biochips with integrated electronics for signal detection and processing.Fujihira. It is certainly amazing that just one monolayer of organic fragments can nullify the harsh reactivity of the clean Si surface.

The prominent white bar is a line of surface-bound molecules.8 V. The practical criterion that characterizes covalent adsorbates on semiconductor surfaces is that every dangling bond generated by the truncation of a single crystal should be terminated by an adsorbate. The . causing molecules to appear bright (topographically elevated) and of nearly constant height across the line. G. but the molecules nearest to the dangling bond remain prominent. Despite those prospects of practical applications. molecular p-states are ‘‘turned on’’. molecules appear darker. 1 (b) Schematic view of hydrocarbon adsorbates covalently bonded on Si(111) surface. (a) Single-chain alkyl fixed by one C−Si bond. have not been always well recognized. (b) At an intermediate bias of −1. 435. (Figure 1 of P. At increased sample bias of −2. Nature 2005. Pitters et al.. (a) Fig. which directly influence the quality of surface. explained on the basis of molecular-orbital calculation.4 V. G. Piva. (a) With negatively charged dangling bonds labeled DB1 and DB2. 658 [19]). DiLabio.6 V.158 1 Preparation of Monolayer Modified Electrodes C H Si C-Si bond (a) Fig. L. 2 (b) (c) Visualization of the electrostatic potential emanating from a point source for a styrene chain on H:Si(100). (c) In the absence of a negative dangling bond all molecules would appear dark at −1. (b) Bridging hydrocarbon fixed by two C−Si bonds. increasingly so at greater distances from DB1. J. A. the details of structure and composition of the organic adlayer.

showing retention of molecular orientation across step edges. This sort of full-coverage adlayer can be expected only when the adsorbate is small enough to be contained within one (2 × 1) supercell. 3 . S553 [23]). most of the organic moieties cannot make one-by-one termination of Si(111) in a macroscopic area [12]. On clean Si(100). A 1998. Long-chain alkyls and aromatics cannot be accommodated without such spacing species [25].3 SAMs on Hg Electrodes and Si 159 dangling bonds on surfaces of Si and Ge are reactive with O2 and other components of air and would result in the deterioration of the whole surface. Figure 3 shows STM images of cyclopentene molecules bonded in parallel to the dimer rows of Si(100)-(2 × 1) terraces. H. or silicon oxide. On Si(111). OH. (Figure 3 of J. (b) Clean surface of 4◦ -miscut Si(001) showing double-height steps. (a) Cyclopentene adsorbed on ‘‘on-axis’’ Si(001). such as designated (m × n) periodicity (m. Hamers et al. (c) Cyclopentene adsorbed on 4◦ -miscut Si(001).1. (2 × 1) adlattices can be formed by cycloaddition of cyclic olefins onto surface Si−Si dimers [21]. This sort of monolayer usually exhibits a good robustness and is as useful as fully terminated surfaces. that in which the stoichiometric full coverage is attained. n: integer). presented a highly ordered adlayer terminating all Si atoms just by exposing clean Si(100)-(2 × 1) to gaseous cyclopentene (C5 H8 ) in UHV environment [22]. the adsorbates are arranged randomly [26]. The discovery of H:Si(111)-(1 × 1). Hovis. S. There are some typical cases in which every surface Si atom is actually terminated by one C−Si bond. fills most of the space over a single-crystalline Si(111) surface when every surface Si is terminated by one CH3 group [24]. the smallest alkyl moiety. If the surface is supposed to be handled in air or in liquid. J. Phys. Liu. Appl. On the basis of fundamental surface science on single crystals. complete rejection of dangling bonds should be achieved by appropriate reaction and handling conditions. Fig. on which every surface Si is monohydride terminated [20]. Hamers. namely. Attempts to make an adlayer with species bulkier than those typical adsorbates inevitably lead to formation of a mixed adlayer with small adsorbates that fill the spacing areas. 66. On real adlayers. Even a C2 H5− group is slightly too bulky to be accommodated within Si(111)(1 × 1) unit cell. Because steric hindrance is anticipated between adsorbates. This is a difficulty in obtaining ordered adlayers due to the lack (a) (b) (c) High-resolution STM images of cyclopentene. was an epoch-making event to open up the field of organic chemistry on semiconductors handled out of ultrahigh vacuum (UHV). such as terminating H. R. it is preferable to arrange organic adsorbates and spacing adsorbates in a well-ordered manner. it was demonstrated that even CH3− .

and Buriak [35] are excellent. we should assess the byproducts and contamination during the process of deposition as well as during the procedure of surface analysis. Oxidation of Si substrate cannot be avoided completely in treating H:Si(111) in aqueous/nonaqueous solvents in conventional sealed glassware. Hydrochloric acid-Peroxide Mixture. Another microscopic structural issue to be tackled is the detailed bonding arrangement near the anchoring part. Oxidative reagents should be avoided in solutions. which dissolve different kinds of organic debris. the review articles by Yates et al. Bent et al. APM). The most frequently used method of organic deposition is called hydrosilylation. Then. [7. HPM). some topics on hydrogen-terminated Si(111) and chlorineterminated Si(111) that emerged in the last few years are introduced. reported by Allongue et al. The signs of impurities should be carefully watched and quantified by proper methods of calibration under cross-checking with different techniques. the procedures to handle Si wafer surfaces are briefly discussed in terms of deposition reaction and surface analysis. Then the wafers are subjected to extensive oxidation in reagent mixtures such as H2 SO4 + H2 O2 (3:1. Photoadsorption of 1amino-3-cyclopentene in liquid phase onto H:Si(100) seemed to deposit molecules linked to Si by C=C and those by NH2 [28]. heat. which can be put in order by thermalization. 100 ◦ C. HCl + H2 O2 (90 ◦ C. and so on. diluted HNO3 + H2 O (1:1. [31]. The technique of protected derivatives commonly used in organic synthesis was applied on Si(100) surface to deposit amino-terminated hydrocarbons [29]. one should consider not only the formation of isomeric adsorbates but also the reactions at unexpected portions in the reactant molecule. To learn more about the development of this field. In such treatment. Attachment of olefins modified with functional groups is more complicated as the functional groups may be more reactive with hydrogen-terminated Si than terminal C=C. Wolkow [32]. which often obscure the target adsorbates and bother surface analysis.3. The structure of the anchoring part depends on the method of forming the C−Si bond. The sacrifice oxide layer after treatment in such solutions is approximately 10-nm thick. SPM or ‘‘piranha’’ solution). 27]. Sulfuric acid-Peroxide Mixture. is a series of para-substituted phenyl groups grafted by electrolysis of precursor diazonium cations on hydrogen-terminated Si(111). in which hydrogen-terminated Si surfaces are treated in terminally double-bonded olefins with a proper source of excitation (radical initiator. NH4 OH + H2 O2 (AmmoniumPeroxide Mixture. One exceptional case. To obtain a homogeneous thickness of 1. [30]. In general. It is a good idea to use two kinds of solvents.2 . Most surface-sensitive analytical tools can usually present adequate information on contaminants with high fidelity.2. compared with the cases of small admolecules on noble-metal surfaces. Wayner et al. light) or by catalysis. Their STM images were explained to represent a (2 × 1) adlattice composed of phenyls and terminating hydrogen atoms arranged alternately. such as trichloroethylene and acetone.160 1 Preparation of Monolayer Modified Electrodes of mobility along the surface. Handling of Si Specimens for Adsorbate Preparation and Surface Analysis Surface treatment of Si wafers as purchased usually starts with degreasing by sonication or rinsing in organic solvents. 90 ◦ C). 34]. In this article. [33. We also have to be careful of the hydrocarbon contaminants in atmosphere.

The surface is strongly hydrophobic. When the specimen is in the atmosphere. which can hardly be eliminated by extensive hydrogen treatment [43].1. The H:Si(100) (3 × 1) surface is composed of alternate rows of monohydride dimers and dihydride silicon atoms [41]. the vacuum container can be switched to a turbomolecular pump running at top speed. The largest chance of contamination is when the surface is in the stage of initial vacuum pumping. UHV chambers and tubings are convenient for most heating and gas exposure treatments. It is necessary to use an oil-free pump. These surfaces can be prepared by atomic H treatment of clean Si(100)-(2 × 1) or heating in high-pressure hydrogen gas [42]. The surface usually contains unterminated dangling bonds (neutral Si surface monoradicals). The produced surface can be kept clean in air for at least a few minutes. H:Si(100)-(2 × 1) is composed of surface Si−Si dimers with each Si terminated by one hydrogen atom. UHV is ideal in storing the surfaces and is indispensable for handling clean Si surfaces of Si. After quick. For Si(111). Introduction of the Si specimens into a vacuum chamber should be done carefully. H:Si(111) and organic-modified Si are not positively contaminated within a short period. and the latter causes severe hydrocarbon contamination. for evacuation from atmospheric pressure. By this procedure. 39]. The process of adsorbate deposition should be carried out in a well-controlled environment. Spectroscopically useful D:Si(111)-(1 × 1) can be prepared by fluoride solution in D2 O [38. H:Si(100)(2 × 1) and H:Si(100)-(3 × 1) are well known [40]. Immersion of H:Si(111) in water without deaeration promotes oxidation of the surface [9]. The residual gas in the vacuum generated by oil rotary pump is water and oil. In UHV. such as liquid-nitrogen cooled sorption pump or helium cooled cryopump. The specimens should be rinsed and dried under a dry atmosphere after the reaction. etching in dilute HF or 40% aqueous solution of NH4 F at room temperature effectively removes the oxide layer to form ideal H:Si(111)-(1 × 1) [20]. clean evacuation from the atmospheric pressure to ∼10−4 Torr. such as N2 or Ar. Etching of Si(100) in fluoride solutions results in an inhomogeneous surface composed of partially (100)-(2 × 1) and (111) facets [45] and the surface is much less defined than H:Si(111)(1 × 1). H:Si(111) and organic-modified Si surfaces are resistive to air and can be passed between vacuum or purged containers through air. For hydrogen-terminated Si(100). contamination by hydrocarbons and oxidation can be reduced below the limit of spectroscopic detection.3 SAMs on Hg Electrodes and Si 161 the oxide layer. Reactions in organic solvents are successfully performed in airtight glassware or glove boxes purged with inert gas. the wafers are sometimes pretreated in HF (a few percent) to remove irregular precovering oxide layer. However. Due to such dangling bonds. It is difficult to perform liquid-phase reactions on H:Si(111) for an extended period of time in aqueous solutions unless some reducing reagents are added. 37]. electron sources sometimes deliver hydrocarbon contamination on Si. the surface cannot survive in the atmosphere [44]. just a short period of exposure to the atmosphere does not usually oxidize the surface to any detectable extent and the laboratory procedures can be done conveniently. Operation of a B–A gauge placed on a . and microscopic perfection of H:Si(111)-(1 × 1) was well studied by various methods [36.

the reaction between H:Si(111) and terminally double-bonded olefins (1-alkenes) has been accepted as a practical method of organic deposition. generated in the preadsorbate as a result of C−Si bond formation. and the wetting and chemical properties of the whole adlayer usually seem not to be affected by the existence of oxygen adsorbate. The origin of OH might be the peroxide radical initiator or O2 dissolved in the reaction fluid. This category of methods has been most utilized to form adsorbates including functional groups. Adsorption of O can be due to accidental oxidation from the environment. in which the best quality was attained by Grignard reaction on chlorinated Si substrate discussed in the next chapter. The mechanism of hydrosilylation has been elucidated as the ejection of a terminating hydrogen atom to form a Si dangling bond followed by an attack of the terminal double bond in olefin to form C−Si bond [6].3.3 Summary of the Latest Researches 1. Sieval reported aminoterminated alkyl grafted on hydrogenterminated Si(100) by a rather sophisticated amine protection/deprotection process to avoid direct reaction of NH2 and Si surface [50]. Most of the succeeding researches using longchain alkenes lack in assessment of oxygen directly bonded on the Si surface. or by using Lewis-acid catalysis. and the residual amount of surface oxygen is an index of the reproducible. Use of diluted olefins in an inert solvent (such as saturated alkanes) improves the quality of the alkyl adlayer [49]. The leftover . The long-chain alkyls may screen the adsorbates nearest the surface Si atoms.162 1 Preparation of Monolayer Modified Electrodes line of sight from the specimen should be avoided. 1. The deposition reaction was activated by the coexistence of a radical initiator in liquid phase [6]. summarized the extent of substrate oxidation depending on the method of reaction activation [13]. by light irradiation [46–48]. The adlayer of long alkyl chains is robust and convenient to stabilize Si surfaces and to make modifications over the adsorbates. by heating [6].3.1 Adsorption of Terminal Olefins on H:Si(111) Since 1995 when Linford et al.2.2. Linford et al. A complete alkyl adsorbate is then formed. well-defined adlayer. The adsorbates are bulky and the substrate–adsorbate interface did not perhaps affect the function of DNA. The C radical. which is supposed to be oxygen attached to the adsorbates. In some cases the attachment of functional groups to Si surface can be avoided by the difference of reaction rates between the terminating double bond and the functional group [39. A small extent of substrate oxidation was not inevitable. 51]. Small portions of SiO2 deposited during the adsorption process are considered to be the nuclei of SiO2 island enlargement [7]. or just H2 O molecules entangled in the adlayer. and furthermore grafted DNA on the amino group. Oxygen not incorporated in SiO2 at Si surface is often detected by XPS [25] or Auger electron spectroscopy (AES) [9]. first hypothesized that the spacing species to accommodate alkyl chains on Si(111) is OH species according to X-ray photoelectron spectroscopy (XPS) observation [6].3. leaving one Si dangling bond. Webb et al. probably due to the treatment in aqueous solution for hydrolysis. Strother et al. first reported the fabrication methods of long alkyl chains (>10 carbons) [6]. [15] deposited amino-terminated decyl by a similar protection/deprotection method. immediately picks up a neighborhood surface-terminating H.

1. such as C2 H5 AlCl2 . The existence of a bridge type adsorbate on Si(111) has not been recognized widely so far but it will be interesting to find a concrete method of preparation and to exploit its characteristic macroscopic properties. reason presented to reject the secondary type (sec-type). Lopinski et al. The photoadsorption of 1-butene on H:Si(111) did not yield CH3 vibrational signals. such as shown in Fig. the anchoring C−Si part of olefin-originated alkyls can be either of primary carbon or of secondary carbon. The photoreaction was performed in an UHV setup. Strictly speaking. and incorporation of surface-terminating D into alkyl adsorbate was evidenced by vibrational analysis [39]. The primary type (n-type) is simple and usually accepted. They could discern isolated dangling bonds (vacancies of hydrogen termination) and styrene admolecules in UHV. which are considered to be indifferent of H-terminated Si surface. which is formulated as: radical initiator. X=Cl. which the sec-type adsorbates nominally contain. Br.3. I) has been widely used in . This causes the formation of bridge type adsorbates. indicating that the original methyl end in 1-butene was destroyed [39]. [52] Recently.3. Yamada et al. the photoadsorption of allylamine (CH2 =CH−CH2 NH2 ) on D:Si(111)-(1 × 1) was performed.1. The activation by Lewis-acid catalyst. The adsorbates of sec-type were characterized by the vibrational modes of −CH3 group. Adsorption of styrene takes place on a site nearest to a dangling bond. while there had been no (1) (2) (3) lamine appear sequentially according to the increase of total coverage [39]. The dangling bond (·Si) plays the role of chain carrier for the whole process. presented a vibrational evidence that sec-type and n-type adsorbates from gaseous ally. proposed a similar reaction mechanism on H:Si(111)(1 × 1). or hν H:Si(111)(surface) − − − − − − − − → −−−−−−−− · Si(surface) + ·H(This · H dissipates away. may be excited and subjected to bond formation with Si besides the reaction of double-bond end. Another possibility for future in-depth consideration is whether the alkyl chains. and one end of the styrene chain is always accompanied by a dangling bond. which seems to be taken over immediately by adsorbate bonding. was explained to proceed by the generation of surface Si cationic radical [13. Recently. Figure 4 shows these two types of adsorbates for allylamine precursor.2 Grignard Reaction on Halogenated Si(111) The formation of C−Si bond by Grignard reagents (Cm Hn MgX. 1b. which is ideal for impurity rejection and the succeeding surface analysis.3 SAMs on Hg Electrodes and Si 163 dangling bond again captures olefin.) −→ R−CH=CH2 + ·Si(surface) − − R−(CH·)−CH2 −Si(surface) − − − − − − −→ R−(CH·)−CH2 −Si(surface) + H:Si(111)(surface) − − − − − − − − R−CH2 −CH2 −Si(surface) + ·Si(surface) This process is actually visualized by Lopinski et al. 53].2. [17]. who revealed the chain growth of styrene along the dimer row of H:Si(100)-(2 × 1) by STM.

Recently Rivillon et al. Despite imperfect impurity rejection and surface analysis. 59] applied an outstanding method of surface infrared spectroscopy and detected Cl−Si vibration signals. (b) secondary (sec-type) adsorbate. 57] reported well-ordered monolayers of Cl:Si(111)-(1 × 1) and Br:Si(111)-(1 × 1) examined by STM and high-resolution electron energy loss spectroscopy (HREELS) formed by (photo-)reaction in gaseous Cl2 or Br2 on H:Si(111). As one of the most attractive topics in the field of Si surface science. (a) Primary (n-type) adsorbate. and Si(111) was also subjected to Grignard reaction in the early stage. organosilicon synthesis.164 1 Preparation of Monolayer Modified Electrodes H N C Si (a) Fig. 4 (b) Schematic view of allylamine adsorbates anticipated on Si(111) surface. [56. Bansal et al. [54. 5). The mechanism is simply formulated as: RMgX + Cl:Si(111) − − −→ R:Si(111) + MgXCl (4) Grignard reagents are delivered as solutions in diethylether or tetrahydrofuran (THF). The halogenated surfaces were atomically flat with low defect density. Cl:Si(111) and Br:Si(111) slowly react with components of air and should be handled in vacuum or in inert gas. which are commercially available. this work was pioneering in the use of alkylating reagents on Si surfaces. The surface was composed almost solely of monohalide Si atoms. Removal of surface Si atoms as gaseous Si halides is considered to be involved in flattening the modified surfaces. the formation and structure of methyl-terminated Si(111) by Grignard reaction has been . The precursor halogenated Si surfaces had not been put into detailed investigation until recently. [58. 55] chlorinated H:Si(111) in a benzene solution of PCl5 under coexistence of radical initiator and then immersed the chlorinated surface in alkyl–Li solution or alkyl–MgX solution. even better than hydrogen-terminated Si(111) (Fig. Lopinski et al.

51 V.38 nA. studied in detail. Surf. 2005. Kawai. The features representing methyl groups changed according to the STM gap voltage. −1. Chem. Eves. gap voltage = −1.5 × 6. examined a methyl-terminated Si(111) from Cl:Si(111) and CH3 Li by X-ray photoelectron diffraction and spectroscopy aided by synchrotron radiation [60]. G. Lopinski. J. Scan size = 500 nm × 500 nm. Wawro et al. (Figure 2 of B. 19.186 nm. Phys. [55] listed the results for CH3 and longer alkyls and assumed that CH3 can terminate every surface Si atom on Si(111) on the basis of geometrical consideration. −0. 400 pA. The CH3− group is probably the only hydrocarbon species that can terminate Si(111) in (1 × 1) periodicity with practical stability. (Figures 3 and 4 of T. −1. Sci. 2004. [13] also extensively compared the perfection of alkyl adlayers prepared by various methods. 10 nm × 10 nm. −1 V (sample bias). They concluded that the length of C−Si bond vertical to the surface is 0.58 nA. Terry et al. 50 pA.5 × 6. 40 pA. (a) Fig. P. (b) Cl/Si(111)-6. Bansal et al.1. (a) Cl/Si(111)-50 × 50 nm. Yamada. 5 (b) (c) STM constant current images of halogenated Si(111) prepared by gas phase reactions at room temperature. (b) A high-resolution STM image. 61] as high-resolution STM images. Webb et al. preset tunneling current = 2.5 V. M. (c) Br/Si(111)-6.. as well as the lattice of methyl moieties arranged in (1 × 1) periodicity. The . L89 [57]). A.48 V. 121. [24. Figure 6 shows the flatness of the methylated surface viewed in a wide zone. J. 579.3 SAMs on Hg Electrodes and Si 165 (a) Fig.5 nm. (c) 4 nm × 4 nm. 10660 [24]). 2.5 nm. A concrete evidence for methyl (1 × 1) termination was presented by Yamada et al.4 V. 6 (b) (c) (a) A wide-range STM image of methylated Si(111). −0.21 V (sample negative).65 nA.

J.166 1 Preparation of Monolayer Modified Electrodes 106 683 Counts [cps] 507 789 1268 1099 1423 2944 x2000 0 0 Fig. Yu et al. M. 789 cm−1 : CH3 rocking. 7 x50 500 1000 1500 2000 2500 [cm−1 ] 3000 3500 4000 Wavenumber HREELS of the methylated Si(111).5 cm−1 . 1423 cm−1 : CH3 umbrella motion.6 meV. 10660 [24]). performed STM imaging of CH3 :Si(111)-(1 × 1) at the low temperature of 4. HREELS of CH3 :Si(111)-(1 × 1) was also presented (Fig. was controlled below 0. 507 cm−1 : C−Si bending. A. indicating all the characteristic vibration modes including the C−Si stretching motion. 2944 cm−1 : C−H stretching. HREELS incident electron energy 2. Wawro et al. 2004. Chem. the rotation about the C−Si axis vertical to the surface is attractive.. However. (Figure 2 of T. The energy barrier of rotation excitation may be analogous to that of torsion of C−Si bond in an isolated CH3 −SiH3 molecule.7 K [62]. 121. In terms of the movement of adsorbed CH3 group.84 eV. which corresponds to a frequency of 590. The full width at half maximum of inelastic peak = 7. Kawai. 7). The amount of SiO2 impurity. 1268 cm−1 : CH3 asymmetric bending. They claimed that the rotation of every CH3 group was locked at a position of C−H bonds rotated by (7 ± 3)◦ away from the center of the neighboring −CH3 group. features actually represent the electron orbitals. Yamada.1%. sensitively detected by HREELS. 683 cm−1 : C−Si stretching. incident angle = exit angle = 60◦ from the surface normal. Phys. and it is difficult to extrude the geometric arrangement of H atoms in CH3 just by viewing the images. It is interesting to address the electronic property of CH3 :Si(111)-(1 × 1) not only for the purpose of application as . so far no methods have been found to observe this rotation collectively. 1099 cm−1 : Si−O stretching in SiO2 .

3 cases of adsorbate formation on hydrogenterminated Si surfaces have been reported. [61] demonstrated that CH3 :Si(111)(1 × 1) as an electrode in an aqueous redox solution exclusively lowers the peak potential of redox reaction. As for Grignard reagents containing alkyl groups larger than methyl. On flat H:Si(111). The replacement of residual Cl species is probably uncontrollable and introduces more chances of contamination. The robust properties of this surface were found to be the same as those formed by alkene photoadsorption or by Lewis-acid catalysis. This peak corresponds to the electronic state that contributes to electronic conduction through the surface. the space filling of adsorbates does not geometrically allow every Si atom to be terminated. so far. and the Si−MgX species was considered to be quenched in Si−D by the presence of deutrated acetic acid. The formation of C−Si bond in methyl Grignard reaction on H:Si(111) was first evidenced by Yamada et al. The I–V characteristic curve of STM reached a peak at −1. They included a quenching procedure with acetic acid after the Grignard reaction. CH3 :Si(111)(1 × 1) was also applied as the ultrathin channel medium of field-effect transistor [14]. It is certainly easier to replace a part of the terminating hydrogen atoms on H:Si(111) by alkyl groups. which was advantageous in the detection of surface products.3.2.5 eV in the occupied levels additionally to the I–V curve of H:Si(111). [64] The atomic force microscope (AFM) images of alkyl-terminated Si(111) show a flat Si surface without any sign of pit formation related to the backbond breakage. Webb et al. This conducting property is also materialized in an electrolytic phenomenon. Niwa et al. By using CH3 COOD. Such Cl atoms are considered to be replaced by oxygen-containing species during rinsing or by exposure to air. and a certain part of terminating Cl atoms must be left over in the space between alkyl adsorbates. Boukherroub et al.1. explained this process by dissociative insertion of R−MgX into Si−Si bonds just below the surface (called backbonds). Replacement of terminating H with decyl groups was recognized. [5]. This interpretation fitted with a rather rough surface of porous Si. Grignard Reagents and H:Si(111) H:Si(111) is less likely than Cl:Si(111) to react with alkylmagnesium reagents according to the classic formulation of Grignard reaction. many 1. The formation of Si−R and Si−MgX was assumed. Kim et al. Kim et al. reported that highresolution XPS did not detect Cl after deposition of C2 H5− or C6 H5− CH2− on Cl:Si(111) rinsed in methanol [25]. This issue is discussed in the next chapter. concluded that a new mechanism of Grignard reagent should be proposed to replace terminating H [64]. [63] first reported derivatization of hydrogen-terminated porous silicon by Grignard reagents.3 SAMs on Hg Electrodes and Si 167 the lithography resist layer but also as the basis of nanoelectronic devices. The STM images of CH3 MgBr-treated H:Si(111) showed that methyl groups just formed small lattice patches and adsorbates were randomly placed with . The possible terminating species was anticipated to be hydrogen. However. rinsing in a THF solution of CF3 COOD did not introduce D−Si [65]. incorporation of Siterminating D species was detected. Formation of decyl (C10 H21− ) adsorbates by decyl Grignard reagent on H:Si(111) was first performed by Boukherroub et al.3.

alkali solutions [64]. Craighead et al. J. a limitation was recognized in detecting organic adsorbates and terminating hydrogen by infrared spectroscopy. K. Sci. 108. 39. G. can be deposited with adequate stability. 106. 68]. Whelan. The mechanism of H:Si(111) replacement by Grignard reagent has not been elucidated on the basis of concrete experimental evidences. The adlayers formed are constantly a mixture of alkyl and H regardless of the chain length.[5] This fact influences the interpretation of spectra of CH3 :Si(111) formed by electrochemical anodization in a Grignard reagent solution. J. 3240. proposed a mechanism involving a trace amount of alkyl halide residue contained in the Grignard reagent solution [69]. Chem. More varieties of hydrocarbons. 1996. the H−Si signal was apparently detected on surfaces prepared under the same condition. 3. the hydrocarbon groups are transferred to the Si surfaces within the precursor Grignard reagents without isomerization and component detachment. or even in a Cu-plating solution containing F− for a short period [9]. RMgX. The chance of unwanted substrate oxidation during the fabrication process can be minimized. Sci. Sugimura. Niwa. we can expect the application of alkyl halides as the alkylation reagent to open a new route to organic deposition on Si. H. indicating that the adsorbate-wise areal density is constant. The H−Si stretching signal at 2090 cm−1 became invisible to IR as the coverage of organic increased [26]. Hirao. . Phys. 4140. Lie. Yamada. However with HREELS. The Grignard reaction on H:Si(111) is probably the most useful method to obtain robust Si surfaces for practical purposes. Infrared spectroscopy seems to be more affected by adsorbate screening effects than HREELS. The C signals of AES [26] and XPS [55] indicating the saturation coverages are proportional to the chain length. Vac. Treatment of H:Si(111) in pure tetradecyl bromide yielded a finite amount of alkyl adsorbate and a significant amount of SiO2 . Technol. T. 4. Decyl bromide intentionally added in a diethylether solution of decyl magnesium bromide significantly accelerated deposition of decyl groups. and Si. Careful use of D:Si(111) and HREEL showed C−Si stretching signal at 678 cm−1 [5]. Lercel. H. 7057. W. Homma et al. J.168 1 Preparation of Monolayer Modified Electrodes a significant open area [66]. that 100% methylated surfaces were obtained [67. Recently Fellah et al. The alkylhydrogen mixed adlayers are strongly hydrophobic and resistive toward dissolved oxygen in water [9]. 2. D. 4085. References 1. Vac. such as branched or unsaturated hydrocarbon moieties [26. indicating that Grignard reaction cannot completely remove original terminating hydrogen atoms. Y. The effects of alkyl halide were scrutinized by voltammetric electrolysis of Grignard reagent. 65]. Although this analysis was not completed. regardless of the chain length. M. Fedorov. C. by using n-type and p-type silicon.. N. Chem.. B14. K. Phys. B14. A 2002. At the same time. Nakagiri et al. B 2004. In nearly all the cases. 1996. J. S. The HREEL spectra always contain H(D)–Si stretching signal. Technol. G. J.. Okiguchi. compared to the case for Cl:Si(111). and by considering the electronic and thermodynamic energy levels of RX. D. It was difficult to compare the reaction kinetics with the Grignard reagent.

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because optoelectronics and molecular electronics have become areas at the frontier of materials science [6].4. 2. such as fatty acids. including the earliest scientific paper on the effect of oily films on water by Benjamin Franklin in 1774 [3]. Japan History of the Langmuir–Blodgett (LB) Film Surface films of materials that have very poor solubility in the supporting liquid phase but exhibit interesting and useful properties. γ is the most fundamental quantity.Rubinstein. The materials forming the so-called insoluble monolayers. we can empirically define γ by the following equation: γ = f 2L (2) Encyclopedia of Electrochemistry.Rusling Copyright  2007 Wiley-VCH Verlag GmbH & Co. 1. The first formal report describing the preparation of built-up films did not appear until 1935 [1]. under Langmuir’s guidance. KGaA. has higher energy than the molecule in the bulk phase. Miss Katharine Blodgett had succeeded in transferring fatty acid monolayers from water surfaces to solid supports. the number of molecules in energy-rich interfacial positions increases.4 Langmuir–Blodgett (LB) Films on Electrodes 1. began their stimulating experiments on monolayer organization [5]. and J. while floating monolayers at the air–water interface are called Langmuir films. When increasing the surface of a liquid.1. The LB method was the first technique to provide a chemist 1.J. Stratmann Vol. ISBN: 978-3-527-30402-8 . A self-assembled monolayer (SAM) was introduced as a possible alternative to the LB films. In surface science. But a molecule at the surface misses the contact with the neighbors on top (Fig. have been recognized for centuries. Edited by M. A series of their pioneering works are introduced in the book by Gaines [2] together with the contributions of other early investigators.2 Basic Principles of Surface and Film Surface Tension A molecule in a liquid bulk phase is bound to the neighboring molecules surrounding it. Hans Kuhn et al. the reader is referred to a relevant textbook [7] as well as to the Gaines’ book mentioned earlier. In the mid-1960s.4 Langmuir–Blodgett (LB) Films on Electrodes 171 1. 10 Modified Electrodes. Weinheim. For more details of the historical aspects. Yokohama. Considering such a situation as illustrated in Fig.F. 1). By 1919. Japan Masamichi Fujihira Tokyo Institute of Technology. Yokohama.4. Such a molecule. Edited by A.Fujihira.4. The LB and SAM films have attracted much attention recently.1.1. and the preparation of the first monolayers at the air–water interface by Agnes Pockels in 1891 [4].1 with the practical (and still the most extensively used) capability to construct ordered molecular assemblies. The free energy change with increasing the surface area by a small amount dA in a reversible way is proportional to dA: dG = γ dA (1) The proportionality constant γ is called surface energy or surface tension. Bard and M. are essentially insoluble in water but are still surface active. Such built-up monolayer assemblies are now referred to as Langmuir–Blodgett (LB) films. I. therefore.1 Photoelectrochemistry Masaru Sakomura Yokohama National University.

The liquid surface near the three-phase contact line is oriented almost vertically. 3). F . platinum. the surface tension drags the plate downward. twice Lγ should be balanced with f . g is the gravitational acceleration. w. glass. immersed to a depth h in a liquid (as shown in Fig. the dimension of which is (N m−1 ). ρP is the material density of the plate. In the Wilhelmy method [8]. is given by F = 2γ (t + w) cos θ + ρP glwt − ρL gtwh (3) where θ is the contact angle. 2 Withdrawing a soap film. The second and third terms on the right-hand side of Eq. (3) represent the downward gravity force and the upward buoyancy force. From the viewpoint of this empirical law. mica. Thus. For a rectangular plate of dimensions l. The Wilhelmy plate is commonly employed in the usual LB apparatuses to monitor the change in the surface pressure. 1 Higher energy of a molecule at the surface than in the bulk. L Fig. There have been various methods for measuring the surface tension [2]. the net downward force. respectively. Because the film has a front and back side. The usual procedure is to choose appropriate materials for the plate (quartz. and t. we call the proportionality constant surface tension. and filter paper) that should .172 1 Preparation of Monolayer Modified Electrodes Surface Pulled into the bulk Average force is zero Liquid Fig. the force balanced with the surface tension is determined by a plate vertically suspended and partially immersed in the water phase. and ρL is the density of the liquid. f where f is the force required to withdraw a soap film from a surfactant solution by lifting a movable frame and L is the length of the movable frame. Figure 3 illustrates the experimental configuration.

in its chemical structure. 3 A Wilhelmy plate: (a) front view. the presence of the surfactant decreases the energy required to expand the interfacial area. The change in force F is then related to the change in surface tension γ by γ = F 2(t + w) (4) w. θ = 0) and measure the change in F for a stationary plate (h = const. Figure 4 illustrates the basic molecular structure of surface-active materials. the terms hydrophobic and hydrophilic are quite frequently employed in place of ‘‘lyophobic’’ and ‘‘lyophilic.’’ respectively. In water-based systems. or to form colloidal aggregates in solution at very low molar concentrations. Hydrophobic tail group .4 Langmuir–Blodgett (LB) Films on Electrodes Fig. however. the surface tension of the solution is decreased. Wilhelmy method can be used without any correction factors. so that t γ = F 2w Thus. the water structure will be unfavorably distorted. then (5) If the plate is thin. This entropy. If the hydrophobic tail group is present in an aqueous phase. Such a distortion (in this case ordering) of the water structure surrounding the hydrophobic group decreases the overall entropy of the system. Since less energy is required to bring surfactant molecules to the air–water interface relative to water molecules. which has a strong attraction for the solvent. The fundamental principle of the surface activity is expressed by the Gibbs adsorption equation: =− c dγ · RT dc (6) Hydrophilic head group Fig.e. Such materials are also referred to as being amphiphilic. A surfaceactive material possesses ‘‘lyophobic’’ part. is regained when surfactant molecules are transported to the water surface and the associated water molecules are released. 173 To microbalance l h (a) q (b) w t be completely wettable by the liquid (i. and ‘‘lyophilic’’ part. Surface Activity The chemical species given the general name of surface-active agents or surfactants have a special tendency to adsorb at interfaces. 4 Typical structure of surface-active molecules. If the water molecules on the surface are replaced by adsorbed surfactant molecules with lower specific excess surface energy.).1. which has little attraction for the solvent. (b) side view.

when the area of the saturated surface is more expanded. a fatty acid molecule that consists of a hydrophilic part (carboxyl group) and a hydrophobic part (a long hydrocarbon chain). c. When the surfactant is enriched at the surface.174 1 Preparation of Monolayer Modified Electrodes This equation relates the surface tension γ to the surface excess (i. therefore. which prevents the molecule from dissolving in the aqueous phase. −dγ /dc. Since the decrease in surface tension is directly related to the surface excess adsorption of the surfactant by the Gibbs adsorption equation (Eq. the amount of surfactant per unit area of surface). determines the molecular occupied area. Surface Pressure In a traditional way. The adsorbed molecules forming the insoluble monolayer are essentially isolated on the surface. for example. Such a molecule forms an insoluble monolayer on a water surface. Gibbs and Insoluble Monolayers The adsorption of surfactant molecules at the surface of a liquid can be so strong that a monomolecular film (Gibbs monolayer) of unidirectionally ordered surfactants is formed (Fig. increases with the concentration of the surfactant. . The reader will find discussions about such structure–property relationships in a relevant textbook [9]. the formation of the Gibbs monolayer can be monitored by decrease of the surface tension. Drops of the solution of the fatty acid in a volatile organic solvent are placed on an aqueous surface and after evaporation of the solvent a fatty acid’s monolayer remains. In contrast. 5). there are practically insoluble amphiphiles. 6). a film balance composed of a shallow rectangular container (called trough) and a movable barrier has been used to study Solution Fig. As for correlations between surface activity and the chemical structures of surfactants. Since the adsorbing species forming the Gibbs monolayer has a sufficiently large solubility in the solvent. the surfaceactive molecules dissolved in the solution will fill in the created area. This process is called spreading. a large body of literature has appeared. Monolayer The cross-sectional area of the hydrophobic chain or of the hydrophilic head group. The maximum number of molecules filling a given area depends upon the area occupied by each molecule. whichever is greater. they can provide good guidance for choice and development of the best surfactant for a given situation. and with the tendency of the solute to decrease the surface tension. Although most of the studies are semiquantitative at best. 5 Formation of a Gibbs monolayer. the surface excess is equal to the added amount of material divided by the surface area.e.

From the viewpoint of this. the barrier is balanced by the same surface tensions on both the sides. the formation of the saturated film accompanying the same decrease of the surface tension will be achieved on both the sides. .4 Langmuir–Blodgett (LB) Films on Electrodes 175 floating monolayers. the surface pressure is mostly measured with the Wilhelmy plate by monitoring the change in the surface tension from that of pure water as mentioned above. whereas in case (b). If the barrier could move freely. The design of the conventional type of a Langmuir or a Langmuir–Blodgett trough system (vide infra) is based on the composition of the traditional film balance. However. it would drift in the direction of the side with higher surface tension. A Gibbs monolayer will be immediately formed by adsorption of the surfactant molecules to the surface on this side. the surface of the subphase is completely clean and the surface tension of each side is that of pure water (γ0 ). In this case. Under the beginning condition of the film balance and the situation in case (a). A schematic comparison of the two situations of the film balance is illustrated in Fig. On the other hand. the surface tension of the side to which the amphiphile is added has been lowered. while the other side remains that of the pure water (γ0 ). An insoluble monolayer gleft = gright < g0 will be formed on this side. 6 A comparison of (a) Gibbs and (b) insoluble monolayers. the surface pressure π is defined as the difference between the surface tension of the clean subphase γ0 and the surface tension of the subphase covered by amphiphiles γ : π = γ0 − γ (7) The surface pressure can be determined by direct measurement of the force acting on the barrier in the differential way. The trough is filled with pure water and the left and right side of the surface is separated. 6. a soluble surfactant is placed on one side of the trough. in the usual Langmuir–Blodgett trough systems. the barrier moves in the direction to decrease the clean water surface. The surfactant molecule in the aqueous phase can diffuse to the opposite side of the barrier. while the aqueous surface of the opposite side will be kept clean even after any practical period of time. therefore. At the beginning. gleft < gright = g0 f Diffusion via subphase (a) (b) Fig.1. In case (a). an insoluble amphiphile is spread on one side of the trough. while the residual molecules will be dissolved in the subphase. in case (b). A liquid phase (called subphase) is added in the trough until a meniscus appears above the rim and the area of the surface is controlled with the movable barrier that rests across the edge of the trough. The barrier movement looks as if a lateral pressure due to the film is acting on the barrier. There are numerous modifications of the early film balances as reviewed in Gaines’ book [2]. after the system reaches equilibrium.

which is a two-compartment type trough with a flexible membrane fixed to the movable barrier [10. Wilson. there can be a first-order phase transition to the liquid state. We can consider at least two types of liquid phase. monolayer films exhibit characteristics that can be almost equated to the solid. A liquid-expanded (LE) phase appears first. The Gibbs monolayers can be compressed by using the PLAWM (named by the combination of the first letter of Pockels. Analogous to three-dimensional bulk materials. As the monolayer is compressed on the water surface. liquid. Collapse Solid (S) Surface pressure p [mN m−1] Liquid condensed (LC) LC/LE Liquid expanded (LE) LE/G Gaseous (G) Molecular area A [nm2] Fig. and McBain) trough. 11]. 6). the lowering of the surface tension is expected from the Gibbs equation (Eq. Liquid (L): When compressing a gaseous film. 7 Schematic π − A isotherm of a monolayer. It shows the following phases: Gaseous (G): The molecules are relatively far apart and have significant surface mobility.176 1 Preparation of Monolayer Modified Electrodes Surface Pressure – area (π − A) Isotherm Experimentally. phase transitions between these analogous states should occur and the changes could be detected by the measurement of the π − A isotherms. The molecules act essentially independently and the surface pressure is almost zero (γ ≈ γ0 ). Langmuir. the molecules are touching each other but there is no lateral order. Figure 7 shows an example of the π − A isotherm. As for Gibbs monolayers. A pressure-area (π − A) isotherm measured by the above procedures gives us very important information about physical nature of the film and molecular characteristics of the adsorbed materials. . the compression of the film cannot be performed by using a Langmuir trough because amphiphiles would diffuse via the subphase to both sides of the barrier. Adam. one can spread a known amount of material (too small to saturate the starting area) on a subphase in a trough at constant temperature and move a barrier to compress an insoluble monolayer formed on the surface by slowly decreasing the available area. In this phase. When the surface excess increases by compression of the film. and gaseous states of matter.

water. pH. deposition follows the sequence of events described in Fig.8 × 105 m) and total organic contamination (TOC) in the ppb (parts per 109 ) level. At higher pH. The molecules are oriented almost perpendicular to the surface. and is established empirically.3 Preparation Methods for LB Films We confine Molecules and Subphase our discussion here to the most popular supporting liquid for monolayer studies. In the most commonly used method. can stabilize the monolayer of the anionic amphiphile. The quality of water is of prime importance to the LB studies. Today. Here. 16]. The water . Many researchers choose an ultrapure water system. the amphiphiles exhibit a tilted phase with a decreasing tilt angle. the substrate (e. we will concentrate on the LB method. Ba2+ . first introduced by Langmuir [15] and applied extensively by Blodgett [1. and Cd2+ ). donors. ‘‘touching’’ [12] and ‘‘lifting’’ [13. and then.4 Langmuir–Blodgett (LB) Films on Electrodes 177 After passing a plateau of the first-order phase transition. 1. facilitate monolayer transfer on solid surfaces. which can form an insoluble monolayer on a water subphase. In order to secure the reproducibility of the π − A isotherms. If the slide is used as a hydrophilic surface. Solid (S): The films are rigid and densely packed with high surface viscosity. This technique involves the vertical movement of a solid substrate through the monolayer/air interface. ultraviolet sterilizer. 8. stearic acid behaves like a neutral molecule. see the relevant textbooks [5–7]. The effect of the ion binding to reduce the extent of electrostatic repulsion between charged head groups allows for close packing of the monolayer.g. where the long hydrocarbon tail group (CH3 (CH2 )16 −) is hydrophobic.g. Ca2+ . it is crucial to keep temperature. acceptors. Such molecular engineering is very important. a reverse osmosis unit. LB Deposition Although many different techniques for transferring a floating monolayer to a solid plate have appeared (e. a glass slide) is first lowered through the monolayer so that it dips into the subphase and then withdrawn under a constant surface pressure. A classical example of an amphiphile. which includes mixed anion and cation exchange resins. The reader can find a discussion of the properties of monolayer films of a variety of amphiphiles in Gaines’ book [2].1.4. is stearic acid. that is. a liquid-condensed (LC) phase is reached. and photooxidation unit. For more details. The film is relatively stiff but still more compressible.g. At pH 4. supplying water of high specific resistance (1. many scientists use organic synthesis to construct amphiphiles for different purposes. 14] techniques). acting as counterions. The ionization of the carboxylic group will be suppressed at low pH. and composition of the subphase at the constant conditions. especially in the design of amphiphiles with functional groups such as chromophores. The presence of doubly charged cations (e. and the carboxylic acid head group (−COOH) is hydrophilic. The π − A isotherms are linear and its extrapolation to zero surface pressure gives an area per molecule that corresponds to the molecular crosssectional area.1. the carboxylic group dissociates to form carboxylate ion (−COO− ). The value of surface pressure that gives the best results depends on the nature of the monolayer. and so on.

The second withdrawal exactly resembles the first except that the new monolayer is now being deposited onto the hydrophilic head groups of the monolayer already present. depending on the nature of the monolayer. The ideal structures resulted from the deposition modes are illustrated in Fig. The second dipping into the subphase differs from the first in that the slide is now hydrophobic. Although this is the most frequently encountered situation. The bonding of the monolayer to the slide will only be complete after the intervening layer of water has drained away or evaporated. the deposition speed must be limited by the rate at which the ascending substrate sheds water. in which layers are laid down each time the substrate moves across the phase boundary. it is also possible for monolayer deposition to occur only when the substrate enters the subphase. which acts along the line of contact and so drives out the water film. As the slide is withdrawn. 8 Y-type Langmuir–Blodgett film deposition. therefore. is often used as a measure of . These deposition modes are called X-type (monolayer transfer on the downstroke only) and Z-type (transfer on the upstroke only). The substrate may. the meniscus is wiped over the slide’s surface and it leaves behind a monolayer in which the hydrophilic groups are turned toward the hydrophilic surface of the slide. subphase. there is no mechanism for deposition at the first dipping. the dipping substrate can be moved quite rapidly without affecting the monolayer transfer. with a head-to-head and tail-to-tail configuration is referred to as Y-type deposition. The deposition ratio. the meniscus turns down and a second monolayer is deposited with its tail groups in contact with the exposed tail groups on the slide. be placed in the subphase before the monolayer is spread. This drainage is not due to gravity but is a result of the adhesion between the monolayer being transferred and the material on the substrate. In contrast to the withdrawing process. This type of deposition.178 1 Preparation of Monolayer Modified Electrodes Down Up Fig. (a) (b) Down (c) Up (d) wets the slide’s surface and the meniscus turns up. substrate. 9. To avoid disordering of the film structure on the withdrawing process. and the surface pressure. τ (also called the transfer ratio). It is important not to raise the substrate faster than the rate at which water drains from the solid. The first monolayer is transferred as the slide is raised through the water.

As shown in the figure.g. (a) X-type (b) Z-type 179 the quality of deposition. and there is then a direct electrical readout of surface area. the trough with the single movable barrier can compress a monolayer on the left side of the barrier. As shown in the former section. To achieve the deposition of such alternate-layered structures more conveniently. 10 Cross-sectional view of a Langmuir–Blodgett trough. Wilhelmy plate Equipment for LB Deposition By now. . It is defined as the ratio of the decrease in the area occupied by the monolayer (held at constant surface pressure) on the water surface. it is unlikely that τ will be identical for different surfaces.4 Langmuir–Blodgett (LB) Films on Electrodes Fig. as mentioned in the earlier section. If asymmetric substrates are used (e. to the coated area of the substrate. there is a large but consistent deviation from a value of unity. Under most circumstances a transfer ratio of unity is taken as a criterion for good deposition. Such procedures are very time consuming and wasteful. 9 The multilayer structures formed by (a) X-type deposition and (b) Z-type deposition. AS . The ‘‘well’’ at the left end of the trough offers the depth allowing for the up and down stroke of relatively large substrates on the LB depositions. 10. If one intends to construct alternatelayered structures of two different types of molecules by using the conventional trough. τ= AL AS (8) The area removed from the water surface is easily measured by the mechanism used to maintain a constant surface pressure. some kinds of troughs for Solid substrate Movable barrier Subphase Trough Well Fig. the successive deposition of a monolayer can be easily achieved with this trough. Many types of trough systems are produced by employing the basic design of the traditional film balance. then some care must be exercised in interpreting the measured deposition ratio. Occasionally. this points to a situation in which the molecular orientation is changing during transfer. AL . Variable transfer ratios are almost always a sign of unsatisfactory film deposition. and one would then expect the orientation of molecules on the slide to be very similar to their orientation on the water. the two different materials would have to be alternately spread onto and removed from the subphase surface [17].1. that is. many kinds of the LB deposition protocols have been achieved by developing a variety of Langmuir–Blodgett troughs. a glass slide metalized on just one surface). The most conventional type of trough is like that shown in Fig.

11 is one of the alternate types. The compartments (eight in Fromherz’s design) are separated by walls. the multicompartment type trough will be briefly taken up here. The two fixed barriers placed on the center part of the trough separate the water surface into three compartments (A. Wilhelmy plate Movable arms Fig. The trough with the double movable barriers shown in Fig. 12 Barriers Fromherz multicompartment circular trough. which are slightly lower than the edges of the trough. These arms can move up and down independently and rotate. . Two different monolayers can be formed in the two compartments (A and B) between the movable and fixed barriers on each side. Another compartment C sandwiched by the two fixed barriers at the center of the trough is usually a clean water surface. In addition to the above-mentioned troughs of the single. B. The underarm can transport a substrate dipped thoroughly into the subphase to any compartment without taking it out from the water. and C). The lifter clutching the substrate consists of an upper arm and a lower arm. 11 Cross-sectional view of an alternate type Langmuir–Blodgett trough. 12) was described by Fromherz [21]. A Wilhelmy plate is suspended from the Movable barrier A Fixed barrier C B Movable barrier Fig.180 1 Preparation of Monolayer Modified Electrodes alternate deposition have been designed [18–20]. The multicompartment circular trough with two independent drive barriers (Fig.and the triplecompartment type.

upper part of one of the movable arms. therefore. 23]. guest) the host is harvesting light energy and the guest. When the film compression would be performed. They organized a large variety of monolayer assemblies to investigate intermolecular interactions. Much of the pioneering work in this field has been carried out by Kuhn and his colleagues. The energy migration in the layer of the host depends strongly on the interaction of the molecules. In these films. or in chemical reactions. the investigations of the energy transfer from a sensitizing molecule to an acceptor molecule within the complex monolayer organization will be given here. the monolayer formed between the two barriers can be transported to other compartments with different subphases by the synchronized motion of the two barriers (Fig. host) with traces of dye II (Fig. octadecane acts as a spacer and contributes to the arrangement of the aliphatic region. is trapping the energy. Since the . The film transfer onto a substrate has to be carried out only on a compartment in which a well for the LB deposition is provided. 1. As good examples of their research. A system harvesting light energy and channeling the energy should be of interest as a component in any proposed photoelectrical device for solar energy conversion. the surface pressure is measurable at any compartment. which absorbs at longer wavelength. It can be demonstrated by a quantum mechanical calculation that the exciton hopping time in this very compact arrangement of chromophores is t = 10−13 s. 13 181 Monolayer manipulation using the multicompartment trough. As proposed by Kuhn et al. After the compression. 14. In a monolayer of dye I (Fig. for example.1. 14. for studies on the adsorption between a back surface of a floating monolayer and a soluble material in a subphase [22. 27]. Such monolayer manipulation by the multicompartment trough may be applied.4.4 LB Assemblies Designed for Photoelectric Devices Energy Transfer in Monolayer Organization The Langmuir trough technique enables us to construct simple artificial membrane systems consisting of cooperative molecular components. J aggregates in monolayers prepared by spreading the dyes and the long chain hydrocarbon octadecane in a 1:1 mixture can be regarded as two-dimensional crystals with a brickstone arrangement of the chromophores [5. the barrier held by the arm with the Wilhelmy plate must be fixed and the other barrier would be moved to decrease the available area. 13).1.4 Langmuir–Blodgett (LB) Films on Electrodes Fig. and photophysical and photochemical processes [24–26].

the coupling should be sufficiently strong to get a trapping of the energy absorbed by the host even if there is one molecule of the guest among 104 molecules of the host. respectively. It should be noted that this artificial device for channeling energy is far more efficient than the device used in plant photosynthesis where there is one energy trap among 300 chlorophyll molecules for harvesting energy. They fabricated two LB assemblies as shown in Fig. On the other hand. If an exciton trap is exactly interlocking in this structure. which can excite the host only. an unusual long exciton diffusion path can be expected. we can write I = I0 rd rd + ren (9) where rd is the rate of deactivation by fluorescence and thermal collisions and . A plate where the guest is absent shows the violet fluorescence of the host. fluorescence time of the single molecule is 104 times longer than t. The molecule can substitute a molecule of the host in the lattice.182 1 Preparation of Monolayer Modified Electrodes = = Fatty acid Host ~ Dye I = Guest ~ Dye II = Octadecane Case (a) Case (b) Fig. In the film of case (a). In case (a). If I and I0 are the intensity of the fluorescence of the host in the presence and in the absence of the guest. 14. the host’s fluorescence is quenched but the blue fluorescence of the guest is observed with a plate where the guest is present. respectively. This condition should be fulfilled in the present case where dye II differs from I only by two sulfur atoms instead of two oxygen atoms. The changes of the relative fluorescence intensity of the host are plotted in Fig. it exists in the fatty acid monolayer deposited on a layer of the host. 14). The fluorescence change is due to light harvesting via energy transfer from the excited host to the guest. a considerable quenching of the fluorescence of I and a sensitized fluorescence II was seen even if only one among 50 000 molecules of I is exchanged by a molecule of II (Fig. the guest molecule is incorporated in the lattice of the host. The monolayer assemblies are fabricated on a glass plate and illuminated with UV light. 15. 14 Monolayer assemblies for energy channeling system consisting of dye I and dye II as light harvesting and trapping molecules. whereas in case (b).

where N is the number of molecules of host per molecule of guest) then 1 I = const. = 104 and const. the dye and electron acceptor are in direct contact. 15 A plot of I/I0 (relative fluorescence intensity of dye I) against N (number of molecules of dye I per molecule of dye II) for case (a) (circles) and (b) (squares). For this purpose.0 Case (b) I /I0 0. ren is the rate of energy transfer. = 300 for cases (a) and (b) respectively. 15. they are separated by inserting a fatty acid spacer-layer between . we obtain the full and broken curves in Fig. quenching of fluorescence due to electron transfer from an excited dye to an electron acceptor can also be observed in monolayer assemblies. Kuhn designed LB Case 3 Donor Acceptor assemblies in which dye II in monomeric form and the electron acceptor molecule III (viologen) are incorporated separately in two monolayers (Fig.4 Langmuir–Blodgett (LB) Films on Electrodes 183 1. 16). Fig. This example shows the importance of a well-defined architecture of the monolayer assembly.5 Case (a) 102 103 104 105 N Fig. In case (1). 16 Assembly of monolayers of donor (dye II) and electron acceptor III. Since ren is proportional to the surface density of the guest (inversely proportional to N . In case (2). I0 1+ N (10) Acceptor molecule III Case 1 Case 2 Using the values const.1. Layer-by-layer Assemblies of Electron Acceptor and Dye Molecules With appropriate components and film structures.

where I0 is the fluorescence intensity without acceptor. Therefore.184 1 Preparation of Monolayer Modified Electrodes dye and acceptor layers. the substrate is covered by the dye and then by a fatty acid layer of desired length in the usual manner (Y-type deposition). In case (3). 1 × 1013 s−1 . For nonadiabatic electron transfer. the standard technique of producing monolayer assemblies could be applied since the pyrene was bound to the methyl group at the end of a fatty acid chain while the cationic viologen III is at the hydrophilic head of the molecule. The hydrophilic side of the film must be moderately hydrophilic and well adjusted in its composition to make the intended contact. Now the layer is dipped in water without a surface layer. (9). the water is then covered by an acceptor layer. therefore. ket is described by the following equations [29]: ket = k(r) exp − G∗ RT (11) (12) k(r) = k0 exp {−β(r − r0 )} where k(r) is the preexponential factor of the rate constant. dye chromophore and acceptor are separated by the hydrocarbon substituents of both layers. In cases (1) and (3). If the electron transfer is purely tunneling. the ratio (I0 − I )/I . In the case of pyrene as the dye and again viologen as the electron acceptor. In this case. 11) is available. that is. and totally unquenched in case (3) [28]. half quenched in case (2) if the C16 fatty acid is used as the spacerlayer. measures the rate of the electron transfer. the heterogeneous LB films are formed by Y-type depositions. It is therefore easy in this case to separate chromophore and electron acceptor by a single monolayer of hydrocarbon chains. On the other hand. To realize case (2). On the basis of a similar relation as Eq. This ratio is given by the ratio of the rate of electron transfer (ket ) and rate of deactivation of the excited dye in the absence of the electron acceptor (kd ). the linear relation of log {(I0 − I )/I } against d could also be demonstrated by M¨ bius o [28]. r is the distance between electron donor and acceptor. In each dye layer. This is a somewhat tricky step since rearrangements must be avoided. The fluorescence of each sample was compared with that of the reference sample where the acceptor is absent. the logarithm of (I0 − I )/I plotted against d should form a straight line. Figure 17 shows that this is in fact the case for spacer layers with 14–22 C atoms [24]. d. and β is the parameter of the distance dependence of the rate. the heterogeneous depositions can be achieved more conveniently. If an LB trough of an alternate type (Fig. these monolayer assemblies are easily fabricated with a conventional LB trough (Fig. the rate of electron transfer should be practically independent of temperature and decrease exponentially with increasing r corresponding to the thickness of the spacer layer. G∗ is the free-energy barrier of reaction. The dependence of the fluorescence intensity I in case (2) on the thickness of the spacer layer was also investigated. dye II is diluted by fatty acid (not shown symbolically). and the plate is taken out. r0 is the value of distance r at which k(r) equals some preassigned value of k0 . This fluorescence is totally quenched in case (1). 10) by spreading and removing the different films on a water surface repeatedly in the course of the film depositions. The substrate is taken out by slowly lifting the sample in a horizontal position. . the film of case (2) includes also a Z-type structure.

34]. 50]. within LB monolayers can be closely controlled at known values. and o others [36. As they did.0 C14 C16 Log {(I0/I ) −1} −0. 37] have studied the distance dependence of the rate of photoinduced electron transfer in LB films. where hydrophilic parts and hydrophobic units are indicated by circles and squares. Fujihira et al.4 Langmuir–Blodgett (LB) Films on Electrodes 185 0. and D. Kuhn [24. fabricated the acceptor/sensitizer/donor (A/S/D) type LB multilayer system as a molecular photodiode based on Kuhn’s idea of the light-driven electron pump [32] on a gold optically transparent electrode (AuOTE) [33]. the difference between the energy levels of the excited (or ground state) donor and the ground state (or excited) acceptor [29. In addition to the distance dependence. S. the distances between the three functional moieties. The structure and function of the molecular photodiode of A/S/D are shown in Fig. Three functional compounds tend to orient regularly in the heterogeneous LB films due to their amphiphilic properties. that is. Acceptor/Sensitizer/Donor Multilayer Systems A variety of electronic components with molecular dimensions have been investigated since the introduction of the foresighted concept of molecular diode by Aviram and Ratner [30]. Log{(I0 /I) − 1} is plotted against the spacer layer thickness d for fatty acids with 14-22 C atoms. 18(a). Relationship (13) was first introduced by Marcus where the free-energy barrier for the reaction. A. Mezger and Panetta [31] have made an effort to realize the molecular diode proposed by them. case (b). the effect of the standard free energy difference G◦ for the electron transfer.0 d [nm] Fig. (11) and Eq. M¨ bius [28. 35]. is another important factor in determining the rate of electron transfer. 17 Quenching of fluorescence of dye II (D) by electron acceptor III (A) in the arrangement of Fig. G∗ in Eq.5 C17 C18 C20 −1. 16. 49. (11).0 C22 2.0 2. 26.1. respectively. For example. Their observed dependence agrees in a qualitative sense with the other experimental [38–48] and theoretical [29] results described by Eq. that is.5 3. (12). is . that is.

as a consequence of the inverted region. Once an electron-hole pair is separated successfully. If the forward processes indicated by arrows with solid lines are accelerated. the motion of the nuclei was treated classically. the energy diagram of the A/S/D molecular photodiode is depicted as a function of distance across the LB film. the inverted region. and D amphiphiles.186 1 Preparation of Monolayer Modified Electrodes D A S D A S1 S D (a) ii v vi iv vii i Electrode (b) Fig. where the rate decreases with an increase in large excess of − G◦ . In Marcus’s original theory. 50] to treat the nuclear coordinates quantum mechanically and to modify the equation for the energy gap G◦ . that is. (b) energy diagram. given [29] in terms of the reorganization energy λ: G∗ = λ 1+ 4 G◦ λ 2 (13) The changes in bond lengths of the reactants and the changes in solvent orientation coordinates in the electron transfer are related [29] to λ. to design a better molecular photodiode the distance and G◦ dependence should be kept in mind. Therefore. There have been several attempts [29. 18(b). and (c) structural formulae of A. (13) is most important. 18 S2 hn iii A − − A S D (c) Molecular photodiode with heterogeneous A/S/D LB film on an electrode: (a) structure. the photoinduced vectorial flow of electrons can be achieved. the recombination of . the acceleration by setting G◦ equal to λ is assumed for the forward electron transfer processes (ii) and (iii). The presence of the inverted region has been confirmed experimentally by the use of internal electron transfer systems with rigid spacers and the electron transfer in solutions [51–60]. predicted by Eq. S. In Fig. is assumed for the back-electron transfer processes (iv) and (v). while the retardation. In connection with the design of the proper energy diagram for the molecular photodiode. and the backward processes with dashed lines are retarded by setting the distances and the energy levels appropriately.

and their coworkers used polyimide LB 2 1 4 films consisting of A. 2 layers of a porphyrin derivative with aliphatic polyimide as S.S. electrons should be more readily transferred. By depositing these three amphiphiles on AuOTE. They have reported the preparation and properties of polyimide LB films [64–66].4–0. 20) for constructing more efficient molecular photodiodes [62. 18b. 19) [38–41].S. The three kinds of functional amphiphilic derivatives used for the first A/S/D-type molecular photodiode [33] are shown in Fig.A/S.6 nm). In such heterogeneous LB films.A. the photoelectrical conversion efficiencies of AuOTEs coated with 6 layers of aromatic polyimide itself as A. vii) without quenching by electron transfer. and 6 layers of a ferrocene derivative with aliphatic polyimide as D is enhanced about 10 times larger than those for photodiodes with conventional LB films [62].S/D. (2) a Au wire counterelectrode. Imai.4 Langmuir–Blodgett (LB) Films on Electrodes Fig. the photocurrent in opposing directions depending on the spatial arrangement of A/S/D or D/S/A is detected [61]. 19 187 A cell for photoelectrochemical measurements: (1) an LB modified AuOTE. for example. 63].D. the long alkyl chains are intervened between the A and S and between the S and D moieties. The direction is in accordance with the energy profile across LB films in Fig. 0. in spite of the inability of the substrate electrode to rectify. in the form of A.A. The AuOTE is a metal electrode and hence does not by itself possess a rectifying ability as does a semiconductor electrode [38–41]. the hole-carrier property of the D layer was further improved by the use of triphenylamine in place of ferrocene as the D moiety [63]. as shown in Fig. LB Assemblies of Synthetic Molecular Photodiodes Another approach to shortening the distances between the functional moieties is the use of synthetic molecular . Much higher photocurrents can be observed [33. 18(b).D/S.S/A. S. Yet. 3 the pair across the large separation by LB film (process (vi)) is hindered by the distance dependence. and by the use of the resulting electrode as a working electrode in a photoelectrochemical cell (Fig. (4) a cell container. The directions of the photocurrents also agree with those expected for the multilayered systems. 61] for stacks of multilayers of each component. 18(c) together with porphyrin sensitizer S2 used later.S.D and D. (3) a saturated calomel electrode (SCE) with a salt bridge. 18(a). Later.A. and D units (Fig.D. Since polyimide LB films have no long alkyl spacer between the layers (monolayer thickness. To cope with this problem. parts of the excited sensitizers were deactivated by the emission of photons (Fig. Kakimoto.S. the photoinitiated vectorial flow of electron is achieved and detected as photocurrents.1. For example. As a result.

fast. called photosystems I and II (PSI and PSII). that is. and efficient electron transfer steps. triads. Following light activation of antenna pigments. [67–69] In biosystems. porphyrins. Such intramolecular charge separation systems are also studied as model compounds for a natural photosynthetic reaction center (RC). tetrads. The multistep electron transfer reaction through the array of the redox species with appropriate energetics and spatial coordination arranged by transmembranal span of the complexes in the plant or bacterial cell culminates in a long-lived charge-separated state. have been studied in connection with photosynthesis and reported by several groups [70–88]. So far. 20 photodiodes. the molecules organize themselves into complex functional entities with cooperating components of molecular dimensions. and A components of polyimide heterogeneous LB film molecular photodiode. a variety of synthetic polychromophoric model systems. and so on. aromatic imides. For design of artificial photosynthetic molecular devices. it is of great interest to mimic the elaborate molecular machinery. S. whereas bacteria make do with a single reaction center. photon energies are harvested and funneled to the special pair acting as the initial donor in a series of short range.188 1 Preparation of Monolayer Modified Electrodes O O Fe N C H O D O O N O N O NH N A N HN O O n O N O N O O O N H m N O N O n H C N n S Structural formulae of D. pentads. since the structural determination of bacteria’s photosynthetic reaction center to atomic resolution using X-ray crystal analysis by Deisenhofer et al. Higher plants use two different reaction centers. in particular. where chromophores and redox moieties are linked covalently. All reaction centers in plants and bacteria are complexes containing protein subunits and donor–acceptor molecules. Fig. The well-organized and asymmetric molecular arrangement across the membrane plays an important role in charge separation in photosynthesis. The electron-transport components. and fullerenes are commonly employed by . quinones.

and a neutral electron donor (D. a dicationic electron acceptor (A. The early amphiphilic triads [33. Because of the folded form of the oriented molecules on a water surface. A–S–D Triad Monolayer Systems Since 1985 [33]. 21 Structural formulae of the folded-type triads. viologen (V2+ )). in which the dicationic hydrophilic A moiety of the triad is oriented toward water and two hydrophobic alkyl chains terminated by S and D subunits extend into the air. However. a neutral sensitizer (S. two steps of intramolecular electron transfer would be initiated through light absorption of . 22a) under high surface pressure. mimicry of the farther aspects of photosynthesis including chemical processes driven by the chemical potential in the form of the longlived charge separation is still difficult and has only been reported in a few works [89. were combined in the order of S−A−D (Py–V2+ –Fc). the triad forms stable mixed monolayer with arachidic acid. ferrocene (Fc)).1.4 Langmuir–Blodgett (LB) Films on Electrodes 189 S−A−D C11 S−A−D C16 Fig. the spatial arrangement of the three moieties in the order of acceptor–sensitizer–donor was expected (Fig. respectively. owing to the difference in the length of the two alkyl chains (C6 and C11 or C16 ) linking A to S and D. In this highly ordered folded-type S–A–D triad. In these amphiphilic triads. pyrene (Py)). At an air–water interface. three functional moieties. 91] are shown in Fig. Fujihira’s group has been studying amphiphilic triad molecules that can spread and form monolayers on water surfaces. singlet energy transfer between pigments. 21. and photoinduced electron transfer from excited singlet states to give long-lived charge-separated states in high yield have been realized with some of these artificial systems. 90]. The primary event of photosynthetic solar energy conversion including absorption of visible light. in which the active components were linked by sigma-bonded tunneling bridges. the S–A–D triads were called the folded-type triad. many of the reaction center models. In such monolayers.

23 Structural formulae of linear-type triads. 22 (b) (c) Schematic representation of (a) oriented folded-type S−A−D triad and (c) oriented linear-type A–S–D triad.190 1 Preparation of Monolayer Modified Electrodes D A S hn A S D (a) Fig. 92–94] were synthesized. 22c). In order to achieve the spatial arrangement of the A. therefore. to the AuOTE under controlled potential may occur. and D moieties more readily and completely. the sensitizer moiety. 23) [71. And then electron transfer from the resultant long+ + lived charge-separated state. and D. and the photodiode function played by the highly oriented triad molecules of the folded type is successfully observed. S. linear-type A–S–D triad molecules I−V (Fig. If the oriented triad molecules were transferred onto a AuOTE as they are on the air–water interface using the LB technique. The mixed monolayers of the I II III IV V Fig. Py–V • –Fc • . In these triads. Such photoelectric conversion devices are readily fabricated. S. 22(b). the three moieties are combined linearly in the order of A. . asymmetric spatial arrangements of them in monomolecular layers should be in the same order (Fig. It was found in the early studies that the appropriate spatial arrangements for the charge separation of the folded-type triads were attained only under high surface pressures [91]. the photodiode function of this molecular device would be expected from the energy diagram shown in Fig. and (b) corresponding energy diagram.

4 Langmuir–Blodgett (LB) Films on Electrodes 191 linear-type triads with behenic acid exhibit much higher photocurrents than those of the folded-type triads. (d) the deposition of a triad monolayer on a hydrophobic surface of a Au electrode by the LB method. (b) the corresponding energy diagram. For the purpose of the study. and a counter (Au wire) and reference (saturated A hn (a) Down (b) SCE Thiol-coated Au electrode Quartz window Counter electrode Aqueous subphase (c) Fig. a new type of photoelectrochemical cell (Fig. the electrode is released to fall inside the cell. An aqueous subphase is poured into the trough. The cell container is first put into the Langmuir trough. and D moieties are attained in the linear triad molecules ordered in the mixed monolayers. A Au mirror electrode is first treated with a thiol compound with a short alkyl chain (C3 ). The fabrication of the new type of photoelectrochemical cell is performed by the following procedures. the photocurrent of the AuOTE modified with the triad monolayer with opposite directional orientation (Fig. 24 (d) Schematic representations of: (a) molecular orientation of A–S–D triad on a Au electrode. S. . 24 c) equipping such an LB Cathodic D S modified AuOTE are developed [94]. The cell container is then taken out of the trough together with the subphase solution and the Au electrode in it. a hydrophilic Au surface was changed to a hydrophobic thiol-modified surface. By this treatment. 24) should be examined. The hydrophobic Au electrode set just above the cell container is dipped into water. More of the supporting electrolyte is added. At the end of film deposition. and then the triad monolayer is formed on the aqueous surface. This indicates that more ideal spatial arrangements of the A.1. A favorable orientation for the photoelectric conversion of the linear-type triad was also accomplished at a relatively low surface pressure of 15 mN m−1 in contrast with the inactive orientation of the folded-type triad molecule deposited at the same surface pressure. To confirm that the triad absolutely acts as a molecular photodiode in the monolayer. (c) the new type of photoelectrochemical cell.

such as scanning tunneling microscopy (STM) [102] and atomic force microscopy (AFM) [103]. from molecular arrangements at interfaces to electronic structures in semiconductors [99]. The SPMs. the photoinduced dipole change of the triad molecules unidirectionally oriented in LB monolayers on electrode surface can be easily detected as a change of CPD by Kelvin method. 25 Schematic diagram of SMM. The work functions can be changed by adsorption of molecules with different dipole moments. But detailed structures of LB films had not been clarified until these films were studied by scanning probe microscopies (SPMs) [95–101]. These SPMs. information about the orientation of amphiphilic molecules in the monolayers is important. For the studies of LB monolayer assemblies. The CPD for clean metal surfaces is given by the difference in the work functions of the two materials.Z piezo X-. cathodic photocurrent consistent with the energy diagram for the opposite direction can be observed.Y. the LB technique is suitable for making highly oriented molecular assemblies. The Kelvin method of measuring the CPD makes use of the vibrating capacitor. The controllability of the direction of the photocurrent clearly indicates that the oriented triad rectifies the photocurrent and acts as a molecular photodiode. have been used to analyze surfaces of many levels.Y-signal Z-signal Fw SPI 3600 Z-piezo controller F2w 2w Lock-in amplifier Fig. Therefore.192 1 Preparation of Monolayer Modified Electrodes calomel electrode. Alternate Multilayered Systems for Scanning Maxwell Stress Microscopy As already described. provided only limited information about the chemical nature of systems studied. With this new type of cell. however. . 2w) w VDC Excitation laser light X. as well as determination of the chemical functionalities. The Kelvin method [104] is a well-established technique for determining the contact potential differences (CPDs) between reference electrode and a metal sample. A modified version of the AC scanning force microscope with a Kelvin probe Preamplifier Position sensitive detector Laser light Au-coated tip LB-coated AuOTE or ITO electrode Maxwell stress AC: sin(wt) DC Bias Lock-in amplifier f (w. SCE) electrodes are set into it.

28. In the LB assemblies. 25) [107–113]. a lateral image of the variation in CPD on the surface on a submicron scale can be observed. the electron and hole can be separated unidirectionally. 27. For the fabrication of these LB assemblies. . With these methods. The method was further simplified and named the scanning Maxwell stress microscopy (SMM) (Fig. The resulting photoinduced changes in dipole moments of the highly oriented triad molecules are detected as the surface potential changes of gold electrodes covered with the LB films by SMM under illumination as shown in Fig. 106]. For the SMM studies of LB films containing unidirectionally oriented A–S–D triads.1. the alternate LB multilayer systems shown in Fig. linear-type A–S–D triads are arranged unidirectionally in two ways with the D tail of the triad toward the air (a) or toward the substrate plate (b). 114].4 Langmuir–Blodgett (LB) Films on Electrodes 193 tip is called a Kelvin probe force microscope (KFM) [105. 96. By photoexcitation of the S moiety. 2 Layers S D D S A D S A S D A S D A A S D A 30 Layers 30 Layers S D D S A D S A A S D A 5 Layers 3 Layers (a) Fig. respectively. but with opposite directions in the LB films as in the same way as the primary process in photosynthesis [70. 26 are constructed [95]. 26 (b) Unidirectionally oriented A–S–D triad in LB assemblies. a fatty acid is used as a spacer and a diluent. The change in surface potentials of the LB films of cases (a) and (b) with a pulse illumination of the excited light of 125 ms are shown in Fig. The polarities of the surface potential changes are again consistent with the molecular orientations.

.194 1 Preparation of Monolayer Modified Electrodes Tip for SSPM D S A a Au-coated quartz plate D + S A − hn Laser off Laser on Fig. 2-3 s with a He−Cd laser light in a total reflection mode. 27 Detection by SMM of the change in photoinduced surface dipole moments in highly oriented A–S–D triads in artificial photosynthetic reaction centers as the local surface potential changes. Light off 60 A S D S D A 40 A S D A S D 30 layers 20 Surface potential change [mV] 0 Light on 0 Light on −20 D S A D S A D S A −40 D S A D S A D S A 30 layers −60 Light off 0 10 20 Time [s] 30 40 50 Fig. 28 The change in the surface potential by step illumination for ca.

in the A–S–D triad monolayer. A –A–S–D structure is used for its efficient charge separation [68]. in the reaction center of natural photosynthesis. The exponential-like decays after shutting the illumination down reflect the decrease in the number of the separated charges by recombination.4 Langmuir–Blodgett (LB) Films on Electrodes Lateral hole diffusion D D D + D e− D + D D 195 S S Slo Lateral electron diffusion e− A A _ mb eco wr S i ion nat S S A A _ hn A A A Fig. The much slower recombination can be interpreted as arising from further charge separation via a lateral diffusion mechanism of photocreated anion and cation radicals [117–119]. the increase in the lifetime of the charge separation perpendicular to the film by adding a second door D’ or an acceptor A to form A–S–D–D or A –A–S–D quadruplet should be examined. Because of laboriousness of quadruplet syntheses. the layer can act as a second donor layer with a sufficient driving free energy. The drastic increase in the surface potential is attributable to the efficient lateral diffusion because of prolonged lifetime of the perpendicular charge separation by the A–S–D/D quadruplet system. therefore. 50 ns) [71. If the charge separation and recombination proceed only within the triads. respectively. LB Assemblies for Simulations of Key AsThe pects in Natural Photosynthesis development of an artificial photosynthesis system is one of the most fascinating . as illustrated in Fig. In fact. 116]. via intramolecular processes. Figures 30(a) and (b) show the surface potential changes of the LB assemblies without and with a pure bilayer of D . The ionization potential of the donor moiety in D molecule is smaller than that of the D moiety of the A–S–D triad. A–S–D Triad Monolayer and Second Donor Bilayer Alternate Systems To increase the charge separation efficiency. that is. respectively. it seems that the observed recombination rates are too slow in comparison with the intramolecular recombination rates for folded-type triads (ca. under step illumination for 125 ms with a laser light and the schematic representations of the corresponding film structures. Anion and cation radicals on the A and the D moieties were created by photoexcitation of the S moieties followed by charge separation. 29. 29 Schematic illustration of slow charge recombination via lateral diffusion of electrons and holes in the A and the D layer. the quadruplet structure by depositing a D (16-ferrocenylhexadecanoic acid) monolayer on a D end of an A–S–D monolayer is constructed [120]. 25 ps) [115] and a linear-type triad (ca. It is remarkable that the photoinduced surface potential change increased about 1 order of magnitude by addition of the D layer.1.

respectively.196 1 Preparation of Monolayer Modified Electrodes 15 A−S−D system 10 D S A D S A Surface potential change [mV] 5 (a) A−S−D/D′ system 2 bilayers 0 200 150 D′ D′ D′ D′ D′ D′ D′ D′ D′ D′ 100 D′ D′ D′ D′ D′ D′ D′ D′ D′ D D S S A A 2 bilayers 50 (b) 0 −2 0 2 4 Time [s] 6 8 10 Photoinduced surface potential change under step illumination by He−Cd laser (441. are used.6 nm) for the LB assemblies (a) without and (b) with a pure D bilayer. the monomolecular layer assembly including a triad and a synthetic antenna molecule is designed to mimic the two successive aspects of a primary process in natural photosynthesis: antenna and reaction center [93]. Because of the good overlap of the emission spectrum of the antenna pyrene moiety (Py) and the absorption spectrum of the sensitizer perylene moiety (Pe) of the triad (Fig. For the amphiphilic linear triad molecule. 350 and 470 nm are found. 31. 32). as the S unit. as the A and the D units. Maxima of anodic photocurrents at ca. the excitation energy of the perylene moiety should be converted to electrical energies via multistep electron transfer across the monolayer as described above. For the light-harvesting (H) antenna pigments. 32). . Fig. Figure 33 shows the photocurrent spectrum of the mixed monolayer of the triad and the antenna with a molar ratio of 1:4. an amphiphilic pyrene derivative [121] is used. The result indicates that charge separation in the triad molecules was initiated by light absorption both with perylene sensitizer itself and with the pyrene antennas followed by the energy transfer. Thus. The A–S–D mixed monolayer consists of A–S–D (V) and 22-tricosenoic acid (1:5). These correspond to the adsorption maxima of pyrene and acylated perylene (solid curves in Fig. an acylated perylene moiety. As illustrated in Fig. and viologen and diacylated ferrocene moieties. light energies harvested by the antenna molecules are efficiently transferred to the sensitizer moiety of the triad. 30 challenges.

1.4 Langmuir–Blodgett (LB) Films on Electrodes 197 Triad V A−S−D Antenna dye H hn E fro ner m gy H tra to ns S fe L ra ate r l en erg ig ym rati on hn Charge separation D A H H H S Electron transfer across the membrane Lateral energy transfer Fig. and charge separation via multistep electron transfer. To focus only on the energy transfer process from Py to Pe. The result indicates that the most efficient energy transfer . 31 Schematic representation of the artificial photosynthetic reaction center by a monolayer assembly of antenna (H) and A–S–D triad molecules for light harvesting. energy migration and transfer. the dependence of sensitized emission intensity on the ratio of H with an energy acceptor molecule is also examined [122].

a much more efficient light harvesting can be attained by the combination of the energy donor. from Py* to Pe is attained with the molar ratio Py:Pe = 30 : 1. dye I. reaction center.198 1 Preparation of Monolayer Modified Electrodes Absorption Emission Intensity [au] Py Pe 300 400 500 Wavelength [nm] 600 Fig. 250 molecules of cyanine can harvest light for excitation of one Pe. is examined [124. 125]. Next. and quinone pool. a further advanced LB assembly as a biomimetic model system to seek to mimic the three successive aspects of photosynthesis. 32 UV and visible absorption (solid line) and fluorescence (dashed line) spectra of antenna H pyrene (Py) and monoacylated perylene (Pe) derivative in ethanol. 33 Photocurrent spectrum of the mixed monolayer of antenna H and triad V with a molar ratio of 4:1 (solid line). and the energy acceptor. 4 Formal quantum efficiency × 105 Py 2 Pe 0 300 400 Wavelength [nm] 500 Fig. The antenna effect of dye I in this system is such that ca. antenna pigment. Pe [123]. While in the mixed monolayers of the cyanine (dye I in Fig. In natural photosynthesis . 14) and the pyrene amphiphiles.

Fig. The photoelectric conversion with the LB assemblies is attained by the processes (i)–(iv). 100 Surface potential change [mV] 80 60 40 20 0 0 2 4 Time [s] 6 8 10 lex = 441. plastoquinol (PQH2 ).4 Langmuir–Blodgett (LB) Films on Electrodes 199 systems of higher plants. whereas at 325 nm. the excited state S∗ is induced via energy transfer from H∗ . The electrons from PSII can be accumulated within the plastoquinone pool in the reduced form of plastoquinone. The S moiety of the triad is directly excited by the 441. 34 A−S−D Triad D′ Schematic illustration of the LB assembly for simulation of the primary process in natural photosynthetic reaction center.6 nm S S* lex = 325 nm H H* S* Photoinduced surface potential change under step illumination at 441. The film structure and the expected photophysical processes are schematically illustrated in Fig. Not only the electron link but also an electron buffer in the form of a pool is a D′ D′ D′ D′ D′ D′ D′ D′ D′ unique function of PQ. 34. After the light A bilayer structure of pure D′/ASD+H(1:30) system iv) lateral hole diffusion + + D′ D′ D′ D′ D′ D′ D′ D′ D′ D′ D′ D D H S H H A S H H A D′ D′ D′ e− D′ D′ D (i) photo-excitation (ii) light harvesting at 325 nm H* e− (iii) normal charge separation S A e− - 3 bilayers of 22-tricosenoic acid He−Cd laser H Au OTE Fig.1. 35 . that is. PSI and PSII. a lipid soluble and diffusible quinone called plastoquinone (PQ) acts as a mobile component of the electron transport between two different photosynthetic reaction centers.6 nm irradiation.6 nm (solid curve) or 325 nm (dotted curve).

1987. 20. Wilhelmy. Myers. . Chem. Weissberger. 1940. New York. Kuhn. 64. 16. But the film added by D bilayer. A. Faraday Soc. Petty.200 1 Preparation of Monolayer Modified Electrodes harvesting (ii) and successive charge separations (iii) proceed similarly as in the former monolayer of A–S–D and H. 49. 1/35 against that at 441. 1991. 25. 6. Soc. Soc.6 nm (a solid curve) and 325 nm (a dotted curve) [124]. J. gave large surface potential change at both wavelengths. D. 382–387. Ford. 1976. Franklin. F. C. 19. Appl. Waterhouse. G. Vol. J. P. 83–88. Fromherz.6 nm. Wiley. 24. L1377–L1380. W. H.6 nm. 43. A. K. Rev. the change in surface potential would not be detectable with such diluted A–S–D layer alone because prolonged intermolecular distances suppress lateral charge migrations. B. New York. Blodgett. H. Gaines. Fukuda. 26. I. B. Roberts. P. L. B¨ cher. Langmuir-Blodgett Films. 1380–1385. New York. Kato. V. 1937. 1934. the mixed A–S–D monolayer with H with the molar mixing ratio 1:30 is added by a D bilayer. FEBS Lett. 5. 244–249. S. Biophys. Ulman. 445. McBain. McBain. 1975. An Introduction to Ultra Thin Films from Langmuir-Blodgett to Self Assembly. Am. Kuhn. Rossiter). Considering the difference between the resulted signals at 325 and 441. 1966. 2105. References 1. G. 1935. 225. Marcheva. Thin Solid Films 1985. H. W. which acts as charge diffusion layer. Langmuir. Soc. D. 1938. Kuhn.6 nm of the He−Cd laser used. V. Barraud. Chem. 17. B. Soc. Thin Solid Films 1985. Spink. J. A. R. 1863. Am. 4. J. 11. whereas excited perylene sensitizer is induced by energy transfer from excited pyrene of H to the perylene in the grand state under illumination at 325 nm. D. Am. 46. 60. 1 (Eds. Chem. B. 1–9. Jpn. 1007. J. 25 times larger than that of perylene at 441. The number of the photons of the incident light at 325 nm is ca. Biochim. Nature 1891. hole diffusion (iv) via hole migration in the second donor layer and hole and electron accumulations in the D and A plane are expected to occur in this system. Schaefer. 146. 356. I. Interfaces and Colloids. J. Leloup. W. With the light illumination at 441. G. in o u Techniques of Chemistry. Normally. R. L. J. D. Schulman. 22. R. 2. 1979. Instrum. 62. A. 329–333. Photochem. J. Kapil. Philos. 8. 1975. 72. 1990. D. Trans. 54. 12. Holcroft. Palacin. 9. Fromherz. the perylene sensitizer in A–S–D is directly excited and H contributes as a diluent similar to fatty acids. 21. Chem. 13. 62–74. 121]. 1972. B.: A. 10. J. Academic Press. T. 577–702. On the basis of the energy transfer study of the Py−Pe system mentioned above. Figure 35 shows the change in surface potential measured with the (A–S–D + H)/D system under the step illumination of 441. Colloid Interface Sci. Chem. 78. P. Chem. Langmuir. Am. Wilson. 133. Wilson. Trans. London 1774. H. Insoluble Monolayers at Liquid Gas Interfaces. 119. Acta 1971. Plenum Publishing. B. 134. 1920. 57. 7. Sci. 430. 77–95. 111. H. it can be concluded that the light energy harvested by the antenna molecules is mostly funneled to the sensitizer moiety of the A–S–D triad molecule. 495. Colloid Interface Sci. 1351–1360. K. Soc. A. 53. 342–343. K. K. 1981. Wiley. Blodgett. M¨ bius. J. Roberts. G. Surfaces. 15. 3. Pockels. Fromherz. 23. Srivastava. 1991. J. 1956. J. J. 1979. Nakahara. 56. pp. 14. H. T. J. Phys. J. 117–123. J. 10. A. Kolloid-Z. 437. Ann. VCH Publishers. Phys. Kato. 18. 177–217.6 nm [95. New York. K. New York. A. The pyrene absorbance of the film at 325 nm is estimated to be ca. Pure Appl. T. M. Kolloid-Z. Vinograd.

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Conjugated redox-active compounds are candidates for ‘‘molecular wires’’ and are expected to be a convenient tool for the construction of molecular electronic devices. These phthalocyanines undergo up to five reductions at the modified electrode. The formation of thin fullerene films including fullerenelipid hybrid and fullerene-lipid composite bilayer membranes is of interest both from a fundamental and practical application point of view.4. Japan chemical and biochemical design of functional carbon nanotubes. 7].4 Langmuir–Blodgett (LB) Films on Electrodes 203 1. and carbon nanotubes (CNTs) is described. and specific functions.1. The fifth reduction had been theoretically Introduction In this chapter. through the LB monolayer.2. Tsukuba. The unimolecular electrical rectifiers prepared by using LB techniques are useful for the construction of molecular electrode devices [1–5]. Japan Naotoshi Nakashima Kyushu University. and thermal properties. to hexacyanoferrate(II) ([Fe(CN)6 ]4− ) in solution [6.2 Langmuir–Blodgett (LB) Films on Electrodes (B) Electrochemistry Takashi Nakanishi National Institute for Materials Science (NIMS). Potential-step chronocoulometric responses revealed that the LB monolayer acts as an organic ultramicroelectrode array. It is of interest to use monolayer and LB films of enzymes.4. mechanical. proteins and fullerene derivatives. encouraging the application of such techniques to biomimetic membranes in aqueous media. and antibodies as biosensors or biomolecular switches because of their high sensitivity for their substrates and antigens.2. We describe here how to make ultrathin films of nanotubes on substrates. constructed electrical rectification systems using LB monolayers of substituted quinolinium tricyanoquinodimethanides (Fig. Fukuoka. 1. artificial lipids. 2) were mixed with amphiphilic matrices and cast on electrodes as thin films [8–10]. the electrochemistry of Langmuir–Blodgett (LB) films of functionalized molecules including ‘‘molecular wire’’ compounds. We have reported that LB films of π-conjugated electrochemically active quinolinium complexes transferred on to gold electrodes show rectified transmembrane electron transfer. Multiwalled carbon nanotubes (MWNTs) and single-walled carbon nanotubes (SWNTs) are novel nanomaterials that have remarkable electronic. The use of electrodes modified with immobilized redox-active molecules provides a simple methodology by which to study the ultrathin film electrochemistry of water-insoluble redox-active molecules. respectively. Ultrathin films of electrochromic molecules such as multireducible doubledecker phthalocyanines are one important possible component of color display devices. 1) on electrodes by scanning tunneling spectroscopy (STS) [1.4. proteins.2 Electrochemistry of LB Films of ‘‘Molecular Wires’’ and Phthalocyanines It is known that LB techniques can be applied for the construction of thin film electronic devices and molecular rectifiers [1–5]. phthalocyanines. The double-decker lutetium(III) phthalocyanine molecules having long alkyl chains (Fig.1 . 3]. Metzger et al. Soluble carbon nanotubes in aqueous and organic systems are of interest since their study allows the 1.

13]. Fig. brownred. are observed at LB films of octakis-substituted heavy rare-earth metal double-decker phthalocyanines in contact with an aqueous electrolyte [11]. green. reported that LB films of rare-earth metal double-decker phthalocyanines deposited onto indium tin oxide (ITO) microelectrodes have sensing properties for NO gas and vapors of volatile organic compounds such as alcohols. 2 Chemical structures of the alkylthio substituted double-decker lutetium(III) phthalocyanines. and purple. use of cationic matrices is important because reduced anions of the phthalocyanines can be stabilized in these matrices. Oxidation peak currents of a maker ion ([Fe(CN)6 ]3/4− ) in the aqueous phase through the lipid films increased with the addition of Ca2+ ions only when the LB films were in the fluid liquid crystalline phase above the phase transition . aldehydes. 1 + N NC CN − CN Chemical structures of the quinolinium tricyanoquinodimethanides. which are contained in aromas of foods and beverages [12. Saja et al. Okahata et al. that is. predicted but had not been previously observed for any double-decker lutetium phthalocyanines. Multicolor electrochromism. blue. Moreover. LB films of artificial lipids transferred onto electrode substrates could be used as glucose [14] and calcium ion [15] sensors and for hydrogen evolution [16]. coated a SnO2 electrode with LB films of synthetic phospholipids [15].204 1 Preparation of Monolayer Modified Electrodes + N NC CN − CN S O Fig. and esters.

The LB films of glucose oxidase (GOD)artificial lipid monolayers deposited onto Pt electrodes act as glucose-sensing ultrathin membranes with a short response time [14].1. Ariga et al. in which methyl viologen was used as a mediator [16]. reported electrochemical hydrogen evolution using LB films of hydrogenase protein complexed with poly-L-lysine. Thus. in which the monolayer properties of the vitamin B12 mimics were investigated as a mixed monolayer with an organosilane lipid (Fig.2. The lipid LB film modified electrodes provide a suitable interface for the electrochemistry of cytochrome c [18] and myoglobin [19].3 Langmuir Monolayer of Fullerenes at the Air–Water Interface The construction of fullerene ultrathin films with an ordered structure is of interest from both a fundamental and practical point of view [20–22]. Fig. developed a novel type of vitamin B12 -functionalized electrode [17].4. 3). 1. C60 alone and amphiphilic fullerene derivatives form monolayers at the air–water interface and these monolayers can be transferred onto solid substrates [23–27].4 Langmuir–Blodgett (LB) Films on Electrodes 205 temperature since Ca2+ ion can only bind and penetrate into the fluid liquid crystalline phase of the films and disturb or expand the LB membrane structures. 3 . the synthetic artificial lipids provide suitable environments for the electrochemistry of redox-active biomolecules. Miyake et al. The obtained electrodes have the potential to transform environmentally toxic chemicals into nonhazardous ones Lipid (EtO)3Si H N C O Vitamin B12 derivative OR O H RO O O H H RO N N N Co(II) N H through an electrochemical process. The authors [28–38] and others [39–43] have been interested in combining fullerene chemistry and the O C N RO O O OR RO R= O O OR Chemical structures of the organosilane amphiphile and vitamin B12 derivative.

0 nm Water rwater = 1. 37]. 5 Schematic illustration of the nanostructure of the monolayer of the fullerene lipid on water revealed by in situ X-ray reflectometry measurements. . The electronic interaction between the fullerene moieties can be controlled by the phase change of the film.98 nm2 /molecule. the electronic interaction of the fullerene moieties is loosened. there is an electronic interaction between the fullerene moieties in the LB film.2 nm rC60 = 1. 5). suggesting the formation of monolayers with hexagonal and simple square packing. The fundamental property of the self-assembled bilayer membrane film is maintained in the LB film prepared in the dark. respectively [32]. At lower temperatures.206 1 Preparation of Monolayer Modified Electrodes Fig. and characterization of a C60 -bearing triplechain lipid [28. indicating that the molecular orientations of the rlipid = 0. We have reported the design.9 dlipid = 1. 37] (Fig. This lipid forms stable Langmuir monolayers at the air–water interface [32. In situ X-ray reflectometry (XR) techniques revealed the nanostructure of the fullerene-lipid monolayer on water. 4). Upon heating over 47 ◦ C. that is. The LB film prepared in the dark shows temperature dependent UV–vis absorption spectra. 36]. the fullerene moiety was in contact with the water surface and Air rair = 0 the lipid tail extended to the air [37] (Fig. which is the subphase transition temperature of the cast films of the fullerene lipid [28. chemistry of lipid bilayer membranes.0 Fig. 36.78 and 0.3 dC60 = 1. 4 Chemical structure of the fullerene lipid. The surface-pressure–area isotherm of the fullerene lipid gives limiting areas of 0. which may create a novel field in the chemistry and biochemistry of fullerenes. synthesis. 33. 32.

1. poly(allylaminehydrochloride) (PAH). which is regularly packed in a hexagonal array [44]. As an alternative way to avoid the formation of low-quality aggregated structures of fullerenes. Subsequently. The second-harmonic intensity is strongly dependent on the number of layers of the LB films.4 Langmuir–Blodgett (LB) Films on Electrodes 207 fullerene moieties of the LB film and cast film of the fullerene lipid are not significantly different. and n-octadecane in the gas phase [50. have studied basic electrochemistry of C60 fullerene LB films on an electrode in acetonitrile solutions [23]. electrochemical characterization of the higher-quality LB films was performed. 6). developed the electrochemical replacement method to form epitaxial adlayers of fullerenes on Au(111) surfaces [45].1. Bard et al.2. LB films of fullerenes have several intrinsic properties such as nonlinear optical features and gas sensing. The fullerene adlayers prepared by this method showed excellent quality and uniformity. The study on C60 LB films has become a focus of considerable interest. Nerilidol. but this was not observed in all of the cases. This information is useful for the design and construction of functional supramolecular ultrathin fullerene films at the air–water interface and on solid surfaces. it is difficult to fabricate high-quality LB films of pure C60 due to its intrinsic hydrophobicity. Kunitake et al.4 Electrochemistry of LB Films of Fullerenes on Electrodes Electrochemistry of LB films of fullerenes has been widely studied and remains the subject of much research effort from both theoretical and experimental approaches. These donor–acceptor dyad LB film systems are an attractive example for the development of molecular optoelectronic devices. The electrochemistry of LB films of fullerene derivatives in organic solvents showed well-defined reversible multi-electroreductions [47]. This is important from the viewpoint of the introduction of lipid bilayer properties of the fullerene lipids to the LB system. β-caryophyllene. . several functionalized fullerene derivatives with nonpolar or polar groups were synthesized. Spatial control of arachidic acid LB films by introduction of C60 molecules as the spacers to a polymer backbone. The ‘‘wet process’’ method consists of the transfer of Langmuir films of fullerene onto iodine-modified Au(111) surfaces at an air–water interface followed by the electrochemical removal and replacement of iodine adlayers with fullerene adlayers in solution.4. The LB films of a crowned C60 -pyrrolidine [48] and of a 4-acetylphenyl-substituted C60 -pyrrolidine [49] exhibit optical second-harmonic responses. however. citral. A visualizing technique by in situ scanning tunneling microscopy (STM) for the surface morphology of fullerene LB films on iodine-modified Pt(111) surfaces was also developed [46]. described the preparation of LB films of a phytochlorin-fullerene [52] and of a porphyrin-fullerene [53] that show vectorial photoinduced electron transfer reactions (Fig. Models of natural photoreaction centers can be constructed using LB films of fullerene derivatives. 51]. Kajiyama et al. is reported to be a novel sensor for α-pinene. The study indicated that reduction of the fullerene films could form insoluble films with incorporated electrolyte cations or lead to dissolution. Tkachenko et al. applied a multistep creep method as an LB technique for constructing a fairly homogeneous C60 monolayer.

Krstic et al. Preparation of carbon nanotube/polyelectrolyte thin films by the layer-by-layer technique has been reported [67].2. Since the first findings. 11-ferrocenylundecy poly(ethylene glycol). and specific functions [56–59]. [66] described the formation of LB films of SWNTs and behenic acid with densely packed and uniform coverage on hydrophobic Si(100) substrates. Barisci and coworkers [69] reported EQCM studies of SWNTs dispersed in water or in acetonitrile. carbon nanotubes have been at the forefront of nanoscience and nanotechnology because of their remarkable electronic. called carbon nanotube papers [60] and carbon nanotube films by physical adsorption [61] is already known. Ultrathin composite films of carbon nanotubes and amphiphiles are formed by means of the LB technique [62]. respectively.4. Soluble carbon nanotubes in aqueous and organic systems are of interest since their study can lead to the chemical and biochemical design of functional carbon nanotubes. described the formation of monolayers of SWNTs and a surfactant on substrates with lithographically defined electrode arrays [63]. mechanical. The preparation of carbon nanotube sheets. They measured the electrical transport of the electrodes. [64] prepared optically homogeneous and structurally controlled (oriented) LB films from soluble SWNTs.5 current/voltage characteristics showed a nonlinear dependence with steplike features. Carbon Nanotube LB Films Iijima discovered MWNTs [54] and SWNTs [55] in 1991 and 1993. LB film formation of crown ether-modified soluble MWNTs and SWNTs have been reported by Guo et al. whose process was monitored by an electrochemical quartz crystal microbalance (EQCM) [68]. By utilizing soluble nanotubes. 6 Chemical structures of the phytochlorin-fullerene (left) and porphyrin-fullerene (right) dyads. The 1. Carbon nanotube ultrathin films described earlier are considered to possess ordered and oriented structures and therefore these films may be useful for the construction of optical and optoelectronic devices. We have reported the dissolution of shortened SWNTs in aqueous micelle of an electroactive surfactant. [65] Luccio et al. carbon nanotube ultrathin films can be formed. and thermal properties. and then the formation of SWNT films from the solution by electrodeposition.208 1 Preparation of Monolayer Modified Electrodes Fig. . However. Minami et al. reports describing the preparation of thin films with high homogeneity from purified-carbon nanotubes dissolved or dispersed in solution are very limited.

M. 375. Kuriyama.. R.4 Langmuir–Blodgett (LB) Films on Electrodes 209 Conclusions We have reviewed a recent progress on the electrochemistry of LB films and related films of functionalized molecules including ‘‘molecular wire’’ compounds. 327–329. 11. Chem. Y. K. Chem. L.. H. Ebato. Murakami. Nakashima. Zhou. 91.. C. A.2. Chem. Langmuir 2001.. Kalashnikova et al. 660. 1373. F. 1998. 1995. Ariga. A. Y. New Horizons for the Chemistry. Yilmaz. Thin Solid Films 1998. T. Gorbunova. M. Nassar. 2000.. Nakanishi. W. 1641. A. Chem. N. H. Ohwaki. G¨ rek et al. V. Tanaka et al. D. Am. D. Zorin. Sagara et al. I. Engl. VCH. 10. N. Chem. B 2001. N. Liu. Y. Langmuir 1988. Morita.. Physics and Astrophysics of Carbon. 340. H. 1766. Martin. Sagara et al. Phys. A. Adv. H. 1993.. R. 2671. Nakashima. Chem. 3442. 5004. F. 1998. New York. I. T. B 1999. Lett. Buckminsterfullerenes. 304. The Netherlands.. Chem. Y. Lett. 13. J. 2. 1993. K. 17. 3343. Ed. Chem. M. 8. Liu. Langmuir 2002. I. H. 257. ı e I. Kunitake.. 38. 7.. Hungerb¨ hler. J. 1994. Chem. E. Chem. 2272. Chem. T.. Chem. 227. Ed. Echyegoyen et al. Tsuruta. 20. Guldi. Chlistunoff. Bull. 18. M.. Noda. Mitsuishi. Luengo. Am. Murakami et al. 31. M. Nonaka et al... Bard. Nonaka. Yilmaz. Metzger. 12. A. Jaiswal. Peterson. Y.. 3386. J. Y.. 12789. T. Am. M. 2001.. 18. 440. 3803. H. Chem. Azumi et al. Lett. 1998. J. 8. 19. Chem.. Langmuir 1994. 1775. J. Lakshmikantham et al. M. 3. Chem. B 2001. M. N.. T. (Eds. K. V.-D. u J. Tanaka. Jpn. Murakami.-E. Ishii. Nakanishi.6 References 1... 1021. J. Gorbunova. u Porphyr. 382. The construction of such artificial nanomolecular devices is a great challenge in the near future. Y. Nakashima. Kunitake. ı e J. M. J. Nakashima et al. Int. Chem. E. 37.. H. W. Ariga et al. T.4. 33. 36. Y. Tokunaga. 19. 7280. Int. Okahata. 22. Lett. 25. 166. Engl. 39. 2003. 2003. 105. Matsui. J. T. 1997. 2003. M. Cambridge. 14. 1. Murakami.. Soc. Chem. 2002. Nakashima. and carbon nanotubes. phthalocyanines. 23. 9817. K. proteins and fullerene derivatives. 17. 14. 35. Aoki et al. Jpn. M. 4484. R. D. 42. 7. Langmuir 1995. Sagara et al. Ebara. Nakanishi. Phys. Cambridge University Press. 108. Phys. R. 1993.. 1995. O. J. Nakashima et al. A. 7754. Rev.. I. K. Samuel. R. Amaresh. Tokunaga et al. 12. Nakashima. J. 11. 3. Ijiro et al. Soc. Nakashima. Cardullo. Faraday Trans. 34.. Narikiyo. B 2003. 37. Rodr´guez-M´ ndez. T. L. Nakashima. I. 102. 7. 4. N.). Nakanishi. K. T. From Synthesis to Optoelectronic Properties. 9560. Nakanishi. Langmuir 1998. Shigehara. M. Y. 1996. 65. Tachibana. Nakanishi. 18.1. T. M. Billups.. M. Ultrathin films with ordered structures on substrates should be promising nanomaterials for future nanoelectronic and molecular-information transducers with controllable and fine structures at the molecular level. 10. A.). Narikiyo et al. L. Guldi. Y. 24. Fullerenes. A. 67. J. B 1998. T. Ciufolini. H. Katagiri et al. D. 10042. T. Nasu. 32. K. 4. Phys. Angew. 113. 2497. Diederich. 28. A. W. Watanabe. Soc. T. 26. . Thin Solid Films 1995. Langmuir 2001. S. 14. M. 520.. T. Asu mus. Kroto. F. 5. Nakamura et al. 29. The Fullerenes. P. 1991. Soc. Nakanishi. Campbell. Abe. 2002. I. 15. 1955. Eur. 103. R. Mouri. K. N. Beeby et al. Bull. Langmuir 2003. 9. N. Chem. Kadish. K. Nasu. H. 1219. J. Srdanov et al. 2001. N. Phys. T. A. Soc. W. Langmuir 1998. 2267. 633. Matsumoto. 21. Hara et al. 9043. Angew. Nature 1996. Sluch. Nakanishi et al. N. K. Chem. S. 115. Qiu et al.. 68. 105. de Saja. 118. Chem. 639. Chem. Eur. T. Phys. 27. J. Metzger. Chem. 6. J. 7328. H. Nakanishi. G. Y. Nakanishi. T. Murakami. Mater. N. artificial lipids. Xu.. J. Soc. N. M. Phthalocya. Funct. M. 107. Shirakusa et al.. E. T. Kluwer Academic Publishers. 2002. K. K. Phys. Chem. Rodr´guez-M´ ndez. T. Manabe et al. T. H. B 2004. (Eds. 16. Hirohashi et al. Phys. G¨ rek et al. 30.. Cliffel. 103.

. Zhou. Cassell. Vuorimaa.. K. 76. Krstic. S. Mamedov. R. 2004. Ed. G. Properties and Applications. K. S. R. Zhou. T. Chem. Dai. J. Iijima. W. G. 284. H. Burger. M. A. 46. 2000. Soc. Chen. 1340. Science 2001. 1999. S. P.. 366. 2403. 68. Soc. Langmuir 2004.. Iijima. 603. 62. Yanagida. Sakata. C. N. Chem. A. Nobutsugu et al. Wallace. Nikkanen et al. 42. 323. 245. . S. S. 1997. 56. N. 102. F.. Taniguchi et al.. Shiratori. Soc. Appl.. J. Uemura. C. Am. Di Luccio. 2002. Zhou. 58. The Science and Technology of Carbon Nanotubes. A. 59.. Chem. 42. Tanaka. Barisci. A. Phys. Synth. 327–329. Oxford. Bull. Williams. S. 41. Elsevier. 66. T. G. Baughman.. Goldenberg. Mater. 2077. J. Met. V. R. G. K. 354. Met. 73. S. J. 65. 52. Krstic.. Tkachenko. Chu et al. Hirayama et al. (Eds. Harris. S. 2000. M. 245. P. S. Berlin. Shiratori. 1999. F.. L. Uemura. Phys. 50. 61. 2000. D. 16. 1944. Asplund. 3773. Nature 1991. 291. 20. Vehmanen. 110. D. Fukui. Int.210 1 Preparation of Monolayer Modified Electrodes 40. Avouris. R. (Eds. Duesberg et al. 6371. T. 47. Ikezaki. Actuators. Gan. V. 1999. 43. Carbon 2004. C. N. J. 1996. 60. N. Kajiyama. S. Kesti et al. 70. 747. D. 103. C. Chem. 46. Synth. 509.). Kobae. 1429. M. G. Structure. Prato et al. M. Chem. 69. Kohno. Maultzsch. Chem. 2000. Chem. 2540. Carbon Nanotubes: Basic Concepts and Physical Properties. Tkachenko. E. Murakami. J. 118. M. Acta 2000. 1997. B 2000. T. M. Nakashima.. S. 456. M. L.. J. Nat. Zhu et al.. C. Angew. 67. Condens. S. S. 45. 655. Takahara. I. A 2000. A. Nature 1993. Rajan et al. G. B. J. 38. 2002. J. B. Jpn.. Duesberg et al. Tour. S. A. Ashwell. Bryce et al. 1310. Commun. 17. Sakata. Guo. Mauzerall. H. Langmuir 2001. Yamabe. M. Mimami. Chem. Reich. Minami. N. Zakhidov et al. Phys. Carbon Nanotubes: Synthesis. Met. Ishii et al. Electrochim. 64. Aversa et al. Faraday Trans. Baughman. Synth. P. K. H. 64. Phys. K. 2003. Dresselhaus. Chem. Lett. 2719. J. 1993. 44. Cui. Science 1999. V. Thomsen. 2002. Wiley. T.... 51. T. Thin Solid Films 1998. G. N. Sano. 190. M. Cambridge. Shimizu. L.. 56. Matter 2002. Engl. Ichihashi. 55. 5791. J. L. 1999. 135–136. 53. 63. 93. Y. Carbon Nanotubes and Related Structures. Lett. Muster. H. Dresselhaus. 57. Antolini. 9198. 49. Chem. C. Soc. N. Physica. 54. 5. Q. M. 891. Springer-Verlag. Kotov. Langmuir 2000. M. 1119. 235. Sens. V. Y. M.). Oishi. Berlin. Kim. V. 3. Niu. 48. 1. Cambridge University Press. Luo et al.-P. K. Sold State Commun. M. Yamada. Burghard. 104. 363.

Soluble carbon nanotubes in aqueous and organic systems are of interest since their study allows the 1. respectively. We have reported that LB films of π-conjugated electrochemically active quinolinium complexes transferred on to gold electrodes show rectified transmembrane electron transfer. phthalocyanines. and J.Edited by A. Electrochemistry of LB Films of ‘‘Molecular Wires’’ and Phthalocyanines It is known that LB techniques can be applied for the construction of thin film electronic devices and molecular rectifiers [1–5]. Japan chemical and biochemical design of functional carbon nanotubes. 10 Modified Electrodes.J. The fifth reduction had been theoretically 1.4. the electrochemistry of Langmuir–Blodgett (LB) films of functionalized molecules including ‘‘molecular wire’’ compounds.1. Fukuoka. The double-decker lutetium(III) phthalocyanine molecules having long alkyl chains (Fig.2. Japan Naotoshi Nakashima Kyushu University. The formation of thin fullerene films including fullerenelipid hybrid and fullerene-lipid composite bilayer membranes is of interest both from a fundamental and practical application point of view. proteins and fullerene derivatives. encouraging the application of such techniques to biomimetic membranes in aqueous media. 3]. Ultrathin films of electrochromic molecules such as multireducible doubledecker phthalocyanines are one important possible component of color display devices. proteins. 1) on electrodes by scanning tunneling spectroscopy (STS) [1. 7]. and specific functions. and antibodies as biosensors or biomolecular switches because of their high sensitivity for their substrates and antigens. The unimolecular electrical rectifiers prepared by using LB techniques are useful for the construction of molecular electrode devices [1–5]. artificial lipids. Stratmann Vol. constructed electrical rectification systems using LB monolayers of substituted quinolinium tricyanoquinodimethanides (Fig. Tsukuba.1 Encyclopedia of Electrochemistry. to hexacyanoferrate(II) ([Fe(CN)6 ]4− ) in solution [6. We describe here how to make ultrathin films of nanotubes on substrates. 2) were mixed with amphiphilic matrices and cast on electrodes as thin films [8–10]. Conjugated redox-active compounds are candidates for ‘‘molecular wires’’ and are expected to be a convenient tool for the construction of molecular electronic devices.F. Multiwalled carbon nanotubes (MWNTs) and single-walled carbon nanotubes (SWNTs) are novel nanomaterials that have remarkable electronic. mechanical.2 Langmuir–Blodgett (LB) Films on Electrodes (B) Electrochemistry Takashi Nakanishi National Institute for Materials Science (NIMS).Fujihira. Edited by M.4. Bard and M. and carbon nanotubes (CNTs) is described.2. KGaA.Rubinstein.ISBN: 978-3-527-30402-8 . Potential-step chronocoulometric responses revealed that the LB monolayer acts as an organic ultramicroelectrode array. Metzger et al. I.4 Langmuir–Blodgett (LB) Films on Electrodes 203 1. and thermal properties. It is of interest to use monolayer and LB films of enzymes. These phthalocyanines undergo up to five reductions at the modified electrode.4. through the LB monolayer. The use of electrodes modified with immobilized redox-active molecules provides a simple methodology by which to study the ultrathin film electrochemistry of water-insoluble redox-active molecules.Rusling Copyright  2007 Wiley-VCH Verlag GmbH & Co. Weinheim.2 Introduction In this chapter.

coated a SnO2 electrode with LB films of synthetic phospholipids [15]. Multicolor electrochromism. Oxidation peak currents of a maker ion ([Fe(CN)6 ]3/4− ) in the aqueous phase through the lipid films increased with the addition of Ca2+ ions only when the LB films were in the fluid liquid crystalline phase above the phase transition . and purple. green. blue. and esters. Okahata et al. 1 + N NC CN − CN Chemical structures of the quinolinium tricyanoquinodimethanides. use of cationic matrices is important because reduced anions of the phthalocyanines can be stabilized in these matrices. 13]. Saja et al. that is. aldehydes. reported that LB films of rare-earth metal double-decker phthalocyanines deposited onto indium tin oxide (ITO) microelectrodes have sensing properties for NO gas and vapors of volatile organic compounds such as alcohols. brownred.204 1 Preparation of Monolayer Modified Electrodes + N NC CN − CN S O Fig. 2 Chemical structures of the alkylthio substituted double-decker lutetium(III) phthalocyanines. are observed at LB films of octakis-substituted heavy rare-earth metal double-decker phthalocyanines in contact with an aqueous electrolyte [11]. which are contained in aromas of foods and beverages [12. Moreover. predicted but had not been previously observed for any double-decker lutetium phthalocyanines. Fig. LB films of artificial lipids transferred onto electrode substrates could be used as glucose [14] and calcium ion [15] sensors and for hydrogen evolution [16].

reported electrochemical hydrogen evolution using LB films of hydrogenase protein complexed with poly-L-lysine. 3). The lipid LB film modified electrodes provide a suitable interface for the electrochemistry of cytochrome c [18] and myoglobin [19]. developed a novel type of vitamin B12 -functionalized electrode [17]. Fig.1. The obtained electrodes have the potential to transform environmentally toxic chemicals into nonhazardous ones Lipid (EtO)3Si H N C O Vitamin B12 derivative OR O H RO O O H H RO N N N Co(II) N H through an electrochemical process. The LB films of glucose oxidase (GOD)artificial lipid monolayers deposited onto Pt electrodes act as glucose-sensing ultrathin membranes with a short response time [14]. 3 . Miyake et al. the synthetic artificial lipids provide suitable environments for the electrochemistry of redox-active biomolecules. in which the monolayer properties of the vitamin B12 mimics were investigated as a mixed monolayer with an organosilane lipid (Fig.2. Ariga et al. C60 alone and amphiphilic fullerene derivatives form monolayers at the air–water interface and these monolayers can be transferred onto solid substrates [23–27].4.4 Langmuir–Blodgett (LB) Films on Electrodes 205 temperature since Ca2+ ion can only bind and penetrate into the fluid liquid crystalline phase of the films and disturb or expand the LB membrane structures.3 O C N RO O O OR RO R= O O OR Chemical structures of the organosilane amphiphile and vitamin B12 derivative. Langmuir Monolayer of Fullerenes at the Air–Water Interface The construction of fullerene ultrathin films with an ordered structure is of interest from both a fundamental and practical point of view [20–22]. The authors [28–38] and others [39–43] have been interested in combining fullerene chemistry and the 1. Thus. in which methyl viologen was used as a mediator [16].

which is the subphase transition temperature of the cast films of the fullerene lipid [28. 36. and characterization of a C60 -bearing triplechain lipid [28.3 dC60 = 1. In situ X-ray reflectometry (XR) techniques revealed the nanostructure of the fullerene-lipid monolayer on water.98 nm2 /molecule. suggesting the formation of monolayers with hexagonal and simple square packing.0 nm Water rwater = 1. This lipid forms stable Langmuir monolayers at the air–water interface [32. The electronic interaction between the fullerene moieties can be controlled by the phase change of the film. 4). At lower temperatures. 4 Chemical structure of the fullerene lipid. there is an electronic interaction between the fullerene moieties in the LB film. The LB film prepared in the dark shows temperature dependent UV–vis absorption spectra. 37]. We have reported the design. 5). 32. Upon heating over 47 ◦ C. chemistry of lipid bilayer membranes. synthesis. 36].0 Fig. that is. respectively [32]. . 33.9 dlipid = 1. 5 Schematic illustration of the nanostructure of the monolayer of the fullerene lipid on water revealed by in situ X-ray reflectometry measurements. indicating that the molecular orientations of the rlipid = 0. the electronic interaction of the fullerene moieties is loosened.2 nm rC60 = 1.206 1 Preparation of Monolayer Modified Electrodes Fig. the fullerene moiety was in contact with the water surface and Air rair = 0 the lipid tail extended to the air [37] (Fig. The fundamental property of the self-assembled bilayer membrane film is maintained in the LB film prepared in the dark. 37] (Fig.78 and 0. The surface-pressure–area isotherm of the fullerene lipid gives limiting areas of 0. which may create a novel field in the chemistry and biochemistry of fullerenes.

and n-octadecane in the gas phase [50. but this was not observed in all of the cases. β-caryophyllene. The second-harmonic intensity is strongly dependent on the number of layers of the LB films. have studied basic electrochemistry of C60 fullerene LB films on an electrode in acetonitrile solutions [23].4. The ‘‘wet process’’ method consists of the transfer of Langmuir films of fullerene onto iodine-modified Au(111) surfaces at an air–water interface followed by the electrochemical removal and replacement of iodine adlayers with fullerene adlayers in solution.4 Langmuir–Blodgett (LB) Films on Electrodes 207 fullerene moieties of the LB film and cast film of the fullerene lipid are not significantly different.2. Bard et al. poly(allylaminehydrochloride) (PAH). citral. described the preparation of LB films of a phytochlorin-fullerene [52] and of a porphyrin-fullerene [53] that show vectorial photoinduced electron transfer reactions (Fig. is reported to be a novel sensor for α-pinene. The study on C60 LB films has become a focus of considerable interest. Spatial control of arachidic acid LB films by introduction of C60 molecules as the spacers to a polymer backbone. Tkachenko et al. Nerilidol. electrochemical characterization of the higher-quality LB films was performed. Subsequently.1. however. developed the electrochemical replacement method to form epitaxial adlayers of fullerenes on Au(111) surfaces [45]. it is difficult to fabricate high-quality LB films of pure C60 due to its intrinsic hydrophobicity. Kunitake et al. As an alternative way to avoid the formation of low-quality aggregated structures of fullerenes.4 technique by in situ scanning tunneling microscopy (STM) for the surface morphology of fullerene LB films on iodine-modified Pt(111) surfaces was also developed [46]. The LB films of a crowned C60 -pyrrolidine [48] and of a 4-acetylphenyl-substituted C60 -pyrrolidine [49] exhibit optical second-harmonic responses. which is regularly packed in a hexagonal array [44]. 6). This is important from the viewpoint of the introduction of lipid bilayer properties of the fullerene lipids to the LB system. These donor–acceptor dyad LB film systems are an attractive example for the development of molecular optoelectronic devices. A visualizing 1. 51]. applied a multistep creep method as an LB technique for constructing a fairly homogeneous C60 monolayer. Models of natural photoreaction centers can be constructed using LB films of fullerene derivatives. The electrochemistry of LB films of fullerene derivatives in organic solvents showed well-defined reversible multi-electroreductions [47]. several functionalized fullerene derivatives with nonpolar or polar groups were synthesized. Kajiyama et al. The fullerene adlayers prepared by this method showed excellent quality and uniformity. LB films of fullerenes have several intrinsic properties such as nonlinear optical features and gas sensing. . Electrochemistry of LB Films of Fullerenes on Electrodes Electrochemistry of LB films of fullerenes has been widely studied and remains the subject of much research effort from both theoretical and experimental approaches. This information is useful for the design and construction of functional supramolecular ultrathin fullerene films at the air–water interface and on solid surfaces. The study indicated that reduction of the fullerene films could form insoluble films with incorporated electrolyte cations or lead to dissolution.

described the formation of monolayers of SWNTs and a surfactant on substrates with lithographically defined electrode arrays [63]. and thermal properties. Krstic et al.2. mechanical. Preparation of carbon nanotube/polyelectrolyte thin films by the layer-by-layer technique has been reported [67]. 6 Chemical structures of the phytochlorin-fullerene (left) and porphyrin-fullerene (right) dyads. respectively. carbon nanotubes have been at the forefront of nanoscience and nanotechnology because of their remarkable electronic. The 1.208 1 Preparation of Monolayer Modified Electrodes Fig. [64] prepared optically homogeneous and structurally controlled (oriented) LB films from soluble SWNTs. However. Barisci and coworkers [69] reported EQCM studies of SWNTs dispersed in water or in acetonitrile.5 current/voltage characteristics showed a nonlinear dependence with steplike features. and then the formation of SWNT films from the solution by electrodeposition. called carbon nanotube papers [60] and carbon nanotube films by physical adsorption [61] is already known. and specific functions [56–59]. Ultrathin composite films of carbon nanotubes and amphiphiles are formed by means of the LB technique [62]. Since the first findings. We have reported the dissolution of shortened SWNTs in aqueous micelle of an electroactive surfactant. [65] Luccio et al. 11-ferrocenylundecy poly(ethylene glycol). Carbon nanotube ultrathin films described earlier are considered to possess ordered and oriented structures and therefore these films may be useful for the construction of optical and optoelectronic devices. By utilizing soluble nanotubes. LB film formation of crown ether-modified soluble MWNTs and SWNTs have been reported by Guo et al. Minami et al. They measured the electrical transport of the electrodes. [66] described the formation of LB films of SWNTs and behenic acid with densely packed and uniform coverage on hydrophobic Si(100) substrates. Soluble carbon nanotubes in aqueous and organic systems are of interest since their study can lead to the chemical and biochemical design of functional carbon nanotubes. carbon nanotube ultrathin films can be formed. whose process was monitored by an electrochemical quartz crystal microbalance (EQCM) [68]. reports describing the preparation of thin films with high homogeneity from purified-carbon nanotubes dissolved or dispersed in solution are very limited. The preparation of carbon nanotube sheets.4. Carbon Nanotube LB Films Iijima discovered MWNTs [54] and SWNTs [55] in 1991 and 1993. .

Ebato. 7280. Phys. Ultrathin films with ordered structures on substrates should be promising nanomaterials for future nanoelectronic and molecular-information transducers with controllable and fine structures at the molecular level. 34. Engl. New York. Lett.. T. Bull. Angew. J. Chem. 19. 3. R. 103. Billups. 37. 28. Chem. Sluch.. M. 2267. 327–329. T. 12789. and carbon nanotubes. Guldi. T. Chem. 639. J. Guldi. J. u J. A. Okahata. Chem. J. H. 2003. Langmuir 1998. Langmuir 2001. Cliffel. A..2. 17. 1021. 3803. J. Y. M. 2272. 166. Qiu et al. Y. 3343. S. 9. Echyegoyen et al. Chem. 12. 1775. 26. Jaiswal. Phys. Chem. ı e J. K. Nakanishi. 30. 118. 1991. Ohwaki. Y. Kunitake. Cambridge. K. N. 2003.. E. 14. Kalashnikova et al. J. F. Chem. 9560. Eur. 382. Nakanishi... Ariga. Nakanishi. 1. Nasu. K. T. Int. J.1. 105.. Nakanishi. 2. M. K. 22. Int. Chem. Funct. I. 227. A. 13. E. Ciufolini. R. K. 1993. V. 304. Yilmaz. Soc. R. Lett. Bard. Tokunaga. Diederich. Nakamura et al.. B 2001. phthalocyanines. 21. W. W. 113. 440. T. N. 1993. W. T. Lakshmikantham et al. Asu mus.. V. Phys. A. Jpn. Matsumoto. M. 3442. Bull. A. 16. 67. M.. K. S. Chem. M. I. 2497. T. T. R. Cardullo. Soc. M. Watanabe. Samuel. 14. 42. L. 35. Lett. 1998. L. M. Ed. M. de Saja. u Porphyr. Nakashima. 1996. Nakanishi. Y. 1641. J. I... Langmuir 1994. 105. Zorin. M.. Ijiro et al. 27. Murakami et al. 20. 18. 115. 1766. Nature 1996. D. 9817. 18. Eur. Phys. M. artificial lipids. T. K. H. Ed. Faraday Trans. 107. 10042. N. Beeby et al. Chem. K. Fullerenes. Chem. Phys. K. 1997. C.-E. T. K. Chem. E.. Nakashima. 2002. Shigehara. Langmuir 1998. Buckminsterfullerenes. H.-D. Mouri. Hara et al.. G¨ rek et al. Y. Phys. 1995. 10. T. 11. 17. The Netherlands.. 7328. 2001. Sagara et al. Morita. 103. Cambridge University Press. Thin Solid Films 1998. Chem.. Kadish. Langmuir 2001. Liu. A.. F. 4484. Phys. H. G¨ rek et al. Mitsuishi. H. 68. 31. Chem. Rev. 2000. Chem. 10. Murakami. 520. H. . Murakami. Adv. T. 1219. T. Narikiyo et al. Nakanishi.. 19.. Langmuir 2003. Kroto. Tsuruta. Mater. 1998. 7. R. Am. Sagara et al. Luengo. M. proteins and fullerene derivatives. A. T. L. O.. Soc. Ishii. R.. Soc. J. 2001. Nakashima. 18. T.. Tachibana. N... 5004. T. N. B 2001.. M. J. 108. 2671. B 1999. Langmuir 1988. Hirohashi et al. 9043. 3386. 65. 5. 1993. 1955. Rodr´guez-M´ ndez. Ariga et al. A. Nasu. N. H. 660. 37. Kuriyama. Sagara et al. I. 2002. Nakanishi et al. T. Nakashima. N. 23. Nakashima et al. Noda. Nonaka et al. ı e I. The Fullerenes. The construction of such artificial nanomolecular devices is a great challenge in the near future. Abe. Angew. M. K. A. Y. Chem. H. M. 12. Hungerb¨ hler. Langmuir 1995. 7. Aoki et al. Liu. Kluwer Academic Publishers. A. J. B 2003.). Peterson. N. Murakami. (Eds. N. Chem. 340. 1998. From Synthesis to Optoelectronic Properties. H. 33. Thin Solid Films 1995. Nakanishi. Yilmaz. W. Nakashima et al.6 References 1. D. 257. 15. Nakashima. Nakanishi. J. VCH. Nonaka.. F. Soc. H. Tanaka et al. Chlistunoff. Soc. M.. New Horizons for the Chemistry. 8.). Azumi et al. 39.4. Y. K. Chem. Gorbunova. M. Nakashima. B 2004.4 Langmuir–Blodgett (LB) Films on Electrodes 209 Conclusions We have reviewed a recent progress on the electrochemistry of LB films and related films of functionalized molecules including ‘‘molecular wire’’ compounds. P. Zhou. 24. 36. Campbell. 32. 1994.. Y. Chem. 8. N. Ebara. 1373. N. Y. T. Narikiyo. Langmuir 2002. Phys. 2003. T. Metzger. Y. Engl. 3. Tanaka. H. Matsui. 633. Martin. 1995. 4. Nassar. 4. Phthalocya. Xu. Physics and Astrophysics of Carbon. 375.. 11. J. Shirakusa et al. Am. 7. Gorbunova. G. Amaresh. Chem. Tokunaga et al. Srdanov et al. Chem. Katagiri et al. Chem. Manabe et al. Jpn. Y. 2002. D. I. 29. I. Rodr´guez-M´ ndez. Chem. 14.. B 1998. 38. Lett. 25. D. Am. 102. T. Metzger. J. 91. Murakami. J. Nakashima. Kunitake. Nakanishi. (Eds. 6. 7754..

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The L−B films have been of long standing interest in the chemical.5). critical phenomena. which renders a large fraction of nonionic molecules and some ionic amphiphiles water insoluble. termed Gibbs monolayers.1. phase transitions. amines. California 1. it is also possible to talk about a range of physical phenomena and practical applications that drive research in this area of science.J. 7]. Just as there exist numerous types of amphiphiles such as single alkane chain alcohols. Edited by A. the surface concentration of a compound can be controlled mechanically by sweeping the water surface with a Teflon barrier that confines the known quantity of the spread compound to a specific surface area of a Langmuir trough [2–7]. films of insoluble. typically amphiphilic compounds deposited on the water surface as solutions in volatile solvents such as chloroform. a Kelvin probe – an instrument measuring surface Encyclopedia of Electrochemistry.Rubinstein.5.Rusling Copyright  2007 Wiley-VCH Verlag GmbH & Co.5 Electrochemistry of Monolayer Assemblies at the Air/Water Interface Marcin Majda University of California. and J. and other related phenomena. Another class of structurally similar monolayer films involves water-soluble surfactants.F. ISBN: 978-3-527-30402-8 . KGaA. Langmuir monolayers constitute a relatively easy to control class of systems where physical phenomena such as ordering. As in the case of all liquids.1 Langmuir and Gibbs Monolayers at the Air/Water Interface The air/water interface is a unique platform for the formation of monolayer assemblies. Berkeley.1.5. Weinheim. Surface adsorption and the resulting Gibbs monolayers have long been of interest to scientists interested in surface rheology. molecular level methodology of forming ordered multilayer assemblies of controlled structure and composition [10]. formation of foams and emulsions. 1. form spontaneously at the air/water interface as a result of surface partitioning equilibria [8]. I. 10 Modified Electrodes. and monolayer dynamics [9]. Following spreading and solvent evaporation.2. a surface balance – allowing one to record surface pressure versus mean molecular area (π vs. the water surface is nearly molecularly smooth [1]. High surface tension and high polarity of water allow spreading of Langmuir monolayers. it is important to mention that Langmuir films can be sequentially transferred onto solid surfaces to form the so-called Langmuir–Blodgett films (see Sect. structure.5 Electrochemistry of Monolayer Assemblies at the Air/Water Interface 211 1. 5. Stratmann Vol. Edited by M. 1. Biophysicists regard Langmuir films as model systems of biological membranes and investigate the relationship between their composition. MMA) isotherms [2. A moderately high boiling temperature and partial pressure of water allow one to investigate monolayer films at the air/water interface in the temperature range of roughly 0–50 ◦ C. and materials sciences as a general.Fujihira. Bard and M. physical. Fundamentally. and dynamics of lateral transport can be investigated in 2D. A schematic diagram of a Langmuir trough. Finally. a shallow Teflon dish filled with ultrapure water commonly used to study Langmuir and Gibbs monolayer films is shown in Fig. Such instruments are typically equipped with a precision driven Teflon barrier enabling the control of the area of the water surface. various phospholipids and polymeric amphiphiles. Water is also a liquid of exceedingly high polarity. fatty acids and esters. wetting. These types of monolayers. Water has the highest surface tension of all molecular liquids.

The latter technique allows one to image morphology of surface films during compression. potential that can reveal the dependence of the surface normal component of an average dipole moment of the molecules spread on the water surface as a function of their MMA [11]. indeed. The working electrode resides at the air/water interface. 1 A schematic drawing of a Langmuir trough instrument. the main subject of this review.2 Horizontal Touch Electrochemical Characterization of Monolayer Films at the Air/Water Interface Horizontal touch is a term that can be attributed to Langmuir and Schaefer who . The potentiostatic setup shown in Fig. 1. Its type and design reflect a particular type of electrochemical experiment to be carried out to characterize monolayers on the air/water interface.5.212 1 Preparation of Monolayer Modified Electrodes Potentiostat Kelvin probe Surface balance Brewster microscope ca CC m D er a La se r Barrier W C R R a Fig. in Volume 3. Scanning Electrochemical Microscopy (SECM) is the subject of Sect. and (2) two-dimensional (2D) electrochemical measurements involving line microelectrodes positioned in the plain of the air/water interface. 13]. Several examples of this approach to the studies of Langmuir films were reported by Unwin and coworkers [14–17]. 1 and a working electrode touching the water surface are used to electrochemically characterize the surface monolayer film. Current versus distance dependence is recorded and analyzed as the disk microelectrode is slowly brought into a close proximity of a Langmuir monolayer film.8. This indirect method of probing charge transport in Langmuir films involves a disk microelectrode held in the subphase. Application of the electrochemical methods in the studies of Langmuir films is. For the sake of completeness. Since then two classes of experiments have been developed: (1) horizontal touch (HT) experiments involving a planar working electrode held directly above the air/water interface and contacting a monolayer film spread on the water surface.2. it is worth adding that scanning electrochemical microscopy (SECM) has also been applied to investigate Langmuir films. In the following sections. The use of electrochemistry to characterize Langmuir films directly at the air/water interface was introduced in the mideighties. and a Brewster angle microscope (BAM) [12. 3. we discuss these approaches and present key experimental results. directly underneath the water surface.

2 -bipyridine and bpy-C19 is a bpy ligand with a single stearamido moiety attached to one pyridine ring in 4-position) aggregate upon spreading forming large.5 cm2 ITO electrode touching Ru(bpy)2 (bpy-C19 ) film of submonolayer coverage (240 and ˚ 600 A2 /molecule). Compounds such as Ru(bpy)2 (bpyC19 ) (bpy is 2. solid domains within which each Ru(bpy)2 (bpy-C19 ) occupies an ˚ area of ca.1.’’ Early on. 120 A2 /molecule. The authors observed stochastic behavior in these experiments. The ECL emission was collected with a CCD camera to generate photographs of a section of the Langmuir monolayer contacted by the electrode surface. 1. In the third direction of their research. The wellknown sequence of reactions generated an excited state of the ruthenium complex. Their work proceeded in three directions. These experiments offered confirmation of the heterogeneous structure of the Langmuir monolayers of the ruthenium complexes. 20]. and then assayed electrochemically by HT voltammetry yielding detection limits of .2. Not every act of placing an electrode on the monolayer covered water surface resulted in making contact with the monolayer material. This technique was further developed by Miller. The authors proposed that experiments of this type. could be interpreted in terms of the average size of the 2D aggregates. and clearly reflected the fact that only a fraction of the water surface was covered with the solid aggregates of the compound. They demonstrated that µL volumes of such compounds can be deposited on the water surface in a miniature Langmuir trough.3) Horizontal touch electrochemistry carried out with a working electrode just touching the interface was first demonstrated by Fujihira and Araki [21]. These reacted with oxalate ions purposefully added to the subphase in a Langmuir trough. The probability of recording a voltammetric signal due to Ru(bpy)2 (bpyC19 ) oxidation depended inversely on the MMA of the ruthenium surfactant.1. Miller and coworkers developed a Langmuir monolayer imaging technique involving the electrogenerated chemiluminescence (ECL) phenomenon [23].5 Electrochemistry of Monolayer Assemblies at the Air/Water Interface 213 described a transfer technique of a monolayer from the air/water interface to a flat surface of a solid substrate [18]. They showed that by contacting a Langmuir film of a surfactant derivative of anthraquinone with a flat glassy carbon electrode. if done with electrodes of different surface areas. Repetitive HT voltammetric experiments were carried out each with a freshly cleaned 0. This involved lowering a plate onto the water surface ‘‘in a nearly horizontal position.5. they showed that HT voltammetry can offer sensitive means of detecting the presence of solid domains in Langmuir films [22]. they were able to electrochemically address the molecules forming the Langmuir film. In the second related direction of their research. On the one hand. HT voltammetry of Langmuir monolayers of Ru(bpy)2 (bpy-C19 ) (and of other ruthenium complexes) was used to generate Ru(III+) species. Their experiments involved indium-doped tin oxide (ITO) and pyrolitic graphite electrodes. Miller and coworkers used a similar methodology to transfer monolayer films on mercury electrodes and carry out electrochemical experiments with the resulting Langmuir–Blodgett (LB) type films in the subphase [19. Miller and Bard also relied on HT voltammetry of Langmuir monolayer films to develop a trace analytic method of determination of water insoluble redoxactive species [24]. Bard and coworkers [22–24]. The electrochemistry of LB and self-assembled films on mercury has been reviewed by Guidelli (see Sect. 2D.

Overall. The existence and the structure of the surfactant aggregates near the metal surface were investigated by reflectance spectroscopy and light scattering measurements [29]. At a sufficiently negative potential. The second conclusion of Lipkowski’s research is a discovery that the application of a negative potential results in the formation of small micelle-like aggregates of the surfactant desorbed from the metal/solution interface. Integration of the charge versus potential data yields plots of the surface pressure versus the electrode potential. Lipkowski and coworkers used the HT electrochemistry to study electrochemically inactive compounds such as octadecanoic acid in Langmuir monolayers under controlled surface pressure conditions [26–32]. The HT voltammetry with gold electrodes was also recently used to measure the surface partitioning constant of a soluble. The surface pressure of a monolayer at the water/air interface and at the metal/solution interface is the same only at the potential of zero charge. The surface pressure is at a maximum at a potential of zero charge. The results of these experiments can be summarized in the following two conclusions of fundamental importance. It then decreases with an increasing negative potential and thus increasing negative charge at the metal/solution interface. the surface pressure becomes zero. and that the process is reversible resulting in monolayer respreading at the metal/solution interface at less negative potentials [30]. The first one concerns the effect of the electrode potential. the HT measurements of the Gibbs monolayer formation constant were in agreement with their surface tensiometry and Brewster angle microscopic measurements [25]. They relied on the fact that the surface tensions of the air/water interface and of the liquid alkane/water interface are similar [8]. Lipkowski’s measurements demonstrated that in the HT experiments the electrode potential is the parameter controlling the surface pressure of a monolayer film at the metal/solution interface just as the surface pressure of a Langmuir monolayer is controlled mechanically by adjusting the surface area of a Langmuir trough [30]. The latter technique allowed the authors to precisely measure the charge density at the metal solution interface as a function of potential. These experiments involved single crystal gold (111) electrodes flamed prior to each HT experiment and then suspended slightly above the water surface (the hanging meniscus method) trapping a Langmuir monolayer at the metal solution interface.214 1 Preparation of Monolayer Modified Electrodes ca. Surface pressure is defined as the difference between interfacial tension in the absence and in the presence of the surfactant. The subsequent electrochemical experiments involved measurements of the interfacial capacitance and chronocoulometry. and corresponds therefore to the highest monolayer packing density. 2. redox-active surfactant at the air/water interface [25]. Malec and coworkers modified the surface of gold electrodes by self-assembly of short alkane chain thiols in order to mimic the thermodynamic properties of the air/water interface. The authors conclusively demonstrated a direct relationship between the electrode potential and the surface pressure of the surfactant monolayer on the metal/solution interface. indicating a complete desorption of the monolayer film. Lower detection limits were anticipated if much smaller electrodes and Langmuir apparatus were to be used. Additional electrochemical and spectroscopic work probing the questions of monolayer . The summary of these results is shown in Fig. Indeed. 1 pmol.

28). The answer was offered independently first by Miller [37] and coworkers and then by Lipkowski [38]. The straight line. The HT step led to the formation of a lipid bilayer structure at the metal/solution interface in which the bottom half of the bilayer constituted a Langmuir film on the water surface. the rate of this transport depends on the surface pressure gradient as well as on the structure dependent monolayer fluidity.0 [ −1 −0. 2 Thermodynamics of the octadecanol (C18 OH) monolayer films at the air/water (GS). Unlike the previous authors.4 0.2 Fig. represents conditions under which the surface pressure of the C18 OH film is the same at both interfaces (from Ref.5 Electrochemistry of Monolayer Assemblies at the Air/Water Interface 215 50 45 40 35 30 25 20 15 10 5 0 40 30 pMS [mNm−1] 20 −0. 39–41]. desorption and aggregation was reported by Bizzotto and coworkers [33–36]. The HT investigations of redox inactive Langmuir monolayers raised the question of whether monolayers at the metal/solution interface could respond to surface pressure changes at the adjacent air/water interface. and the electrode potential. It appears that a lateral monolayer flow from the air/water interface to the metal/solution interface is possible in cases of liquid films. Three-dimensional representation of the film pressure at the MS interface as a function of the film pressure at the GS interface (at the time of an HT experiment in which a freshly flamed Au (111) electrode is placed at the GS interface). and metal/solution (MS) interfaces investigated by the HT electrochemical methods.0 0. An entirely different application of electrochemical methods involving a horizontal touch approach was developed recently by Miller and coworkers [37. typically octadecane thiols. Miller used a gold electrode coated with a monolayer of long alkyl chain molecules.2 0. V .6 nal 8 − E Ratio] −0. Several different variations of this general 0 [m pG Nm S −2 ] 10 . drawn at E = Epzc . As discussed next.1.

In this experiment. Admittance data were collected for 18 different compounds forming Langmuir films. The FPs of different monolayer forming compounds were measured and shown to linearly depend on the square root of the surface pressure of a Langmuir film (see inset in Fig. 40. 4. The admittance – MMA isotherms correctly reflected the phase behavior. 4A). 3).216 1 Preparation of Monolayer Modified Electrodes scheme were developed and used for different purposes. At the triple line associated with the outstroke. Numerous lipids with different .63 and 0. at the electrode/air/solution triple line associated with the instroke. packing density. and with a constant segment of the cylindrical surface contacting the Langmuir monolayer coated water surface.10 cm. AC admittance is used to follow the time-dependent interfacial capacitance of the metal–alkanethiol/solution interface as the Langmuir monolayer flows into. The FP was shown to be a quantity characterizing the structure and dynamic properties of the two monolayer films involved in the flow experiments. that only liquid Langmuir films. respectively [37]. Steel and Miller used a rotating cylinder gold electrode with its cylindrical surface modified with an octadecane thiol monolayer [39]. Miller and coworkers devised a way to measure the flow rate of a Langmuir monolayer along the metal–alkanethiol/solution interface [37. such as oleic acid. metal-alkanethiol-monolayer/solution with a different interfacial capacitance. w is the length of the monolayer flow path into the metal/solution interface and CBi and CSAM are the values of the capacitance of the bilayer assembly and of the alkanethiol monolayer.7 rev/min. and subphase composition effects such as ion-inclusion and interactions with the monolayer films investigated by this new technique. The experiment begins when an amphiphilic compound of interest is spread on the water surface to form a Langmuir film at a given surface pressure (see Fig. FP [cm s−1/2 ]: FP = m w CBi − CSAM (1) where. The cylinder was rotated 0. In this position. respectively. This intricate arrangement of the modified cylindrical surface rotating against a Langmuir monolayer allowed the authors to continually measure the AC admittance of the metal/bilayer/solution interface as a function of the surface pressure of the Langmuir film. m is the measured slope of the capacitance versus t 1/2 plots. the author defined a flow parameter. In a different application of HT electrochemistry involving an alkanethiol-coated working electrode. 41]. or penetrates that interface to form a new interface featuring a bilayer assembly. 4. the rotation of the cylinder resulted in the monolayer transfer onto the section of the cylindrical surface contacting the subphase. are capable of laterally flowing into the gold-alkanethiol/water interface and exhibit measurable FP values. as well as their dynamic interactions. To interpret the capacitance versus time transients. the bilayer assembly formed at the metal/solution interface delaminated releasing the Langmuir monolayer. In their first paper. It can be clearly seen in Fig. The radius and the length of the cylinder were 3. Fluorescence microscopy imaging was also used to follow the progress of the lateral monolayer flow into the metal/solution interface. The electrode was positioned with the cylinder’s axis oriented parallel to the water surface. The plots of the capacitance versus time obtained for the oleic and stearic acid monolayers are shown in Fig. an alkanethiolcoated gold electrode is initially touching a clean water surface.

A compound that forms a Langmuir monolayer is deposited on the water surface. a slow. these authors showed that in the limit of long time equilibration (10–19 h).5 Electrochemistry of Monolayer Assemblies at the Air/Water Interface 217 Glass substrate Gold SAM Flowing monolayer Aqueous subphase Langmuir film source Wilhelmy plate Electrode Pt SCE Teflon trough Fig. The working electrode is touching the air/water interface. first a monolayer and then a bilayer of C15 –Py is formed on the gold/solution interface. surface pressure driven flow of 4pentadecylpyridine (C15 –Py) monolayer from the air/water interface to the gold (111)/solution interface was also documented by Lipkowski and coworkers [38]. the Langmuir film flows across the triple phase boundary into the SAM/water interface forming a bilayer. 41]. It immediately spreads to cover the entire interface. and Cd2+ ions [40]. This led the authors to develop a chemical sensor in which measurements of the FP were related to the concentration of H+ . Ca2+ . Using in situ neutron reflectivity measurements. 37). We also point out that electrochemically induced surface . The inset shows the Au-coated glass slide working electrode modified with a self-assembled monolayer (SAM) of dodecanethiol. Subsequently. The lateral flow is completed when the entire electrode/solution interface is coated with a bilayer (from Ref. The former involved a change of orientation of the C15 –Py molecules as it crossed the triple phase line of gas/liquid/metal to allow the pyridine head group to be oriented toward the gold surface. The effect of molecules and ions partitioning into the bilayer assembly was also discovered and investigated. structural features were investigated to develop correlations between FP and lipid molecular structure [37. The tail-to-tail type bilayer is then formed.1. In the independent investigations. 3 Schematic depiction of the Langmuir trough apparatus and the positioning of the electrodes used in the lateral monolayer flow experiments.

where a planar electrode touches a large section of a Langmuir film on the water surface.5. 1.40 Capacitance [mF cm−2] 1.20 1.00 0. Fig.60 1. Thus. 4 pressure gradients in Gibbs monolayers and the resulting monolayer flow phenomena (referred to as Marangoni effect) were investigated by Abbott and coworkers using different methods [42–44]. 37).80 0 120 240 360 480 600 720 Time [s] Lateral flow measurements of oleic and stearic acids at a 1-dodecanethiol modified gold electrode. The solid line is the best fit through the linear portion of the capacitance drop used to calculate the flow parameter (from Ref.00 0 5 10 15 20 25 Time1/2 [s1/2] 0.218 1 Preparation of Monolayer Modified Electrodes A 1. Plots of the electrode capacitance versus time for a C12 SH modified gold electrode prior to and after the application of excess oleic acid (filled circles) and stearic acid (open circles) to the air/water interface. or 2D electrochemistry refers to the methodology in which a ‘‘line’’ microelectrode is placed in the plane of the air/water interface to probe the dynamics of lateral processes that are evolving in a Langmuir monolayer near the line microelectrode [45].3 Two-dimensional Electrochemistry Unlike in the case of HT electrochemistry.20 1. two-dimensional. Inset: the capacitance data for oleic acid are plotted versus the square root of time.40 1.80 1.60 Capacitance/mFcm−2 1. there is a direct analogy between 2D electrochemistry and classical electrochemical measurements. Just as .

The latter is a direct result of the ‘‘confinement’’ of a chemical system to a quasi-2D Langmuir film [45]. As demonstrated quantitatively by Charych and coworkers. It consists 3D 2D w l .1. and thus this substitution does not change the units of the equation where this product appears. the equation expressing the diffusion controlled peak current in cyclic voltammetry ˇ c (the Randles-Sevˇ ik equation) is: ip = 2. are identical to those known and used to study 3D systems – except for the reduction of dimensionality.5 Electrochemistry of Monolayer Assemblies at the Air/Water Interface 219 a generic planar electrode immersed in a solution of redox species has been used to electrochemically investigate 3D systems.5. Reduction of dimensionality converts the product of the electrode length (l) and a reagent bulk concentration (C ∗ ) appearing in the cylindrical diffusion equations into the surface concentration ( ∗ ): C ∗ l ⇔ ∗ (see text and Ref. Figure 6(a) shows the pattern of the vapor-deposited gold film. 46). The drawings shown in Fig. by the product of the surface concentration of the electroactive species and the electrode length ( ∗ l) to obtain the 2D versions of those equations.69x105 n3/2 D 1/2 v 1/2 ∗ l (2) where D is the diffusion constant and v is the scan rate. and so on. As shown in Fig. It is also important to note that the diffusion constant defined by the Fick’s first law has the same units in 2D as in 3D. one must use cylindrical diffusion equations [46]. 6 illustrate the fabrication procedure and the positioning of a microelectrode at the air/water interface. cyclic voltammetry.3. chronoamperometry. 1. For example. 5.1 Fabrication and Characterization of Line Microelectrodes The exact positioning of the line electrode in the plane of the air/water interface is of critical importance. The two types of diffusion processes are analogous. It is accomplished by a self-positioning phenomenon involving a sharply defined gradient of wettability at the edge of a gold microband electrode. the 2D electrochemical techniques. Reduction of dimensionality can be accomplished by substituting the product of the bulk concentration of the electroactive reagent and the electrode surface area (C ∗ A) appearing in many 3D electrochemical equations. Note that the units of C ∗ A and ∗ l are the same. radial diffusion in 2D sets in. While the range of problems that can be addressed using 2D electrochemistry is different from those investigated by the classical (3D) electrochemical methods. the reduction of dimensionality eliminates the length dimension of the cylinder. and a hemi-circular diffusion profile near a line electrode in 2D experiments. the 2D version of Fig. When the length of a line microelectrode becomes short relative to the diffusion layer thickness. in such cases. the development of the line microelectrode created the opportunity to study lateral processes in Langmuir and Gibbs monolayer films at the air/water interface. 5 A cartoon illustrating development of a hemi-cylindrical diffusion profile near a band microelectrode in 3D.

These steps render all the surfaces of the gold-coated substrate hydrophobic (see Fig. and a strip of gold (typically 500 µm in width) running between them. a monolayer of octadecyltrichlorosilane (OTS) is formed on the glass surfaces of the gold-coated electrode substrates. Following vapor deposition of ∼100-nm thick gold film. 6b). only the OM monolayer on the gold surface is shown.220 1 Preparation of Monolayer Modified Electrodes Glass Gold 0. 10 × 30 mm2 ) can be used. the gold and glass surfaces were coated with monolayers of OM and OTS. (b) A side view of one half of the original gold-coated glass slide and its positioning on the water surface. The next step creates two line electrodes: the goldcoated glass slide is fractured in half along a line perpendicular to the gold strip drawn with a diamond pencil on the side of the glass substrate not coated with gold. respectively. Each of the two halves can be positioned at the air/water interface by touching the water surface with the clean. This exposes clean and therefore hydrophilic edge surfaces of the two halves of the slide. Prior to fracturing. (c) A line electrode at the air/water interface. The line of wettability formed spontaneously along the edge of the gold . of two circular areas. For clarity. The width of the gold strip can be varied from ∼1µm to a few millimeters. hydrophilic edge of the electrode substrate as shown in Fig.1 cm OM + OTS ~1. (a) The pattern of vapor-deposited gold on a glass substrate. It determines the length of the line microelectrode. The dotted line shows the fracture line of the glass slide creating two line electrodes. later used as electrical contact pads. 6 Design of a line microelectrode and its positioning at the air/water interface. and results in a substantially lower background current relative to a more commonly used thin Cr under layers. a monolayer of octadecane mercaptan (OM) is self-assembled onto the gold surface. The major steps include the following: The glass slides are first chemically treated with 3mercaptopropyltrimethoxysilane (MPS) to form a thin film that assures adhesion of the vapor-deposited gold layer via Authiol chemical bonding [50]. The detailed fabrication procedure of line electrodes can be found in the literature [46–49]. Thoroughly cleaned. Subsequently. The water contact angles on the treated gold and glass surfaces should be 110–115◦ . standard microscope glass slides (ca.5 cm ~ 500 µm H2 O (a) (b) (c) Fig. 6(c).

To this end. as well as on the cleanliness of the entire Langmuir apparatus. as shown in Fig. of the spreading solvent and monolayer samples. 1. Thus. While the list given in the following is perhaps not complete as the development of the 2D electrochemical methods continues. simple wetting of the gold microband results in self-positioning of the line electrode in the plane of the water surface. it outlines the main areas of research and suggests some future directions. The placement of the line electrode at the air/water interface should follow a monolayer spreading and solvent evaporation. the Langmuir monolayer technique offers accurate and precise means of controlling the surface concentration of the surfactant [2. 54] and 2.5. the necessary parameters to interpret voltammetric current in terms of D. This behavior results in linear plots of D versus MMA.2.1 Dynamics of the Lateral Diffusion of Surfactants on the Water Surface The lateral diffusion coefficients (D) of the electrochemically active amphiphiles can be readily measured using 2D chronoamperometry or voltammetry (see Eq.2. Those Fc derivatives with more polar groups such as amide diffuse slower than Fc ester derivatives carrying the least polar head group moiety in this group . Well-behaved line microelectrodes exhibit characteristics consistent with their nominal dimensions.6-tetramethyl1-piperidinyloxy free radical [25] were investigated as a function of their surface concentration. 51]. stable performance of each line electrode at the air/water interface is reproducible for as long as 30–60 min.2 2D Electrochemical Investigations of Langmuir Monolayer Films The ability to place a line microelectrode in the plane of a monomolecular film at the air/water interface opened the possibility of investigating phenomena intrinsic to this class of chemical systems. however. between the hydrophilic gold cross-sectional area and the hydrophobic (OM-coated) front face of the gold strip. The charge due to the underpotential deposited Pb ad-layer is also commensurate with the geometric cross-sectional area of the Au microband [48]. and monitoring current limited by the resulting lateral diffusion. We point out that by generating a gradient of redox species in a Langmuir monolayer. Thus. 1. In all cases. 2 given earlier and the related discussion).5 Electrochemistry of Monolayer Assemblies at the Air/Water Interface 221 microband. Inevitably. 7 featuring data for several Fc-dodecane amphiphiles with different polar groups [54]. and the chain length. functions as the line electrode. We also learned from these results that the head group polarity is the second important parameter. the lateral diffusion constant was found to decrease with the increasing surface concentration suggesting that the monolayer viscosity is an important parameter.6.3. Depending on the purity of the water. 7]. The latter has been used to probe lateral diffusion of the fluorescently labeled phospholipids in Langmuir monolayers [52] and in supported lipid bilayers and biological membranes [53]. the 2D electrochemical measurements are analogous to the fluorescence photorecovery after photo-bleaching (FRAP) [4. the polarity of the group linking the redox moiety to the alkane chain. This process tends to be irreversible and the electrode must be discarded.3.1. charging current recorded with a 500-µm long electrode on a 50-mM HNO3 subphase in a 100 mV s−1 voltammetric scan is typically 10 pA [49]. Several amphiphilic derivatives of ferrocene (Fc) [48.5. their performance begins to deteriorate due to adsorption of impurities. 5.

0 50 60 80 70 Mean molecular area (Å2/molecule) 90 C D 100 Fig. .5 × 10−6 B 1. 54).0 × 10−6 2.5 × 10−6 A D [cm2s−1] 2. 7 Structures of four ferrocene amphiphiles with different head group polarities and the corresponding plots of their lateral diffusion constants versus MMA obtained using 2D electrochemistry on the water surface (1 M HClO4 ) at 26 ◦ C (from Ref.0 × 10−7 0.0 × 10−6 5.0 × 10−6 1.5 × 10−6 3.222 1 Preparation of Monolayer Modified Electrodes O O Fe (a) O Fe (b) HO Fe (c) O N H Fe (d) 3.

5 Electrochemistry of Monolayer Assemblies at the Air/Water Interface 223 of compounds. this discrepancy is due to the effect of the viscous drag of the polar head groups in water.1. Counter intuitively. where Af = A − A0 . 1. was more than 3 orders of magnitude smaller [54]. A far more complete picture regarding surfactants lateral mobility was obtained for the 2. Specifically. respectively. and only a small fraction originates in the monolayer’s hydrocarbon region. It revealed that the lateral diffusion constant of the Fc amphiphiles does follow the expected linear dependence on the relative free area. The surface concentration dependence of the lateral mobility of Fig.4 A. 65]. Finally. Similar observation was reported recently in the case of viologen surfactants [59]. 8) [54]. in a slab of the same height and a certain viscosity bounded by a medium of a different viscosity.5.2. 56]. 8 was related to the modulation of the amide group immersion depth by chain–chain interactions. These values depended neither on the surface concentration of the Fc surfactants nor on the viscosity of subphase. To account for these results. (See the structure of C 16 Tempo. those Fc-amide derivatives with longer chain length exhibited slightly larger diffusivities.2.0 A and 6. Clearly. The data discussed earlier concerned the lateral mobility in the liquid region of the Langmuir films spanning a range ˚ of MMAs of ca. which are supercritical fluids at room temperature and thus do not undergo a L/G phase transition [49. 64. as discussed in Sect. to the subphase solutions. a surface inactive compound. and A0 is the molecular area of a surfactant molecule. h. 50–100 A2 /molecule. This treatment of the experimental data also showed that over 90% of the viscous drag experienced by a surfactant molecule diffusing in a Langmuir monolayer is due to its immersion in the aqueous subphase. A = MMA. It also revealed that the slope of this dependence which is expected to inversely depend on the molecular mass of a diffusing particle. As expected. Af /A0 .) The discovery of the supercritical nature of the Tempo surfactants (see .3. The latter was varied by adding glycerol. It concerns quasi u 2D diffusion of a cylinder-like particle of height. The latter approach was particularly successful. Our inability to probe surfactants’ mobilities at lower surface concentration was related to the liquid/gas (L/G) phase transition. we invoked the Saffman and Delbr¨ ck theory [60–62].6tetramethyl-1-piperidinyloxy free radical (Tempo) derivatives. The theory was developed to treat protein diffusion in lipid bilayers [60]. but it was also used to analyze lipid diffusion in membranes [63]. as well as in view of the Enskog theory of dense gases [57] extended by Alder’s molecular dynamics calculations to liquid densities [58]. Using this theoretical model. The notion that the polar groups of surfactants are immersed in water was proven by observing a linear correlation of D values with the inverse of the subphase viscosity [54]. a factor not included in the Enskog theory. our data analysis yielded the immersion depths of the C16 –Fc-amide and C12 –Fc˚ ˚ amide to be 4.6. the anomalous chain length dependence of Fig. the former does decrease slightly with increasing MMA.2. 7 was analyzed in terms of the free-volume theory of hard sphere liquids of Cohen and Turnbull [55. the effect of the alkane chain length was also investigated in the Fcamide series covering the range of 12 to 16 carbon atoms (see Fig. The latter observation also suggests that surfactant’s polar group is at least partially immersed in the subphase. and that the immersion depth is yet another parameter influencing lateral mobility.

0 × 10−6 5.5. 1. C16 Fc and C12 Fc vs.0 B C 50 60 70 80 90 100 Mean molecular area [Å2/molecule] Fig.0 50 60 70 80 90 B C 100 Mean molecular area [Å2/molecule] 2. 65]. O N N H O Sect. 9.05 M HClO4 subphase containing (A) 0.7 cP. respectively (from Ref. 54).0 × 10−6 A C16Fc D [cm2s−1] 1.0 × 10−7 0. Comparison of the data obtained for three different Tempo derivatives with the chain length ranging from C8 to C18 shows essentially no differences in the lateral mobility [25]. This range is extended to MMAs as high ˚ as 800 A2 /molecule [25.5 × 10−6 1.2) allowed us to measure their lateral mobility in a far broader range of surface concentrations.1.3. We concluded that .9.5 × 10−6 2. The viscosities of these solutions were 1.0 × 10−6 5. and (C) 40 wt% glycerol.2. (B) 20.0 × 10−6 1.0 × 10−7 0. MMA measured on the 0. and 3.224 1 Preparation of Monolayer Modified Electrodes 2. as shown in Fig. 1.5 × 10−6 A C12Fc D [cm2s−1] 1. 8 Plots of the lateral D values of the ferrocene-amide derivatives (see structure D in Figure 7).

a significantly higher concentration range was investigated. and the effect was related to the dependence of the surfactant’s immersion depth on the chain length and not directly to the chain–chain interactions. we have recently examined the orientation of C18 Tempo on the water surface using X-ray reflectivity [65]. To this end. The latter . As shown earlier. but not by the chain–chain interactions. This phenomenon is perhaps related to the change in the dynamics of intermolecular collisions. Analysis of the various conformations of this head group suggested that it is not possible for both the nitroxide and amide groups to be immersed in water without also immersing a large fragment of the piperidine ring. 25). This effect was observed in the Fc studies [54] and is consistent with the behavior of particle–fluid suspensions [66. and C18 Tempo (open squares) (adapted from Ref. In the limit of very low surface concentrations. their mobility is limited primarily by the viscous coupling of their polar fragments to water. 9 Plot of the lateral diffusion constants versus MMA of C8 Tempo (closed circles). the nitroxide (>N−O). 8. since in that case. 9 at higher MMAs. 67]. C14 Tempo (open circles). this water insoluble surfactant features two polar fragments located on the opposite ends of the hydrophobic piperidine ring.5 Electrochemistry of Monolayer Assemblies at the Air/Water Interface 20 225 15 D × 106 [cm2/s−1] 10 5 0 0 100 200 300 400 500 600 Mean molecular area [Å2/molecule] 700 800 Fig. it is interesting to point out the change of the slope of the D versus MMA plot in Fig. This suggests that the analysis of the lateral diffusivities of surfactants with known and shallow immersion depths can reveal the dynamic properties of the water liquid/gas interfacial region. and their surface concentration. and the amide that serves as a linking group between Tempo and the alkane chain. the surfactant mobility appears to be limited solely by the viscous coupling of the polar head group to the subphase. 9 reflects the decreasing effective viscosity of the monolayer in the head group region as the concentration of the diffusing particles decreases. Finally. We also point out that this result is not inconsistent with the ferrocene-amide surfactant data of Fig. The increase of the D values with mean molecular area of the surfactants in Fig.1.

6tetramethyl-1-piperidinyloxy.226 1 Preparation of Monolayer Modified Electrodes Model 1 Model 2 89 Electrons 137 Electrons O 156 Electrons N O C NH 108 Electrons N C H Fig. Consequently. The detailed account of these measurements is beyond the scope of this review. we deconstruct the two C18 Tempo conformations of Fig. 10 into a stack of two boxes containing a different number of electrons (also shown in the figure). as it diffuses along the air/water interface. 10 O N O Schematic representation of two different conformations of C18 Tempo at the air/water interface at ˚ 52 A2 /molecule. This allowed us to simulate the X-ray reflectivity response and to compare the two models with the experimental results. 26. we report here on the X-ray reflectivity measurements at a single pressure of 21 mN m−1 (corre˚ sponding to an MMA of 52 A2 /molecule). is likely energetically too costly.2.2 vs. and are presented elsewhere [65]. The comparison is shown in Fig. Within each model. Briefly. 65). 69]. These were proposed assuming that either the amide group (Model 1) or the nitroxy group (Model 2) is hydrated. water-soluble surfactant [70]. Recently.6.1). Tempo itself. These are shown schematically in Fig.5 × 10−4 cm2 s−1 ) indicated that the air/water interfacial region is as much as four times less viscous than the bulk water [70]. a weak. A large lateral diffusion constant of Tempo (1. and present the key result that allowed us to distinguish between two opposing confirmations of C18 Tempo on the water surface. Thus. It is clear that Model 1. from Ref. the dotted line separates the molecule into two ‘‘boxes’’ with different numbers of electrons shown in the figure (see text. 10 where Model 1 assumes the dominance of the amide group and Model 2 assumes the dominance of the nitroxide group as the polar fragment immersed in the aqueous subphase. X-ray reflectivity is a technique sensitive to the gradient of the electron density in a molecular film at an interface [68. 11. Our investigations suggested that. we have also examined 2. Tempo is coupled to the interfacial region via a single water molecule hydrogen-bonded to its oxygen atom. While this result . assuming immersion of the amide group. offers a significantly better agreement with the measurements as quantitatively reflected in a much smaller χ 2 value (6. we postulated that only one of the two polar fragments is immersed.

This and later experiments carried out with the Tempo surfactants [49] showed that a line electrode functions as the monolayer gas phase nucleating site. the issues concerned with liquid. The latter is due to the fact that the amphiphile’s concentration in the gas phase is much smaller than that in the corresponding LE phase. these results illustrate how 2D voltammetry of shallowly immersed surfactants can contribute to the investigations of this important interfacial system. Measurements of the LE/G Phase Transitions and their Critical Temperature Characterization of the phase behavior of Langmuir monolayers.5 Electrochemistry of Monolayer Assemblies at the Air/Water Interface Fig. 12. specifically liquid expanded (LE).2 0. The solid and the dashed lines are fits to the data using the box models discussed in the text and shown in Figure 10 (from Ref. 65). and particularly its relationship to the lipid’s molecular structure. is of fundamental importance to the understanding of their behavior.5 ± 0. 1 Model 2 c2 = 26. Recent work involving monolayer X-ray diffraction methods [71] and BAM [12. not unlike the well-known ‘‘boiling chip’’ phenomenon. it gives the first direct experimental assessment of the dynamic nature of the aqueous interfacial region.3.2.5 ◦ C [49].4 0. apparently involves preferential wetting of the line electrode with the freshly nucleated bubble of the 2D gas phase and results in loss of electrochemical signal.6 0. 13] led to a rapid progress in the structural characterization of ordered condensed phases of Langmuir films of numerous types of lipids. and gaseous monolayer states and the related phase transitions and critical phenomena have not been systematically studied.5 A2 /molecule at 23. This property.2 behavior is illustrated in Fig. Johnson and coworkers reported recently that a line electrode residing in the plane of the air/water interface is a sensitive sensor of the onset of an LE/G phase transition [64].2 0. A set of BAM micrographs recorded near the LE/G transition of C22 Tempo is shown .5.3 0. Furthermore. In comparison. The phenomenon is reversible upon monolayer recompression.1.1 0. Line electrodes were found to be very sensitive and reproducible sensors capable of indicating the position of the LE/G phase transition. This sensing 1. 11 227 R(qz)/RF(qz) X-ray reflectivity data for C18 TEMPO at 21 mN m−1 at 21 ◦ C (points with error bars).7 qz (Å−1) is still somewhat preliminary. where sudden disappearance of cyclic voltammetric signal due to oxidation of a tetradecane ferroceneketone (C14 Fc) was observed during its monolayer expansion over just ˚ 3 A2 /molecule near LE/G phase transition.001 0 0.5 0.01 Model 1 c2 = 6. Using this new 2D electrochemical capability.1 0.1 0. Johnson and coworkers determined the position of the C22 Tempo LE/G phase ˚ transition to be 98. Brewster angle microscopy was employed to verify this measurement.

Indeed.5 2 1 1 A set of four consecutive 2-D voltammograms recorded during a slow expansion of a C14 Fc keton monolayer on a 50-mM HClO4 subphase. The disappearance of the voltammetric ˚ signal at 66–67 A2 /molecule is due to the onset of the LE/G phase transition (adapted from Ref. 66. diffusive charge transport. Electron hopping may proceed in parallel and compete with translational diffusion. in comparison with BAM.2 Potential vs. 64).6 0.3 0.5 0. However. 13. and where the electron hopping transport is most effective. ˚ and 68 A2 /molecule.3 Kinetics of Electron Hopping in Langmuir Monolayers Rapid electron exchange between adjacent molecules of different oxidation states in a Langmuir film is an alternative mechanism of the lateral. and convenient. Johnson and coworkers also measured the critical temperature of C20 Tempo to be 28 ◦ C [49]. All shorter chain Tempo derivatives were found to be supercritical at temperatures down to 0 ◦ C. 67.7 0.5.4 0.2.5. and the resulting decrease of the chain–chain interactions [49]. The mean molecular areas corresponding to the voltammogram 1–4 are: 65. the ability of Tempo to change its orientation at the air/water interface during monolayer expansion results in the shortening of the effective length of its hydrocarbon chain and thus in a decrease of the cohesive van der Waals interactions normally associated with a LE/G phase transition. 12 1. no increase of the voltammetric current due to translational diffusion was observed rendering . careful observation of the texture of a Langmuir monolayer at each stage of its gradual expansion allows one to determine the position of the phase transition. The i-E curves were recorded with a 500-µm line microelectrode at 0. 1.3. This hypothesis was supported by the surface potential measurements [49] and by recent X-ray reflectivity data [72]. where the rate of the Fc translational diffusion is at a minimum.1) even under the conditions of high surface concentrations. 2D electrochemistry was proven to be not only equally accurate but more precise. In other words.5 0 4 Current [nA] 3 0.5 0.2 V s−1 . Fig. 1.9 0.3. It is also free of false negative type measurements intrinsic to the BAM observations. reliable. we showed that the ferrocene rate constant of self exchange is not high enough for the electron hopping process to compete with the observed surfactants lateral diffusion (see Sect. SCE [V] in Fig. Consequently.2. The molecular origin of this rather unusual phenomenon was postulated to involve rotation of the Tempo head group leading to an increase of its crosssectional area. in the case of Fc surfactants. respectively.228 1 Preparation of Monolayer Modified Electrodes −0. For example.8 0.

are shown in Fig. A quantitative agreement with 2D percolation theory was demonstrated by plotting the normalized apparent diffusion constant due to electron hopping obtained from the electrochemical measurements of Fig. Unlike in the cases of Fc [54] and Tempo surfactants [25]. when the hopping dynamics is averaged over sufficiently large areas of this 2D system.7-diphenyl-1. Upon spreading of this large. nonamphiphilic osmium complex on the water surface. where 2D voltammetric current decreased with increasing surface concentration in response to the increasing monolayer viscosity. Fig.10-phenanthroline perchlorate (Os(DPP)3 ) [73–77]. 13 . and ˚ 130 A2 /molecule. Three such plots. The onset of 2D voltammetric activity coincides with the rise of the surface pressure during compression of the Os(DPP)3 monolayer. 49). 15 [75]. The length of the horizontal edges of these images corresponds to 430 µm (from Ref. 15 versus the fractional surface concentration of Os(DPP)3 on the water surface. corresponding to the 2D experiments carried out with the line electrodes of increasing length. This effect was conclusively related to the electron hopping percolation [78. 105. Electron hopping was unambiguously observed in solid monolayer films of osmium tris-4. Os(DPP)3 forms 2D solid aggregates that can be imaged by BAM (see Fig. 14). as can be seen in Fig. their mutual connectivity increases resulting in an increase of the extent of the electroactivity of the entire film. the opposite effect of the monolayer compressing was observed in this case. 16.5 Electrochemistry of Monolayer Assemblies at the Air/Water Interface 229 characterization of the hopping process impossible [48]. However. 79]. on–off type behavior that deviates from the percolation theory is observed. on a 50-mM HNO3 subphase at 23.5 ◦ C. It is interesting to note that when line electrodes with a length comparable to the aggregate size are used. by using line electrodes with lengths Brewster angle micrographs of C22 TEMPO monolayer recorded at (from top to bottom) 99.1. Upon compression of the solid aggregates of Os(DPP)3 .

57 A [75]. The ˚ lattice spacing of 10.230 1 Preparation of Monolayer Modified Electrodes Three Brewster angle microscopic images of Os(DPP)3 ˚ monolayer on a 50-mM HClO4 subphase recorded at 360 A2 /molecule showing typical shapes and sizes of 2D aggregates formed on the water surface upon spreading. 14 that are large compared to the average aggregate size.89 A gave the Os−Os ˚ distance of 12. Fig. These measurements showed that the Os(DPP)3 forms a hexagonal lattice in the plane of the air/water interface. 75). we first carried out structural characterization of the Os(DPP)3 films by grazing incidence angle X-ray diffraction [71]. It is interesting to compare the 2D crystal structure of . the system’s behavior reflects predictions of the 2D percolation theory [75]. In order to interpret the maximum value of the lateral diffusion constant in terms of the electron transfer–rate constant. The length of the vertical edges of these images corresponds to 730 mm (from Ref.

15 Os(DPP)3 with the isostructural Ru(DPP)3 complex described in the literature [80]. A more accurate measurement of the electron hopping diffusion constant.1.576 A.2 A set of 2D cyclic voltammograms of Os(DPP)3 monolayer at the air/water interface recorded concurrently with the monolayer compression. compression of the 2D aggregates imaged in Fig. Ru(DPP)3 chloride crystallizes in a monoclinic space group P 21/c with the distances between nearest Ru−Ru ˚ neighbors range from 13. 120 to ˚ 90 A2 /molecule (from Ref. can be interpreted to yield the unimolecular rate constant (k1 ) of electron transfer between adjacent Os(DPP)3 sites according to the following equation: D = 1 k1 r 2 4 (3) This gives k1 = 4.2 V s−1 . The latter corresponds to the bimolecular rate constant of electron exchange kex of 2. which may make that assumption uncertain.57 A) metal–metal spacing.7 × 108 s−1 [75]. the 2D crystal structure features a higher symmetry unit cell and shorter ˚ (12. Increasing current corresponds to decreasing mean molecular area of Os(DPP)3 from ca.5 Electrochemistry of Monolayer Assemblies at the Air/Water Interface −2 231 icathodic −1 0 1 ianodic 1. was obtained with a novel 2D electrochemical technique relying on a tandem of two collinear 40 µm long line microelectrodes spaced by 10 µm and acting as a generator probe and a collector probe. the maximum value of the electron hopping diffusion constant.085 to 16. and of the related kex . Ag/AgCl] 0. The CVs were recorded with a single 400-µm line microelectrode at a scan rate of 0. Thus. However. This assessment of the electron hopping kinetics involved an assumption of complete electroactivity of all Os(DPP)3 sites in the Langmuir monolayer.8 0.8 × 108 M−1 s−1 .4 2 0.0 0. a precursor complex ‘‘equilibrium constant’’ [48.6 E [V vs. Fig. It was obtained relying on the precursor complex model in which kex is expressed as a product of k1 and Kp .8 × 10−6 cm2 s−1 . 81]. 14 likely results in defects at the domain boundaries. In 3D. that did not require the assumption of 100% electroactivity of the Os(DPP)3 film. referred i (nA) . With these data in hand. D = 1. In this method. 75).

Fig.0 0.4 mm electrode 0. one important advantage of this method worth mentioning here is that it does not require surface concentration of .0 The plots of Dapp /Dmax vs.2 0. the diffusion of Os(DPP)3 (III+) species physically involved electron hopping process.6 x(OsDPP) 0.8 1.0 0.4 0. Naturally.6 x(OsDPP) 0. monitored their diffusive arrival rate [77].0 0.0.4 0.6 0.8 1.4.0 mm long line microelectrodes (from Ref. 75).8 0. held at the reducing potential.2 0. X(Os(DPP)3 ) obtained on the basis of several series of cyclic voltammetric experiments as those in Figure 13 carried out with 0. and 6.0 0.8 Dapp/Dmax 0. 16 0.232 1 Preparation of Monolayer Modified Electrodes 1. While the experimental details of 2D ETOF are beyond the scope of this review.4 0.0 0.2 (a) 1.4 0.0 0.0 0.8 1.0 6 mm electrode Dapp/Dmax 0.4 (c) 0.0 1 mm electrode 0.6 0. one line electrode generated Os(DPP)3 (III+) species and the other.4 0.6 0.6 x(OsDPP) 0.8 Dapp/Dmax 0. 1.2 0.0 to as 2D electrochemical time-of-flight (2D ETOF).2 0.0 0.2 (b) 1.

The effect of five solvents on electron-transfer kinetics was investigated. 5. Chem. 1966. a 2D voltammogram was recorded to measure the rate constant of electron transfer (see Eq. D. 1985. Solvation of the Os(DPP)3 molecules in its Langmuir monolayer and the dynamic solvent effects on electron hopping kinetics were investigated by Charych and coworkers in a set of solvent exchange experiments [74]. Insoluble Monolayers at Liquid-Gas Interfaces. L. This correlation is consistent with a highly adiabatic character. Lett. Phys.5 Electrochemistry of Monolayer Assemblies at the Air/Water Interface 233 redox species as an input parameter to interpret the experimental i –t transients. o 41. Annu. M¨ hwald. Wiley-Interscience. nonactive sites are in the regions near grain boundaries of the 2D aggregates. 1982. A. Physical Chemistry of Surfaces. M. 1990. 4th edition. Addition of some solvents such as acetonitrile resulted in an increase of the electron hopping kinetics. We obtained kex = 1. Science 1990.0 × 109 M−1 s−1 which is more than 1 order of magnitude higher than a literature value obtained for Os(DPP)3 (III+/II+) couple in an acetonitrile solution [82]. S. Knobler. 870–874. Braslau. 114–117. 1992. C. Pershan et al. 207–236. 3). Phys. Phys. M. Deutsch. [77]. Other solvents such as benzonitrile had the opposite effect. Adamson. a strong electronic coupling existing between the Os(DPP)3 molecules in their 2D solid aggregates discussed by Wittek et al. W. New York. 54. G. This rather substantial enhancement of the electron-transfer kinetics in a solid Os(DPP)3 monolayer could be due to one or both of the following factors. A. Knobler. 441–476. (1) The distances between the osmium centers and a particular alignment of the DPP ligands could result in a higher electronic coupling between Os(II) and Os(III) relative to those prevailing when these ions collide and exchange an electron in a homogeneous solution. Gaines. C. P. 4. or in other words. 43. (2) The reorganization energy of the Os(DPP)3 molecules in a monolayer at the water surface could be smaller due to a partial solvation. References 1.. This revealed a good correlation between the nuclear frequency factor. administered by the ACS for partial support of his research. Annu. New York. This measurement allowed us then to recalculate the rate constant of electron hopping. extracted from the measured values of the electron-transfer rate constant and the inverse longitudinal relaxation time of the solvents used in the solvent exchange experiments [74]. J.1. These experiments carried out by Wittek and coworkers showed that only 73% of all the Os(DPP)3 species are electrochemically active and participate in the electron hopping process [77]. organic solvent to the aqueous subphase supporting a compressed Os(DPP)3 monolayer on its surface. These involved incremental addition of aliquots of a polar. 3. Rev. C. Rev. M. . 2. Additional support has been provided by the National Science Foundation. Acknowledgments The author gratefully acknowledges donors of the Petroleum Research Fund. Charych and coworkers analyzed these measurements in terms of Marcus theory. We argued that the remaining. Rev. Chem. H. 249. John Wiley & Sons. Rashmi. 6. This sequence of solvent additions and 2D voltammogram recordings was continued until the rate constant achieved a new constant value forecasting a complete resolvation of the Os(DPP)3 molecules. Following each addition and equilibration.

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carbon is also finding use in the emerging field of molecular electronics [10].1 Introduction Electrochemical technologies make use of carbon electrode materials with different microstructures and properties. Michigan 1. carbon fibers. and sensor applications [6–9]. exerting a strong influence on the electric double-layer structure. molecular adsorption. The carbon electrode surface chemistry can be quite variable from material to material and depends on the past history [11–16]. Also. Swain Michigan State University. and surface chemistry differ from carbon material to material. and how the material was handled and prepared for use. and J. 10 Modified Electrodes. First.Fujihira. have begun to be studied and employed as electrochemical electrodes [2–5]. good chemical stability in a variety of solvent systems. It has long been known that electrochemical reactions at carbon electrodes are dependent on the type of carbon. energy storage and conversion devices. Carbon electrodes. in general. The relationship between the surface microstructure and chemistry. and electrode reaction kinetics. 17–39]. Weinheim. like highly oriented pyrolytic graphite (HOPG). KGaA. 11–16]. even though all are carbon. the properties of a particular type of carbon Encyclopedia of Electrochemistry. and Greg M. sp3 bonded carbon materials have begun to be investigated as electrodes because of their interesting and.6 Recent Trends in Chemically Modified sp2 and sp3 Bonded Carbon Electrodes Doug Knigge. unique properties [2–5. The surface chemistry plays a key role with carbon electrode function. and electronic properties is often difficult to unravel for at least three reasons. sp2 carbon electrodes have been extensively studied over the past four decades [1. sp2 bonded carbon materials. and carbon nanotubes. Faradaic electrochemical processes involve electron transfer across an electrified interface (electrode–electrolyte). I. The concept of chemically modified electrodes was. Attention is often paid to an electrode’s surface chemistry for catalytic and mechanistic purposes. For instance. More recently. the properties of GC are vastly different from those of HOPG or boron-doped diamond.J.F. born out of the electrochemist’s desire to control the chemical nature of the electrode surface so as to influence the electrode reaction kinetics and mechanisms. Stratmann Vol. in some cases. in part.6. 11–16]. Edited by A. the electronic properties. such as diamond and tetrahedral amorphous carbon (Ta−C). activated carbon powders. offer a wide working potential window. The relationship between the electrochemical behavior of a carbon electrode and the material’s physical. and the electrochemical properties of these materials has been thoroughly reviewed elsewhere [1. electrically conducting sp3 bonded carbon materials. glassy carbon (GC). Pushwinder Kaur. East Lansing. and the redox reaction kinetics and mechanisms are often strongly influenced by the physical structure and chemical properties of the electrode surface. Nowadays. and renewable properties via surface pretreatment. surface microstructure. Bard and M. and chemical sensors [1]. chemical. ISBN: 978-3-527-30402-8 .Rubinstein.236 1 Preparation of Monolayer Modified Electrodes 1.Rusling Copyright  2007 Wiley-VCH Verlag GmbH & Co. More recently. Edited by M. have been used for several decades in electroanalysis. The rich surface chemistry of most carbon materials affords the possibility for chemical modification using a number of well-established strategies.

increased noise. surface chemistry and microstructure) making it difficult to elucidate structure–function relationships. the surface chemistry. on the other hand.g. generally lead to increased voltammetric and amperometric background currents. as these polar and sometimes charged functional groups promote the strong adsorption of polar molecules (e. the nature of any pretreatment applied. then there needs to be a judicious choice of redox systems to probe this relationship with. and the only one that is inherently low in surface oxygen because of the hydrogen-rich environments in which . surface carbon–oxygen functionalities on sp2 carbon electrodes increase the heterogeneous electron-transfer rate constant for aquo Fe+3/+2 but exert little influence on the rate constant for Ru(NH3 )6 +3/+2 [40]. the variety of surface oxygen functional groups that can exist.1 M HClO4 [41]. most structurally stable. 12–15. 12–16]. wettability. diamond is the most chemically inert.g. Second. and the electrode’s past history. It is important to note that if the goal is to understand structure–function relationships at carbon electrodes. For example. These functional groups exist mainly as a consequence of the electrode being used and ‘‘activated’’ in air. 40]. specifically. and the increased electrode area that accompanies their formation on sp2 bonded carbon electrodes.g. 5. On the other hand. Good electrical conductivity is essential for all electrodes. surface oxides are one of the main reasons carbon electrodes can be rapidly deactivated by impurity adsorption. The factor that probably most complicates the study of structure–function relationships at carbon electrodes is the surface chemistry. so the electronic properties affect the electrode reaction kinetics of all redox systems. many pretreatment methods have been developed for ‘‘activating’’ carbon electrodes for electron transfer. There are also a large number of chemical and electrochemical treatments that introduce the functionality. The surface chemistry. On one hand. Surface oxides. Third. 12–15].1. and are difficult to control. The redox activity depends on the potential range and the ionization depends on the solution pH.6 Recent Trends in Chemically Modified sp2 and sp3 Bonded Carbon Electrodes 237 from two different sources or sometimes even from the same source can be quite variable. For instance. As a consequence of the variable nature of pretreatments. can influence the kinetics and mechanisms for some redox systems more than others. The oxygen functional groups influence the electrode polarity. Of the different sp2 and sp3 carbon electrode types. carboxylic acids). and electronic properties can influence the electrode reaction kinetics and mechanisms for redox systems to differing extents [1–5. The oxygen functional group type and coverage depend on the exposed carbon microstructure. specific functional groups can be influential both kinetically and mechanistically for certain redox reactions. particularly on sp2 bonded materials [1–5. Carbon–oxygen functionalities can be both friend and foe. complicating one’s ability to relate the electrode surface structure to the electrochemical response [1. surface carbonyl functional groups on GC and HOPG are known to catalyze the Fe+3/+2 redox reaction in 0. Pretreatments often affect more than one electrode property (e. carbon electrode surfaces tend to vary greatly from laboratory to laboratory and from day to day. molecular adsorption. contaminants). microstructure. and the electric double-layer structure. and reduced signal-to-background ratios because some types are redox-active (quinones/hydroquinones) and some types are acidic and ionizable (e.

Modifying carbon electrode surfaces can make them more monofunctionalized. GC surfaces prepared in air and/or used in aqueous environments have edge plane and defect sites that will be terminated with surface oxides of varying type and coverage [1]. Chemical modification is an approach for reducing the complexity of the carbon electrode surface chemistry. New chemical modification strategies and improved spectroscopic probes of modified surfaces have rejuvenated this field of research in recent years. the surface carbon atoms are terminated by strong covalent bonds with hydrogen prior to use. One more recent modification strategy involves the covalent attachment of aryl groups during the electrochemical reduction of phenyl diazonium salts [45]. more reproducible in terms of their electrochemical properties. chemical.2. Monofunctionalizing a surface through covalent attachment of atoms and molecules affords a means to control the surface chemistry. such as polymer deposition and the chemisorption of molecules. 1. carbon nanotubes. 1. This monograph is not a comprehensive review of the entire field of modified electrodes as it has existed for the past four decades. As stated earlier.2 Chemically Modified sp2 Bonded Carbon Electrodes Hydrogen-terminated Surfaces Glassy carbon or GC is one of the most widely used electrode materials in all of electrochemistry.1 . are important but not covered herein. Some of the research trends with chemically modified sp2 and sp3 bonded carbon electrodes are reviewed in this chapter. and less prone to fouling by impurity adsorption.6. but rather summarizes some of the more recent progress. As a consequence.e. such as low defect HOPG. Several strategies for altering the surface chemistry (i. One strategy that is extensively discussed herein is the electrochemically-assisted modification of carbon surfaces via the reduction of diazonium salts [45–55]. In general.238 1 Preparation of Monolayer Modified Electrodes the material is usually synthesized. There are also some sp2 carbon electrodes that are inherently low in surface oxygen. Some of the approaches employed over the years for modifying carbon electrodes include organosilane chemistry [6. modification enables the systematic investigation of how the surface chemistry influences electrode reaction kinetics and mechanisms. the heterogeneous distribution of surface carbon–oxygen functional groups can be a cause for significant variability in the electrochemical response and can lead to poor response stability. less susceptible to degradation because of surface oxidation reactions. and hydrogenated glassy carbon (HGC) [42. and the deposition of various polymers [7]. 43]. removing surface oxides) and covalently bonding molecules to both sp2 and sp3 bonded electrodes are discussed herein. and electrochemical treatment [44]. While the chemical modification of sp2 carbon electrodes has been the subject of much study over the years. the modification of sp3 carbon electrodes (diamond) is a new field of research that has emerged only during the past couple of years. nor are the vast number of modification methods for producing oxygen functionalities on the carbon surface. the introduction of surface carbon–oxygen functional groups via plasma. which had its origins back in the 1970s ([6–9] and references therein). It should be noted that other chemical modification strategies. particularly for electroanalytical measurements.6. the covalent attachment of quinone molecules [8]. 9].

for example. oxygenated) GC. Figure 1 shows a proposed surface structure for HGC. not molecular hydrogen. C3 H3 . it was proposed that the hydrogenated surface is actually composed of aliphatic hydrocarbon moieties (e. 1 Proposed surface chemistry of hydrogenated glassy carbon [42].g.) rather than simply hydrogen. For example.e. is the principal reactant that chemisorbs at the exposed edge plane sites and leads to the replacement of terminal oxygen functional groups [42]. Atomic hydrogen. the oxygen content remains low even during air exposure for weeks due to the stability of the C−H bonds [43].g. HGC exhibits lower voltammetric background current. Relatively rapid electrochemical reaction kinetics were observed for Fe(CN)6 −3/−4 and Ru(NH3 )6 +3/+2 . tungsten) filament.1. This treatment is fundamentally different from vacuum heat treatment or mechanical polishing in an anaerobic environment because it not only removes the surface oxides but also stabilizes the surface carbon atoms by forming strong covalent C−H bonds. C2 H5 . comparable electrochemical activity for several redox systems. both of which lead to pH-dependent changes in the voltammetric and amperometric background current over a wide potential range. CH2CH2CH2CH3 . In fact. and improved response stability compared with freshly polished (i. The hydrogenated surfaces are low in oxygen content (atomic O/C <0. Several approaches have been employed for removing surface oxides from sp2 carbon electrodes including high vacuum heat treatment [56–58] and mechanical polishing in an anaerobic environment [13]. etc. CH3 .g.02). HGC is prepared. quinone/hydroquinone couple) and some are ionizable (e. and quite hydrophobic with an initial water contact angle that is greater than 65◦ .g. while slightly slower kinetics were seen for dopamine and 4methylcatechol. by exposing GC to a hydrogen microwave plasma or to hydrogen gas activated by passage over a heated metal (e. enhanced S/B ratios. as determined by X-ray photoelectron spectroscopy (XPS). carboxylic acid). apparent heterogeneous electron-transfer H CH2CH3 CH2CH3 H OH Fig. carbon fiber. C3 H5 . Hydrogen plasma treatment is another effective method for removing carbon–oxygen functional groups from HOPG. and GC surfaces [42. as the chemisorption of atomic hydrogen not only replaces terminal oxygen groups but causes ring opening reactions that lead to the formation of surface hydrocarbon moieties [42]. Very sluggish kinetics were found for Fe+3/+2 . 43].6 Recent Trends in Chemically Modified sp2 and sp3 Bonded Carbon Electrodes 239 Some of these oxides are redox-active (e. On the basis of static secondary ion mass spectrometry (SIMS) results.

The radicals formed covalently attach to the electrode surface through the amine nitrogen.01 to 0. so only a brief synopsis is given herein. 2. which then covalently attaches to surface atoms. SCE in dry acetonitrile containing 0.240 1 Preparation of Monolayer Modified Electrodes rate constants. ethylene diamine) in nonaqueous medium [60].g. Another type of electrochemicallyassisted modification reaction that has become popular in recent years for controlling the surface chemistry of sp2 . 41]. 59]. Significantly lower rate constants of ∼3 × 10−5 cm s−1 were seen for Fe+3/+2 [42]. described the modification of carbon fibers by the electrochemical oxidation of aliphatic polyamines (e. 1.) [45].5 V vs. Further evidence for the lack of molecular adsorption (polar molecules) was revealed from chronocoulometric measurements performed with anthraquinone-2. This reflects how resistive this hydrophobic surface is to deactivation (fouling) via contaminant adsorption. k o app . modified GC surfaces using a variety of organic amines [61]. This field was recently reviewed by Downard [45]. carboxyphenyl.6AQDS) [39].1 M NBu4 BF4 . Barbier et al.6-disulfonate (2. presumably via the nucleophilic attack of the amine at electrophilic C=C sites and subsequent formation of C−N bonds between the surface and the amine [62]. Deinhammer et al. One reaction described in their manuscript was the attachment of 2-aminoanthraquinone during the polarization of the carbon fiber at 0. However.2. etc. The general reaction scheme for this modification is shown in Fig. Buttry and coworkers demonstrated that both thermal reactions and the electrochemical oxidation of amines at carbon fibers in a non-aqueous medium lead to the covalent attachment of these molecules to the fiber surface. Finally.1 M NaClO4 . low-oxide GC surfaces. The oxidation of the diamine leads to the generation of a cation radical species in the vicinity of the electrode surface.2 Surfaces Modified by Chemisorbed Molecules One strategy that has become popular in recent years for controlling the chemistry of sp2 carbon electrodes involves electrochemically-assisted derivatization. o The low kapp for Fe+3/+2 was attributed to the absence of mediating carbonyl functional groups on the HGC surface [40. The method utilized the electrooxidation of amines to their analogous cation radicals in a nonaqueous medium. This radical species then rapidly reacts at the surface to form a covalently attached admolecule. In another example. alkylphenyl groups/molecules. For example. oxygenated GC [39. The grafting occurred during polarization at 1. and a variety of substituted phenyl diazonium salts (e. SCE in dry acetonitrile containing 0. negligible adsorption was detected on HGC. alcohols. AQDS strongly physisorbs at high coverages on the polar. A wide range of molecules have been covalently attached to sp2 carbon surfaces in this manner including primary and secondary amines.03 cm s−1 were reported for Fe(CN)6 −3/−4 and Ru(NH3 )6 +3/+2 while slightly lower values of ∼5 × 10−3 cm s−1 were observed for dopamine and 4-methylcatechol [42]. nitrophenyl. This relatively versatile chemical modification strategy involves either the oxidation or reduction of a precursor molecule to form a solution radical species at the electrode–electrolyte interface. The voltammetric responses for all five redox analytes were extremely stable even after a 3-month period of air exposure.9 V vs. of 0.6. The results demonstrate that hydrogenation is a suitable modification method for producing stable. in another example.g.

the particular diazonium derivative. a multitude of substituted aryl groups have been attached to various carbon electrodes including phenyl. 3. 52. the applied potential. The derivatization reactions proceed on both the basal and edge plane sites of HOPG. 49]. 50. the edge and basal plane of HOPG and HGC) involves the reduction of substituted phenyldiazonium derivatives (R−N2 + ). the derivatization reaction is performed in a nonaqueous medium (e. CH3 CN) but there have also been a few reports of the successful derivatization of sp2 carbon surfaces in acidic aqueous media [50.g. 2 241 Covalent attachment of amine functional groups to the surface of carbon electrodes by the electrooxidation of amine precursor molecules in nonaqueous medium. 4-alkylphenyl. ultrasonication. 52]. Some 20-plus molecules having been investigated so far [45–55]. 4-nitrophenyl. The coupling reactions tend to be favored by both the adsorption of the diazonium prior to electrolysis and by the relatively positive reduction potential that prevents simultaneous reduction of the aryl radical [48. The structure and thickness of the aryl adlayer depend on the electrolysis (modification) time.1. 3 Covalent attachment of functionalized aryl molecules to the surface of carbon electrodes by the electroreduction of phenyl diazonium salts in nonaqueous medium. H −1e− + RNH2 −H+ +GC RN Carbon RNH2 carbon electrodes (GC. R N2+ + e− N2 + R R + Electrode R Electrode Fig. . but the reaction kinetics are much faster at the edge plane sites [48.6 Recent Trends in Chemically Modified sp2 and sp3 Bonded Carbon Electrodes Fig. 63]. carbon fiber. The reaction sequence is shown in Fig. and exposure to moderate temperatures. the type of carbon electrode material. The oneelectron reduction of these derivatives in nonaqueous solvent/electrolyte produces a reactive substituted phenyl radical in the vicinity of the electrode that then binds to the surface. 4-carboxyphenyl. and so on. for example. It has been shown that the binding is nonselective for the basal of edge plane sites of the sp2 carbon electrode. biphenyl. and the solution concentration of the derivative [48. exposure to different solvents. Mono or multilayer films can form depending on the deposition time [46. These derivatized surfaces tend to be quite stable during storage in air. 49]. As mentioned earlier. Most often. A comprehensive list is given in the review by Downard [45]. 55].

Raman spectra for the covalently attached admolecule were also similar at both surfaces exhibiting prominent peaks at 849. It was proposed that two factors favored the grafting reaction: (1) adsorption of the diazonium salt prior to its electroreduction and (2) the fact that the aryl radical is not reduced at the relatively low reduction potential of the diazonium salt. 48. The above two works spawned the more recent efforts to use this versatile method to chemically modify a variety of carbon and noncarbon surfaces [45. The reaction also proceeds facilely on hydrogen-terminated edge plane sites as McCreery and coworkers have shown HGC surfaces can also be derivatized by the reduction of phenyl diazonium salts [43]. Delamar et al. and 1177 cm−1 . 55]. McDermott [52]. 51. = 14 × 10−10 mol cm−2 . The reduction of nitrophenyl and (trifluoromethyl)phenyl diazonium ion in acetonitrile were carried out with the former and studied in greatest detail. which correspond to the NO2 and phenyl C−H bending motions. They showed that GC and porous graphitic carbon (PGC) stationary phases can be modified with either 4-nitrophenyl diazonium or 4-hexylphenyl diazonium. The presence of the covalently attached admolecule was determined by XPS and by comparing the reversed-phase separation of a series of solutes. and Belanger groups [50]. 55]. [49]. the grafting reaction tends to be nonselective for the oxygen-terminated edge plane and basal plane sites of the sp2 carbon materials. 48. and cyclic voltammetry. .242 1 Preparation of Monolayer Modified Electrodes In the first report of this reaction chemistry. 63]. Important components of these works have been the characterization of the orientation of aryl adlayers by Raman spectroscopy [48. 55]. Raman spectroscopy. The authors estimated the adlayer surface coverage through the integration of the reduction current for the nitro functional group and found that a closed packed monolayer was nearly achieved. described a new strategy for chemically modifying sp2 carbon stationary phases for use in electrochemically modulated liquid chromatography [53]. A detailed study of a number of diazonium derivatives was carried out with GC and HOPG by Allongue et al. As mentioned earlier. The cyclic voltammetric features during the derivatization reaction resembled those for polished GC. 50–55]. Harnisch et al. The main purposes for modifying the stationary phases were (1) to impart some degree of selectivity for the separation of different solute classes and (2) to improve the stability of the carbon support during extended exposure to aggressive mobile phases. as confirmed by XPS. The utility of the modified stationary phases was assessed by the separation of substituted phenols and various pharmaceutical agents. showed that the electrochemical reduction of a 4nitrophenyl diazonium salt in nonaqueous medium results in the covalent attachment of nitrophenyl groups on GC and HOPG electrode surfaces [46]. It was observed that the surface coverage can be controlled by adjusting the concentration of the diazonium derivative in solution and the electrolysis (deposition) time. 1108. the morphology of mono and multilayer films by electrochemical atomic force microscopy (ECAFM) [52]. Notable work has been performed by the McCreery [10. and the role of the aryl adlayer on the electron-transfer kinetics for several solution-based redox systems [50. 47. Downard [45. On GC or graphite electrodes. 51. the reduction of nitrophenyl diazonium leads to the formation of a compact nitrophenyl monolayer.

controlling molecular adsorption. The effect of these functional groups on the GC electrode reaction kinetics for a number of aqueous-based redox systems (Fe(CN)6 −3/−4 . The DNPH reaction was used to selectively derivatize carbonyl groups while dinitrobenzoyl chloride (DNBC) was used to selectively derivatize hydroxyl groups. For example. Feaq +3/+2 . 65]). In a related work. XPS. caused a significant decrease in the electron-transfer kinetics for Feaq +3/+2 . and Vaq +3/+2 ) was also investigated [67]. Specifically. which leads to a resonance Raman-active product with a large scattering cross section. and Euaq +3/+2 . The point that the surface oxide coverage on GC is sensitive . Raman spectroscopy. The authors categorized the different redox systems according to their relative sensitivity to the GC electrode surface structure and chemistry. Ru(NH3 )6 +3/+2 .3 Effect of Surface Modification on the Electrochemical Properties There are a number of reasons for controlling the surface chemistry of carbon materials including promoting the interfiber bonding in carbon fiber composites. as probed by this chemistry. the group probed the presence of carbonyl functional groups on HOPG and GC surfaces by the selective derivatization with dinitrophenylhydrazine (DNPH) [67]. IrCl6 −2/−3 . for example. to determine the surface coverage and to assess the effect of functional group blockage on the kinetics. In other words. was found to increase during electrochemical polarization. The surface carbonyl functional group density. Characterization of the chemical identity and local environment of the surface oxides has been undertaken by the McCreery group using several creative synthetic approaches.1. 64. The DNPH (carbonyls) and DNBC (hydroxyls) reactants were used along with a new fluoroscein mixed anhydride (FMA) reagent for selective binding with hydroxyl groups. chemical derivatization of the carbonyl groups (blocking these) decreased the electron-transfer rate for Fe+3/+2 . by 2–3 orders of magnitude. but had less effect on the other redox systems. The kinetics of the aquated ions were found to be quite sensitive to the presence of these functional groups. but had little effect on the rate constants for Ru(NH3 )6 +3/+2 or IrCl6 −2/−3 . the group used Raman spectroscopy to study how the surface coverage of carbonyl and hydroxyl functional groups on GC changes with pretreatment [68]. and improving the electrode reaction kinetics for a particular redox system (as examples [62. DNPH is a specific reagent for ketone and aldehyde groups. Vaq +3/+2 . the group studied the electron-transfer kinetics for nine aqueous-based redox systems at GC surfaces modified with reagents that react specifically with different oxygen functional groups [68]. The results revealed that FMA reacts selectively with the hydroxyl groups and the FMA-surface adduct is a Raman-sensitive probe of the hydroxyl group coverage. developing platforms for chemical and biological sensing. inhibiting corrosion.2. The specific adsorbers. sp2 bonded carbon electrodes have a rich chemistry with a variety of carbon–oxygen functionalities being present [64–66]. and electrochemical methods were used to confirm the presence of the derivatizing agent. while other redox systems were not nearly as affected. The derivatization permits detection of carbonyl groups down to about 1% of a monolayer. Of particular importance to the electrochemist is an understanding what effect surface chemistry has on the electrode reaction kinetics.6 Recent Trends in Chemically Modified sp2 and sp3 Bonded Carbon Electrodes 243 1. DNBC and particularly DNPH.6.

Belanger and coworkers investigated the effect of 4-carboxyphenyl and 4-nitrophenyl adlayers on the electrochemical response of GC for Fe(CN)6 −3/−4 . Blocking properties were seen for the adlayers.4) and the anionic surface sites was found to dominate the electrochemical behavior. and ferrocene [50]. Several groups have investigated how the electrochemical properties of GC are altered after being modified by the reduction of diazonium salts [50. temperature measurement capability. hot-filament. a throttle exhaust value and controller for regulating the system pressure.3 Chemically Modified sp3 Bonded Carbon Electrodes CVD Diamond Thin-film Growth Electrically conducting diamond is a new type of carbon electrode material that is finding more and more use in electrochemistry. producing a spherically shaped.1 . producing a growth precursor in close proximity to the substrate surface [2].6. 54. hydroquinone. the authors sought to gain better control of the surface chemistry and to make it more homogeneous as compared to a native carbon fiber. the microwave energy from the generator is directed to and focused within a quartz cavity. glow-discharge plasma directly above the substrate.6. microwave power source). Different behaviors were seen for the modified carbon fibers depending on the surface chemistry and the fiber microstructure. the extent to which depended on electrostatic and electrolyte/solvent effects. Under physiological conditions. While the mechanism of film growth differs slightly from method to method. all serve to activate a carbonaceous source gas. as well as various accessories. Most often diamond is grown as a thin film on a conducting substrate like doped Si. A block diagram of a typical CVD system is shown in Fig. 1. or Ti. Through surface modification. The purpose for the work was to use chemical modification to reduce the electrode response time and increase the sensitivity for dopamine.3. or combustion flame-assisted chemical vapor deposition (CVD). The most common method is microwave plasma CVD.g. Diamond can be grown by one of several methods: microwave plasma. a pumping system. the sensitivity of a carbon fiber electrode for dopamine is strongly influenced by the extent of molecular adsorption with the response time being controlled by the adsorption and desorption kinetics. such as mass flow controllers for regulating the source gas flows.244 1 Preparation of Monolayer Modified Electrodes to both the initial conditions and subsequent chemical treatment procedures was emphasized. Bath and coworkers studied the role of surface modification on the carbon fiber response for the catecholamine and dopamine [54]. Ru(NH3 )6 +3/+2 . 55]. The strength of the interaction between the cationic dopamine (pH 7. The electrode surface was modified by (1) physisorbed anthraquinone disulfonate and (2) chemisorbed 4carboxyphenyl or catechols via diazonium salt reduction. 4. W. In the case of microwave-assisted CVD. The substrate can either be positioned outside of (few mm) or immersed within the intense discharge 1. Mo. For example. One reason for this is the commercial availability of such reactor systems. A brief discussion is given below of how the material is synthesized. A typical CVD reactor consists of the growth chamber and equipment associated with the particular activation method (e. and the gas handling system for supplying the source gases.

C. High quality microcrystalline diamond films are deposited from CH4 /H2 source gas mixtures with volumetric ratios of 0. 2 µm (a) Fig.F. 5 500 nm (b) SEM images of (a) a boron-doped microcrystalline and (b) a boron-doped nanocrystalline diamond thin film grown on Si.3 to 1. Figure 5 shows scanning electron microscopy (SEM) images of the two types of boron-doped diamond thin film deposited on Si. The plasma is where the reactive species involved in the diamond growth are formed. There are two types of synthetic diamond thin film routinely produced: microcrystalline and nanocrystalline [2]. M. system pressure. The names for these two film types arise from their nominal crystallite size and morphology.C.6 Recent Trends in Chemically Modified sp2 and sp3 Bonded Carbon Electrodes Microwave generator Mass flow controllers M. 4 Typical layout of a microwave plasma chemical vapor deposition system.F.1.F. . M. M.C.C. and substrate temperature. The key deposition parameters to control are the source gas composition. region.0%. microwave power.F. Substrate Substrate holder 245 Antenna Quartz chamber Gas inlet B2H6 cylinder CH4 cylinder H2 cylinder Ar cylinder Pressure gauge Exhaust valve Rotary pump To vent Fig.

The C2 addition is believed to occur by a two-step growth mechanism [69–79]. There is a fundamental change in the plasma chemistry. microwave powers of 0. The C2 molecule then rotates to insert its other carbon into a neighboring C−H bond on the surface. polycrystalline diamond with crystallite sizes on the order of a few micrometers. and this leads to the higher levels of CH3 • and H•. 78]. growth mechanism. uniform grain size (3–5 nm is typical for high quality ultrananocrystalline diamond) and a small but nonnegligible amount of sp2 bonded carbon at the abrupt grain boundaries [69. nondiamond carbon impurity that forms on the growing surface. A C2 molecule approaches the unreconstructed monohydride surface and inserts into a C−H bond. as can be seen in the SEM image. or greater. in lateral dimension. there is sufficient hydrogen from the CH4 to minimize surface reconstruction to an sp2 bonded phase. 80]. like Ar or Xe. 78. Gruen and coworkers discovered that phase-pure nanocrystalline diamond can be grown from CH4 /Ar gas mixtures with very little or no added hydrogen [69. which serves as both the primary growth and nucleation species [79. compared with those grown from conventional hydrogenrich mixtures.246 1 Preparation of Monolayer Modified Electrodes microwave powers of 0. High quality nanocrystalline diamond films are deposited from CH4 /Ar source gas mixtures using a volumetric ratio of 0. pressures of 35–65 torr. 79]. The added hydrogen serves several key functions: (1) abstraction of hydrogen from chemisorbed methyl substituents on the growing film surface to produce active sites for carbon addition. and the resulting films consist of randomly oriented. The low excitation energy of inert gases. Nanocrystalline films produced in Ar-rich plasma possess a very fine. Apparently. Noble or inert gas addition to hydrogen-rich plasmas (e. The most remarkable difference in films grown using hydrogenpoor Ar gas mixtures. parallel to the newly inserted C2 dimer. and substrate temperatures of 700–850 ◦ C. results in a plasma discharge with a higher electron density. is the nanocrystallinity and smoothness (rms roughness ∼10–30 nm over large areas) of the former. and (3) rapid gasification of any sp2 bonded. and electronic properties that are different from the grains. and film properties as one transitions from a hydrogen-rich to a hydrogen-poor plasma. As can be seen from the image.g. 0. pressures of 130–160 torr.8–1 kW.5% CH4 /H2 ) enhances the growth rate of films by increasing the CH3 • and atomic hydrogen concentrations in the plasma. The original state of the surface is recovered by the formation of a bond between carbon atoms in the adjacent surface dimers. Very high rates of heterogeneous renucleation are observed on the order of 1010 cm−2 . phase-pure grains of diamond with well-delineated grain boundaries [69–79]. A grain boundary is present at the junction between two or more crystallites. during growth. . CH3 • is the primary growth precursor. (2) passivation of dangling bonds on the surface to minimize reconstruction from sp3 to sp2 bonding. A C2 molecule then inserts into an adjacent C−H bond. The individual crystallites are randomly oriented and there is significant twinning. Under these conditions.5 to 1. 77.0% with little or no added hydrogen. hydrogen-poor plasmas have a high concentration of carbon dimer. microcrystalline films are well faceted. growth rate. The nanocrystallinity is the result of a growth and nucleation mechanism involving the insertion of C2 into surface C−H bonds.8–1 kW. chemical. and substrate temperatures of 700–850 ◦ C. C2 . In particular. which has structural.

A common substrate preparation involves either mechanical polishing with small diameter diamond powder (0.3. or ultrasonication in a diamond powder/solvent suspension. Boron-doping levels for highly conductive films are normally in the range of 1019 to 1020 B cm−3 . like GC.6. which is over 1 V wider than GC.2 cm s−1 ) for several aqueous-based redox analytes without any conventional pretreatment (e. Fe(CN)6 −3/−4 ). smooth nondiamond substrates is generally low. and methanol) is common practice.02–0. the largest heterogeneous electron-transfer rate constant for several aqueous redox analytes. Enhancement of the instantaneous heterogeneous nucleation density results from both the physical defects introduced and the highly dispersed diamond seed particles.01–1 µm diameter).1 to 100 cm2 V s−1 . 6 A schematic representation of the hydrogen-terminated diamond surface. Electrical conductivity (typically 100–1000 −1 cm−1 ) is introduced by doping with impurities. (3) superb response 1. so far. 21]. Figure 6 shows the structure of the hydrogen-terminated surface. In general. even during high current density (0. has involved electroanalytical measurements using films with a hydrogen surface termination. The heterogeneous electron-transfer rate constants for several aqueous redox systems have been measured at good quality. Surface Termination Electrically conductive diamond electrodes possess several properties that clearly distinguish them from conventional sp2 carbon electrodes. Therefore.1. 29. with the latter. (2) a working potential window of 3–4 V in aqueous media. and (5) weak adsorption of polar molecules. Ultrasonic cleaning in organic solvents (isopropanol.2 precision and stability due to the stable surface morphology and microstructure. hydrogen-terminated electrodes [2–5. depending on the film microstructure and morphology. substrate pretreatment is a prerequisite for deposition. acetone. and make them attractive for electrochemical use [2–5. with diamond electrodes. Most of the work. such as boron. Most pretreatments also involve subsequent substrate washing to remove polishing debris and clusters of diamond particles.6 Recent Trends in Chemically Modified sp2 and sp3 Bonded Carbon Electrodes 247 The instantaneous rate of nucleation during diamond growth on untreated. For example. 21]. The carbon atoms are covalently bonded to H H H H H H Fig. 39]. (4) relatively rapid electrode o reaction kinetics (kapp 0. like 2. Typical carrier concentrations (holes) in the more highly doped films range from 1018 to 1020 cm−3 with carrier mobilities varying from 0. the lowest level of absorption.6anthraquinonedisulfonate. 21]: (1) background current densities approximately 5–10 times lower than freshly polished GC leading to enhanced S/B ratios. the diamond powder can be suspended in ethanol and the sonication is performed in this medium. as well as the dispersion of some diamond particles over the surface.5 A cm−2 ) electrolysis.g. polycrystalline. . Either pretreatment results in the formation of scratches and other defects. and the most reproducible electrochemical response is observed for the hydrogen-terminated surface [2–5. rendering the material resistant to fouling and passivation [25. boron-doped.

Freedman exposed diamond (111) and (100) surfaces to beams of atomic fluorine and chlorine in the UHV. 85]. Exposure of hydrogen-terminated diamond surfaces to activated fluorinecontaining gases. Figure 7 shows a schematic representation of a fluorine-terminated surface. Activation of these gases. temperature programmed desorption. leads to fluorine substitution [86]. In fact. and their coworkers on understanding the conduction mechanism [80–83]. for example. like HF. The larger chlorine atoms were found to weakly chemisorb on the diamond (100) Fig. and low-energy electron diffraction [86]. The hydrogen surface termination of diamond can easily be altered with two common functional groups. The rate of chemisorption was found to depend on the diamond crystallographic orientation with the difference in behavior being ascribed to variations in bonding geometry.248 1 Preparation of Monolayer Modified Electrodes one another through sp3 hybridized bonds. 7 Schematic representation of a fluorine-terminated diamond surface. several device concepts based on a H-terminated diamond surface have been developed for gas sensors and ion-selective field-effect transistors (FET’s) [84. and absence of in-diffusion of ions [80–85]. The fluorinated surfaces were characterized by XPS. Of special interest is the hydrogen-terminated diamond surface. which occurs after CVD growth or special postgrowth hydrogen plasma treatment. F2 . or CF4 . Fluorine adds to both surfaces to form carbon monofluoride species. Atomic fluorine appears to function much like atomic hydrogen in terms of its ability to abstract surface hydrogen producing reactive sites for diamond growth [86]. 0.75 monolayer at 300 K. . As a consequence of this somewhat unique electrical property.’’ low friction surfaces that can F H F F H F be exposed to a wide range of temperatures and conditions. something that often happens with sp2 carbon materials and leads to the progressive formation of new reaction sites for chemisorption. diamond has recently attracted attention as a semiconductor for chemical sensing due to its large potential window for water stability. 85]. The figure shows that each surface carbon atom is monofunctionalized with hydrogen. There are a couple of reasons for the interest in changing the surface termination: (1) understanding the manner in which the terminal atom affects adsorption. some of the surface atoms maybe terminated with methyl groups. Kohn. There is usually no degradation of the microstructure during treatment. corrosion (oxidation) and electrochemical kinetics. Seminal work has been performed by Ristein. namely. and by Kawarada and his coworkers on the FET sensors [84. which leads to steric hindrance on the (100) surface. produces reactive atomic fluorine. and (2) designing ‘‘slippery. by microwave-assisted plasma CVD. reaching a saturation coverage of ca. Something that is unique about diamond as compared to sp2 carbon electrodes is the fact that the chemical changes are confined to the surface. chemical inertness. fluorine and oxygen. In addition to electroanalysis. It has been found that there is a hydrogen-induced surface conductivity that can be controlled by adsorption of a number of reducing or oxidizing gases [80–83].

5 monolayer at 300 K.18 after plasma treatment. Teflon-like surface). which is shown in Fig. of an electrochemical study of an F-terminated diamond electrode. SHE in 0.5 M H2 SO4 produced C4F9−I 300 K −C4F9(g) F3C CF2 F2C I CF2 up to 800 K FC F F Fig. From an electrochemical point of view. These highly resistive materials are not practical for use as electrodes. it has no practical use as an electrode modification method.6 after decomposition of the attached C4 F9 species. therefore. For example. The first voltammetric scan out to 2. polycrystalline diamond electrodes by exposure to a CF4 radio frequency plasma [88]. 8 Reaction sequence for modifying diamond surfaces with fluorine atoms using perfluoroalkyl iodide and X-ray radiation.5 V vs.16 to 0. 8. The coated surface was then irradiated with X-ray radiation to produce fluoroalkyl radical species that covalently bind to the diamond surface. This is the only example. The fluorinated surface was stable up to 1500 K at which point the chemisorbed fluorine atoms begin to desorb. This fluorination was shown to occur on both bare (desorbed surface hydrogen) and deuterium-terminated surfaces.6 Recent Trends in Chemically Modified sp2 and sp3 Bonded Carbon Electrodes 249 surface at a saturation surface coverage of ca. one might speculate that a fluorine surface termination would render the diamond electrode surface more resistant to oxidation and perhaps even less susceptible to adsorption (e. . The XPS F/C atomic ratio was in the range of 0. a process that removes impurities as well as the chemisorbed hydrogen atoms terminating the surface. In their approach. Angus and coworkers fluorinated borondoped. nevertheless.g. The XPS F/C atomic ratio was 0. Yates and coworkers used X-ray irradiation to modify undoped diamond single crystal surfaces with perfluoroalkyl iodide (C4 F9 −I) radicals [87]. The modified surfaces were thoroughly characterized by XPS. single crystals. to the best of our knowledge. Unlike the fluorinated surface. The modified surface was then heated up to 900 K to decompose the surface C4 F9 groups producing a surface largely terminated by fluorine atoms. C4 F9 −I molecules were first dosed onto a clean diamond (100) surface in the UHV at 120 K. Several other approaches have been used to fluorinate undoped polycrystalline diamond thin films. the chlorinated surface is unstable when exposed to aqueous environments. The X-ray radiation dissociates the C−I hn bond producing perfluorinated alkyl radicals for attachment. and powders [87.1. The irradiation was performed at 120 K and this was followed by gentle heating to 300 K in order to desorb the unreacted C4 F9 −I molecules. The surface was initially cleaned by UHV heat treatment at 1450 K. the surface treatments are worth mentioning because they could be applied to conductive diamond materials. 88]. 0.

respectively. 90]. Most interesting is the fact that the redox charge (ca. at least for these three systems.15 after extensive electrochemical oxidation in HClO4 or H2 SO4 [40.11. Martin and Morrison used IR difference spectroscopy to identify C−OH and C−O−C functional groups on the diamond film surface after electrochemical oxidation [92]. the Ep for Ru(NH3 )6 +3/+2 is relatively unaffected by the surface oxygen at least for the surfaces polarized as they were in this work. The XPS atomic O/C ratio increases from approximately 0. However. Oxygen was incorporated into the surface during cycling as the F/C atomic ratio decreased to approximately 0. the C−F bonds formed are susceptible to oxidation in this medium at potentials of approximately +2. 89. SHE) associated with electroactive sp2 carbon impurities. There is a progressive increase in the cyclic voltammetric Ep for Fe(CN)6 −3/−4 and a positive shift in Eox for ascorbic acid with increasing surp face oxygen coverage [40. that the electrochemical kinetics for Fe(CN)6 −3/−4 and ascorbic acid are strongly inhibited by the presence of surface oxygen.6. after the first scan. The inhibitory effects of the oxygen can be removed by rehydrogenating the surface in a hydrogen microwave plasma.2 V. Contrarily. This indicates that C−F surface bonds are broken and new C−O bonds are formed in this potential range.250 1 Preparation of Monolayer Modified Electrodes two anodic peaks at approximately +1. +1. 90]. The authors proposed that the two anodic peaks observed during the initial voltammetric scan toward positive potentials are due to the oxidation of an adsorbed fluorocarbon polymeric layer that forms during plasma treatment. presumably located at the intercrystalline grain boundaries. 90]. is observed for the hydrogen surface termination. diffuse reflectance FTIR investigations of gas phase oxidized diamond powders revealed the formation of C−O−C and C=O bonds after exposure to oxygen above 300 ◦ C [91]. the onset potential for oxygen evolution shifted back negatively to its original value and the charge associated with the oxidation processes disappeared. in a quantitative way.3 functional groups formed have not been identified yet. Oxygen-terminated Surfaces Oxygen surface functionalities can be introduced by chemical and or electrochemical oxidation of diamond electrodes. However.03 while the O/C ratio increased to approximately 0. how the surface oxygen affects the electrochemical reaction kinetics for different aqueous redox systems has been performed [40. A systematic study of how the anodic charge passed correlates with the surface oxygen coverage and. The onset potential for oxygen evolution was also shifted in a slightly more positive direction from the value observed for the hydrogen-terminated surface. After plasma treatment.3. Work is still needed to identify the types of oxygen functional groups formed and to understand why they inhibit these two redox reactions.0 V or greater. and that the most active response. which are gasified during the plasma treatment. was eliminated after plasma treatment in CF4 . do not play a significant role in the electrochemical response of these materials. return to their original values.01 to 0. in turn.6 and +2. but in related work. This trend indicates that adventitious sp2 carbon impurity phases.83 V vs. The fluorination treatment appears to be effective at removing sp2 carbon impurities from the surface and/or inhibiting the oxidation of grain boundary carbon. Ep and Ep ox for Fe(CN)6 −3/−4 and ascorbic acid. 89. The results demonstrate. . The types of oxygen 1.

Kim et al. The low chlorine and high oxygen incorporation results from the reaction of the chlorinated surface with atmospheric oxygen. hydrogen-free. This was probably due to the presence of surface oxygen. the formation of dimers on the diamond surface is prevented by hydrogen chemisorption.01. perfluorobutyl groups were covalently attached to the surface. Ohtani and coworkers attached pyridine to polycrystalline. and hydrogen-terminated. respectively. A series of annealing experiments revealed that these modes persist even up to 600 K. In one of the first examples of a modified diamond electrode.4 Surfaces Modified by Chemisorbed Molecules Diamond surfaces can also be chemically modified by covalently attaching various molecules. cyclopentene [95].1. This leads to the formation of carbon atoms paired into C=C dimers with a partial π bond [95]. The adlayer was studied using multiple internal reflection infrared spectroscopy (MIRIRS). silicon. The N 1s peak at ca. At these temperatures.6. Hamers and coworkers showed that undoped diamond (001) surfaces undergo [2 + 2] cycloaddition reactions with a prototypical alkene. single crystal (110) diamond surfaces [94]. and germanium share a similar bonding motif in which pairs of atoms can bond to each other via a strong σ bond and a weaker π bond forming a dimer. C4 F9 I physisorbed to form multilayers at 90 K on both surface terminations. The physisorbed C4 F9 I desorbed when heated above 200 K regenerating the starting surface. but they completely disappear by 700 K.3.6 Recent Trends in Chemically Modified sp2 and sp3 Bonded Carbon Electrodes 251 1. The first step involved treating the hydrogen-terminated diamond surface with Cl2 under UV irradiation (>200 nm). however. Normally. This surface is essentially an extended array of alkene-like C=C . XPS revealed O/C and Cl/C atomic ratios for the chlorine-treated surface to be 0. The electronic structure and vibrational spectra of the perfluorobutyl group were calculated for perfluorobutyl chloride and bromide. The characteristic vibrational features of the attached perfluorobutyl group were observed between 1138 and 1355 cm−1 . however. The (001) surfaces of diamond. This is somewhat similar to the strategy developed by Yates and coworkers that was described earlier. which formed during the exposure of the chlorinated surface to the atmospheric as discussed earlier.10 and 0. boron-doped diamond using a multistep procedure [93]. the diamond (001) surface was made reactive for the addition reaction by heat treatment in the UHV at 1375 K. The chlorinated surface was then exposed to boiling pyridine to produce a quarternary pyridinium salt modified surface with the linkage through the ring nitrogen. the authors did indicate that the atomic chlorine-treated surface exhibited very sluggish electrochemical reaction kinetics for Fe(CN)6 −3/−4 as evidenced by a poorly defined waveform with a large peak separation. 400 eV increased after exposure to boiling pyridine. and the MIRIRS of the physisorbed multilayer agreed well with calculated IR spectra. the surface is cleaned of impurities and surface hydrogen desorbs. Limited electrochemical data were reported. This photolysis produced Cl radicals that attack the surface and replace some of the surface hydrogen. After exposing the multilayer at 90 K to UV radiation (200 W Hg lamp) for 30 min and subsequent heating above 200 K. presumably during sample transfer. Similar results were found for both the hydrogenterminated and hydrogen-free surfaces. investigated the low temperature photochemical attachment of perfluorobutyl (C4 F9 I) moieties on undoped.

The reactive diamond surface was then exposed to cyclopentene vapor at 300 K in the UHV.7. in particular. The adlayer was stable to washing and immersion in organic solvents. The Hamers’s group also reported on the attachment of functionalized organic molecules to polycrystalline diamond film surfaces via irradiation of hydrogenterminated diamond covered with liquid films of an appropriately functionalized alkene [96].9. and (3) the trifluoroethyl ester of ωundecenoic acid. 40 ◦ C). The oxidized surface was then reacted with adipoyl chloride in dry acetonitrile under nitrogen with 4-methylmorpholine acting as the Lewis base to produce an acid chloride surface.4.6. The C−H absorption bands at 2953 and 2880 cm−1 were used to confirm the presence of the chemisorbed cyclopentane groups. The admolecule was stable during UHV heat treatment up to 573 K. Some of these organic molecules contained amine and carboxylic acid functional groups that are good starting points for attachment of more complex molecules (e. The authors modified the diamond surface with (1) perfluorodecane (3. The most important of these are the hydroxyl groups. This oxidation treatment introduced carbon–oxygen functionalities. (2) 1-fluorononane.g.6. The covalent attachment of the pyrene through the amine group was observed to be relatively fast with a coverage limited by the steric constraints imposed by the diamond surface structure or possibly by the bridging across two electrode surface sites by two COCl terminal groups of the same adipoyl chloride molecule. After rinsing with ethyl acetate and drying under a stream of nitrogen. The hydrogen-free surfaces react with unsaturated C=C bonds of organic alkenes. UHV−FTIR (internal reflection mode) was used to study the sp3 C−C and C−H bonding. The chemical functionalization was accomplished by placing a small volume of the long-chain organic compound on the diamond film surface to form a thin liquid film. All modified surfaces were characterized using XPS. The results showed that the H-terminated diamond surface could be chemically modified through a UV-mediated reaction with functionalized alkenes.8. The first step involved introducing surface oxides on the hydrogen-terminated surface by exposure to Piranha solution (10 min.5. in particular. the F 1s line at 689 eV and the C1s region near 284 eV. IR reflection–absorption spectroscopy. An optically transparent diamond thin film deposited on quartz was used as the substrate [26]. The covalently bound adlayer was not as ordered as . A [2 + 2] cycloaddition reaction occurred as the π bond of an alkene adsorbate and the weak π bond of a surface dimer were broken and two new σ bonds were formed linking the alkene to the surface through a four-member ring. DNA).4.9.10.10. Figure 9 shows the multistep reaction scheme devised by the authors.252 1 Preparation of Monolayer Modified Electrodes bonds. the trifluoroacetamideprotected 10-aminodec-1-ene and the t-BOC-protected 10-aminodec-1-ene. sealing the coated film in a reaction vessel with a quartz window. ´ Krysinski et al. and irradiating the film/liquid with UV light (254 nm) over a 2-h period. reported on the covalent attachment of admolecules on diamond surfaces using a simple displacement reaction that begins with a hydrous oxide surface [97]. The pyrene-modified surfaces were characterized by electrochemical methods. the terminal acid chloride functionalized surface was then reacted with 1-aminopyrene.5. hydroxyl and carbonyl functional groups. and timeresolved fluorescence measurements.7.8.3. but with a distorted surface geometry [95].10-heptadecafluoro-1-decene).

Hydrogenated diamond surfaces were treated in a solvent containing benzoyl peroxide and an alkane dicarboxylic acid.1. Surface characterization was performed by diffuse reflectance FTIR. 0. but exhibited more organization than amorphous physisorbed adlayers. Ida and coworkers reported on a new method for introducing carboxylic acid groups onto a diamond powder surface [98]. 9 Reaction sequence for the covalent attachment of 1-aminopyrene to the surface of a diamond optically transparent electrode [97]. C6 H5 −COO−OOC−C6 H5 − − C6 H5 −COO• + •OOC−C6 H5 −→ The covalent attachment of phenyl groups to the H-terminated diamond surface probably involves the following reaction steps. The reaction sequence follows a free radical substitution as listed below. Benzoyl peroxide decomposes via the following reaction.5% of full monolayer coverage.6 Recent Trends in Chemically Modified sp2 and sp3 Bonded Carbon Electrodes Cl O Cl O 253 O H H HO H H OH Cl O H H O H H OH NH O NH2 O H H O H H OH Fig. an alkanethiol self-assembled monolayer (SAM) on Au. which corresponds to ca. (diamond)−H + C6 H5 COO• − − (diamond)• + C6 H5 COOH −→ HOOC−(CH2 )n −COOH + C6 H5 COO• − − HOOC−(CH2 )n −COO• −→ + C6 H5 COOH (diamond)• + HOOC−(CH2 )n −COO• − − (diamond)−OOC−(CH2 )n −→ −COOH . The surface coverage was determined to be ∼4 × 10−12 mol cm−2 .

Curves for both 400 600 800 0 −5 −10 −20 −25 Nanocrystalline Microcrystalline −30 −35 −40 Fig. 1735 cm−1 for the C=O groups of the carboxylic acid and aliphatic C−H stretches between 2750 and 2950 cm−1 were monitored to confirm the presence of the attached molecules. The high coverage of covalently bound molecules. on the basis of the XPS data. Scan rate = 100 mV s−1 . indicates that a variety of surface functionalities can be introduced on the normally unreactive diamond surface. achievable by diazonium reduction. Current [µA] −15 . Ag wire) −800 −600 −400 −200 0 200 and/or fluorine (F 1s. Chemical modification of diamond electrode surfaces has also been accomplished by the reduction of diazonium salts. nitroazobenzene and trifluoromethyl phenyl admolecules. and all showed strong XPS signals for surface nitrogen (N 1s. This coverage is too high to be attributed solely to modification of any adventitious sp2 carbon impurity phase. Figure 10 shows typical first-scan cyclic voltammograms for the reduction of 4-nitrophenyl diazonium in 0. as discussed previously. Diamond electrodes were modified with nitrophenyl. showed that substituted phenyl groups can be covalently attached to hydrogen-terminated.254 1 Preparation of Monolayer Modified Electrodes (diamond)• + C6 H5 COO• − − diamond−OOC−C6 H5 −→ IR modes at 3072 cm−1 for the aromatic C−H stretch. ∼402 eV) Potential (mV vs. All adlayers were stable during exposure to air and different organic solvents. 10 First scan–cyclic voltammetric i−E curves for the reduction of 4-nitrophenyl diazonium tetrafluoroborate at microcrystalline and nanocrystalline diamond thin-film electrodes. More recently. Estimated surface coverages of 50–70% of a compact monolayer were achieved.1 M TBAClO4 /CH3 CN. Kuo et al. 3) [51]. boron-doped diamond electrodes during the electrochemical reduction of substituted phenyl diazonium salts in acetonitrile (see Fig. Raman spectroscopy was employed to interrogate the structure of chemisorbed nitroazobenzene on diamond and the spectral features were found to be similar to those observed for derivatized GC. ∼686 eV). our group has been conducting detailed studies of the diazonium modification of diamond electrode surfaces with two types of diamond being investigated: microcrystalline and nanocrystalline thin films. The chemical state of the diamond surface is determined by the relative proportion of [−OOC−(CH2 )n −COOH] versus [−OOC−C6 H5 ] sites.

as shown in the following. The cathodic current is associated with the 1e− reduction of the diazonium to form a nitrophenyl radical. The surface coverage of electrochemically active nitrophenyl groups was also determined on the basis of the charge passed during the reduction of the nitro functional group.25) × 10−2 and 6. The curves were recorded in 0. 11 Reaction mechanism for the electroreduction of the attached nitrophenyl admolecules. respectively. −→ (diamond)−H + •C6 H4 −NO2 − − (diamond)• + C6 H5 −NO2 {abstraction} (diamond)• + •C6 H4 −NO2 − − −→ (diamond)−C6 H4 −NO2 {grafting} For both electrodes.16) × 1017 and 4. At least two radicals are needed for the surface modification.04) × 1017 radicals/cm2 produced.28(±0. There is no anodic current during the reverse sweep as the reaction is chemically irreversible. the number of radicals produced is at least 2 orders of magnitude greater than what is needed to form a compact monolayer. The voltammetric reduction or oxidation charge can be used to calculate the number of electroactive molecules that are attached to the surface. Figure 12 shows cyclic voltammetric i−E curves for the reduction of the bound nitrophenyl groups at both types of modified diamond electrodes.55(±0. the reduction of the attached nitro group involves the 1e− reversible reduction to the anion radical. 35 µA as the geometric area is the same for both. e− Electrode −e− Electrode .6 Recent Trends in Chemically Modified sp2 and sp3 Bonded Carbon Electrodes 255 diamond film types are shown. The cathodic current increases for both electrodes at 200 mV.81(±0. The second radical then forms a covalent bond with the surface.1 V s−1 . These charge values correspond to 3.06) × 10−2 C cm−2 for microcrystalline and nanocrystalline diamond.64(±0. One is required to abstract hydrogen from the diamond surface creating an active site Fig. The peak current for both electrodes is ca. 11. reaching a maximum near −150 mV.1. XPS (N 1s signal) was used to confirm the presence of the nitrophenyl adlayer. Liu and McCreery reported the theoretical coverage for the case of close packing on a flat surface with the nitrophenyl molecule upright. 12 × 10−10 mol cm−2 or 7 × 1014 molecules/cm2 [48]. The reaction is shown below in Fig. The results indicate that the response of both diamond types is similar and that the response for multiple electrodes is quite reproducible. The potential was swept initially in the negative direction from 600 to −600 mV at 0. + for radical coupling. In nonaqueous medium. A radical formed at the electrode–solution interface can then react as a surface site to form a covalently attached admolecule according to the reactions below.1 M TBATFB in CH3 CN NO2 +e− − NO • 2 N2 −C6 H4 −NO2 + e− − − •C6 H4 −NO2 −→ Integration of the reduction peak current gives a charge density of 5.

The authors showed that nanocrystalline diamond thin films can be covalently modified with DNA oligonucleotides and that diamond surfaces provide a stable and selective platform for subsequent hybridization processes. Diamond appears to be a suitable material for integrated sensing and signal processing because of its chemical and electrical properties. 12 −6 Cyclic voltammetric i−E curves for the reduction of the nitrophenyl admolecules on the surface of microcrystalline and nanocrystalline diamond thin-film electrodes. 27 µA cm−2 . After linking DNA to the amine groups.5 × 1014 molecules/cm2 . Comparison of DNA-modified Current [µA] .1 × 10−9 mol cm−2 or 6.025 V s−1 . This step produced a homogeneous layer of amine groups that serve as sites for DNA attachment. The results demonstrate that the diazonium chemistry is a viable method for chemically modifying diamond electrode surfaces and that the admolecules are in good electronic communication with the conducting electrode. hybridization reactions with fluorescently tagged complementary and noncomplementary oligonucleotides showed no detectable nonspecific adsorption with extremely good selectivity between the matched and mismatched sequences. at 0.025 V s− .256 1 Preparation of Monolayer Modified Electrodes Potential (mV vs. The curve shapes were quite stable with cycle number and were recorded after extensive electrode washing to remove unattached physisorbed molecules. The peak current for both electrodes is in the range of 5–6 µA or ca. A photochemical modification scheme was used to first modify a clean and hydrogen-terminated diamond surface. reaching a maximum between −1100 and −1200 mV. the surface coverage of electroactive molecules on both electrode types was calculated to be 1. The cathodic current for the reduction begins at approximately −600 mV for both modified electrodes. Ag wire) −1500 −1250 −1000 −750 −500 −250 0 3 2 1 0 −1 −2 −3 −4 −5 Microcrystalline Nanocrystalline Fig. The Hamers’ group has been particularly active and innovative in recent years with the chemical modification of diamond surfaces for biological applications [100]. On the basis of the oxidation peak charge. Scan rate = 0. and is in good agreement with the value reported by Wang and coworkers for ultrananocrystalline diamond thin-film electrodes [99]. This value is very close to the theoretical monolayer coverage of 7 × 1014 mol/cm2 [48].

methylcatechol. Si. catechol. 1. showed that diamond is unique in its ability to achieve very high stability and sensitivity while also being compatible with microelectronics processing technologies. 13 Diamond Reaction steps in the DNA attachment to diamond thin-film surfaces [100]. Similar blocking layer effects have been reported by Wang and coworkers for nitrophenyl adlayers on ultrananocrystalline diamond [99]. the preliminary work indicates that the nitrophenyl admolecules act as a blocking layer for some systems (Fe(CN)6 −3/−4 and Ru(NH3 )6 +3/+2 ). This may be due to the formation of multilayers [52]. there has been minimal work reported on how the surface modification of diamond affects the electron-transfer and adsorption properties. ultrananocrystalline diamond (produced from CH4 /Ar mixtures) with other commonly used surfaces for biological modification. Figure 13 shows the reaction sequence. Much remains to be done in this area.5 Effect of Surface Modification on the Electrochemical Properties So far. The exception to this is some work on the effect of adding surface oxygen [40. the adlayer seems to exhibit little influence on the voltammetric response for other redox systems (catechols). and glass. Ru(NH3 )6 +3/+2 . Our group has investigated the effect of modifying the surface of diamond electrodes with nitrophenyl admolecules via the aryldiazonium reduction reaction.6 Recent Trends in Chemically Modified sp2 and sp3 Bonded Carbon Electrodes O F3C NH F3C O NH NH2 257 H H H Deprotect 254 nm Diamond − + SO3 Na S Diamond HCl/CH3OH Diamond 5′ DNA 3′ O N O O NH2 N O O O O HN O N O SH 5′ DNA 3′ Diamond Fig.1. GC. The authors concluded that diamond might be the ideal substrate for integration of microelectronics with biological modification and sensing. 89. On the other hand. 90]. such as Au. .6. Using cyclic voltammetry and redox systems such as Fe(CN)6 −3/−4 . and tert-butylcatechol.3.

59–72. pp. 2004. D. Miller. G. The fundamental knowledge gained from this research will enable a better understanding of structure–function relationships with these electrode materials. 1247. 46. Fischer. Bard. SEM and AFM are used to probe the modified electrode surface topography. Karweik. Rubinstein). 2553. McCreery. J. . 5. D. 2004. Chem.: C.6. 13. 221–374. pp. Swain. W. M. M. C. Anal. Electrically conducting diamond is an advanced carbon electrode that meets the requirements for a wide range of applications. 76. New York.. Chem. is fairly well developed. Durst. H. J. Ristein). I.-C. Chem. R. 1985. Research directed toward the development of chemistries useful for modifying the surface of sp2 and sp3 carbon materials will ultimately provide molecular of interactions at electrified interfaces. T. G. E. L. 1940.4 Acknowledgments Conclusions This chapter gives a brief overview of some of the recent trends in the area of chemically modified sp2 and sp3 bonded carbon electrodes. Hupert. A variety of tools are available for characterizing modified electrode surfaces. M. Vol. M. Interface 2004. Y. diamond) that will continue to evolve is the use of this material as a platform for chemical and biological sensing. 14. Powell).258 1 Preparation of Monolayer Modified Electrodes 1. 68. Chem. Prospects in the Analysis of Chemically Modified Electrodes. The Netherlands. pp. W. Swain. Murray. XPS is used to determine the surface chemical composition. Ser. 9. Much remains to be learned. R. both sp2 and sp3 types. A. Murray. M. Amsterdam. 12. P. L.: A. Copyright 1982 by the American Chemical Society. A 1981. Casper. 1995. the chemical modification of sp3 carbon materials is in its infancy. J. McCreery. R. G. 67. 10. Murray. D.g. Anal. 59. Chem. 3574. Elsevier. (Semiconductors and Semimetals) (Eds. 8. R. Fryling. 2004. and Raman spectroscopy is employed to examine the orientation and coverage of admolecules.: L. A.: A. about structure–function relationships at electrically conducting diamond electrodes. 1976. Electrochemically-assisted modification of carbon electrode surfaces. Anal. L. 3958. M. Electrically conducting diamond thin-films: advanced electrode materials for electrochemical technologies in Electroanalytical Chemistry (Eds. The chemical modification of sp2 carbon materials is quite a mature field. C. one area of research with sp3 bonded carbon (e. 188. 7. R. J. Nebel. Chen. Chen. R. Muck. 89–119. Anal. Clearly. McCreery. pp. L. #199 Industrial Applications of Surface Analysis (Eds. 2. 1987. Marcel Dekker. Anal. Mater. I. T. 121–148. The financial support provided by the National Science Foundation (NIRT Program. McCreery. Electroanalytical applications of diamond electrodes in Thin-Film Diamond II. 4. 12. Chem. McCreery. R. 3. 302. M. New York. GC) in terms of several properties and in some of its functioning in electrochemical applications. F. C. Electroanal. A. Bard). 1996. References 1. Philos. CTS-0210366) and the Department of Energy Office of Basic Science (DEFG02-01ER15120) is gratefully acknowledged. 1982. however. on the other hand. J. W. Ewing. Porter et al. 6. Ranganathan. 48. 379A. Show. Vol. Kuwana. Diamond Relat. 1991. Anal. Vol. Elliot. H. L. 11. P. 253. Kuo. Chem. Hu. W. 1995. 2003. 182–277. 13. 17. Soc. A. in Electroanalytical Chemistry (Ed. Trans. J. Karweik. 22. R. Swain. R. Wang et al. 77. Marcel Dekker. G. 71. R. S. For example. 3115.g. London.. ACS Symposium Series. Research has already shown that this material is superior to commonly used sp2 carbon electrodes (e. A. A.

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1 conducting. useful descriptions of the most widely used preparative deposition techniques for thin films of TCO electrodes are presented (see Sect.2). 1. permanent dipole moment). In3+ . To obtain new n-type multicomponent TCO films using ternary Encyclopedia of Electrochemistry. Japan 1.Rubinstein. The most widely used TCO film is Sn-doped In2 O3 (indium–tin oxide or ITO) due to its high conductivity. More recent reviews of TCO films are available [11–16].1 Introduction This chapter describes the chemical modification of various n-type transparent conducting oxide (TCO) electrode surfaces with different organic molecules. the other end is a terminal group with a different functionality (e. In addition. The early published material in this field up to about 1955 has been reviewed by Holland [2]. and CdIn2 O4 were developed prior to 1980 [8. which has better transmission and lower resistivity than CdO.7 Chemically Modified Oxide Electrodes 261 1. Stratmann Vol.1. low cost. Ti2+ . Yokohama.g. in which one end is a binding group. Much better is cadmium stannate (Cd2 SnO4 ) film [18]. Although ZnO films are nontoxicity. material abundance. they are more chemically unstable than ITO films [17]. CdSnO4 .or Al-doped ZnO have been the principle commercial TCO films in practical use [13–15]. ZnO. The principle constituents of n-type TCOs have been simple or binary oxides of SnO2 .F. Conductive ZnO films doped with an impurity have recently attracted much attention as an alternative candidate to ITO. 18].7 Chemically Modified Oxide Electrodes Chimed Ganzorig and Masamichi Fujihira Tokyo Institute of Technology.Rusling Copyright  2007 Wiley-VCH Verlag GmbH & Co. and Cd2+ ) oxides and their corresponding alloys to develop highly transparent and electrically conductive thin films. Since then. CdO is not often used as a TCO semiconductor because of its relatively low bandgap of about 2 eV resulting in excessive light absorption from about 0. Sb-doped SnO2 . most researches have focused on n-type semiconductors consisting of metal (Sn4+ . ISBN: 978-3-527-30402-8 . Edited by A. and CdO. F-doped SnO2 . In2 O3 .7.7. Sn-doped In2 O3 .2. and transparency in the visible spectral range. Studies for the formation of various organic monolayers with carboxylic and phosphonic acids as well as organosilanes on these oxide electrodes are reviewed and discussed comprehensively in this chapter. 9.Fujihira.5 µm down into the ultraviolet [7]. and easily etchable. but their TCO films have not yet been used widely.7. Major developments in this field as regards the deposition techniques of preparation.2 Electrode Preparation General: Transparent Conducting Oxide Films The first report of a transparent conducting oxide (TCO) was published in 1907. Zn2+ . 1. Several examples of organic chemical treatments used for surface modifications of n-type TCO electrodes are presented. and F. KGaA. 10 Modified Electrodes. and these two ends are linked by groups of alkyl chain and π-system. and J. when B¨deker [1] reported that thin a films of Cd metal deposited on glass in a glow-discharge chamber could be oxidized to become transparent while remaining 1. Ternary compounds such as Cd2 SnO4 .J. Bard and M.7. Weinheim. Edited by M. work function. I. properties of TCO films and some applications until the mid-1980s have been summarized in several comprehensive reviews [3–10].

Surfaces of the first category are required for special scientific purposes and these can be only realized in ultrahigh vacuum. particularly during the past years. is known to exist in the amorphous form and in three crystalline modifications. After the cleaning methods of the substrate surfaces are discussed in briefly in Sect. new p-type TCO materials such as CuAlO2 and SrCu2 O2 have been reported recently [19–22]. Cleaned surfaces can be classified into two categories: atomically clean surfaces and technologically clean surfaces. ion beam sputtering. 1. Original works and their useful descriptions of the most widely used deposition methods of preparation for TCO films have been discussed comprehensively in reviews [3–16. There are number of diverse cleaning techniques used in various scientific and industrial cleaning problems [64]. Brookite is not a stable modification and anatase is converted to rutile at high temperatures.4. or solid in its physical state and may be present as a film or in particulate form. Thin films of TiO2 have been shown to possess either a rutile or anatase structure depending upon their mode of deposition. 1. the characterization of TCO thin films is described in Sect. In addition. TiO2 is the most investigated system in the surface science of metal oxides. 24–30]. The low temperature processes such as magnetron sputtering. The cleaning of surfaces is a very important and also a very difficult and delicate operation.2. 31–63] in these deposition techniques for TCO thin films are listed in Table 1.7.7. the substrate can have a significant influence on the properties of thin films. Surface contamination can be gaseous. sol-gel. Mylar. electroplating) and physical methods (evaporation. Cleaning of Substrate Surfaces A number of techniques have been advocated for preparing highly clean substrate before depositing thin films on its surface by various deposition techniques.2. Several different techniques have been tried out to fabricate films of TCO electrodes. and reactive ion plating allow the deposition of oxide films also onto polymer substrates such as plastic. Surfaces exposed to the atmosphere are generally contaminated. 1. In addition to n-type TCO films. cleaning cannot 1. In all cases where handling of the parts and the use of solvents is required. Furthermore. and brookite. liquid. Thin-film deposition techniques are generally classified in two main groups: chemical methods (spray pyrolysis. anatase. it can be ionic or covalent and inorganic or organic in its chemical character. Most scientific and technical investigations and applications. 800–900 ◦ C [2]. several approaches have been studied in recent years [15]. sputtering. Titanium dioxide.7. Depending on the deposition technique. A further distinction must be made between cleaning methods that are applicable in the atmosphere and those that are applicable only in vacuum.2. however. Glass substrates are most commonly used.2 . chemical bath deposition. reactive ion plating. Recent progress in understanding the surface science of TiO2 was reviewed extensively by Diebold [23]. a brief account of numerous methods used for film deposition. Some of the innovations [1. pulsed laser deposition). Any unwanted material and/or energy on a surface are regarded as a contaminant.2.262 1 Preparation of Monolayer Modified Electrodes compounds. rutile.7. Some early references are also cited wherever necessary.2.2.5. 23] and books [2.3 and 1.7. TiO2 . and poly(ethylene-terephthalate) [9]. require clean surfaces. in Sects. chemical vapor deposition.

If cleaning in vacuum. In TiN ZnO:B ZnO:Ga ZnO:F ZnO:Al ZnO:Ga ZnO:In Zn2 SnO4 ZnSnO3 Cd2 SnO4 ZnO:Al be performed in a vacuum. diluted acids or bases and nonaqueous solvents such as alcohols. various cleaning fluids are used. 31–63] Deposition technique Sputtered Cd films Postoxidation of Sn Fuming of TiCl4 Spray pyrolysis Postoxidation of Ti Postoxidation of Zn Spray pyrolysis Spray pyrolysis Reactive sputtering Spray pyrolysis Spray pyrolysis Reactive sputtering Reactive sputtering Reactive sputtering Direct sputtering CVD Magnetron sputtering Direct sputtering Spray pyrolysis Spray pyrolysis CVD Spray pyrolysis Magnetron sputtering CVD CVD Sputtering CVD CVD CVD CVD Magnetron sputtering Magnetron sputtering Pulsed laser deposition Pulsed laser deposition References 1 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 Material CdO SnO2 TiO2 SnO2 :Cl TiO2 ZnO SnO2 :Sb In2 O3 :Cl SnO2 SnO2 :F In2 O3 :Sn ZnO In2 O3 In2 O3 :Sn ZnO SnO2 :Sb ZnO:Al Cd2 SnO4 Cd2 SnO4 ZnO:Cl SnO2 :F ZnO:In ZnO:B. 27.2. 1 263 History of processes for making n-type TCO thin films [1. There are many reports on cleaning of glass by solvents. by heating operations and particle bombardment is used. . Emulsions and solvent vapors are also used.7.1 Cleaning with Solvents In this process. 1. and chlorinated or fluorinated hydrocarbons. Ga. then this is generally conducted inside the deposition system [27]. A distinction must be made between demineralized water or aqueous systems such as water with detergents.2. ketones.1. some examples are given in Refs. 2. 64–67. The type of solvent used depends on the nature of the contaminants [64].7 Chemically Modified Oxide Electrodes Tab. petroleum fractions. for example.

as the first step in a cleaning sequence. the operation can be repeated by further dipping in the same fluid or other cleaning fluids. with the exception of hydrofluoric acid. This method is best suited as a precleaned operation. The solvent is vaporized and forms a hot. that is. which remains in the equipment because the condenser coils prevent vapor loss. A simple and often used cleaning technique is that of immersion or dip cleaning. to produce a clean glass surface. are then dipped in the fluid. chemical reactions can be also exploited for cleaning purposes. If the degree of cleaning is not sufficient. An open tank of glass. Acid cleaning cannot be used for all types of glasses. The lipids and fatty materials are saponified by the bases to soaps. The efficiency of cleaning can be checked by determining the coefficient of friction. There is evidence. as well as mixtures such as chromic and sulfuric acid are used.264 1 Preparation of Monolayer Modified Electrodes Rubbing and Immersion Cleaning Perhaps the simplest method of removing superficial dirt from glass is to rub the surface with cotton wool dipped in the mixture of precipitated chalk and alcohol or ammonia. it is often used as the last step in a sequence of various cleaning operations. In glass cleaning. Pure cleaning fluid vapor has a high solvency for fatty substrates. and . which drips off and is replaced by more pure condensing solvent. 2% Teepol . in special holders. Caustic solutions exhibit a detergency and the ability to remove oils and greases. which are clamped with a pair of tweezers or are inserted in a special holder. Various acids with strengths ranging from weak to strong. 67]. or stainless steel is filled with a cleaning fluid and the glass parts. Attention must be paid to unwanted. These water-soluble reaction products can readily be rinsed off the clean surface. and leaching effects. The basic equipment employed in dip cleaning is easy to construct and inexpensive. Vapor degreasing is an excellent way to obtain highly clean surfaces. stronger etching. contact-angle. but a mild attack of the substrate material itself is often tolerable and ensures that the cleaning process is complete. such as some optical glasses. This is especially true for glasses having a high barium or lead oxide content. The cleaning fluid may be isopropyl alcohol or one of the chlorinated and fluorinated hydrocarbons. and when it condenses on cold glass a solution is formed with the contaminant. A vapordegreasing apparatus consists essentially of an open tank with heating elements in the bottom and water-cooled condensing coils running around the top perimeter. plastic. Such processes may destroy the surface quality and should therefore be avoided. According to a report in [67]. are immersed in the dense vapor for periods ranging from 15 s to several minutes. high-density vapor. a cold diluted mixture of 5% HF. It is desirable to limit the removal process to the contaminant layer. that traces of chalk can be left behind on such surfaces so that after that treatment the parts must carefully be washed off in pure water or alcohol. between 60 and 85 ◦ C. All acids. The process runs until the glass is so hot that condensation ceases [66. must be used hot. Vapor Degreasing Vapor degreasing is a process that is primarily useful for removing grease and oil films from surfaces. that is. in addition to dark-field-inspection. 33% HNO3 . however. In addition to physical cleaning. and 60% H2 O should be an excellent universal fluid for cleaning glass and silica. The precleaned cold glass pieces.

film deposition is performed at higher substrate temperatures. for instance.2 Cleaning by Heating and Placing substrates in a Irradiation vacuum causes evaporation of volatile impurities.7 Chemically Modified Oxide Electrodes 265 thin-film-adhesion measurements. The action of these sound waves gives rise to cavitation at the glass surface/cleaning liquid interface. Highpressure spraying of organic liquids causes problems with surface cooling followed by unwanted water-vapor condensation.1. instead of an organic liquid. desorption is produced here by heating. a hydrogen-air flame. Only in case of ultrahigh vacuum applications is it necessary to use heating temperatures higher than 450 ◦ C in order to obtain atomically clean surfaces. which shows no spotting. The particles will be suspended in the turbulent fluid and carried away from the surface. The applied temperatures are in the range between 100 and 350 ◦ C and the required heating time is between 10 and about 60 min. high-pressure air or gas jets are very powerful. which can leave surface spots. Cleaning by heating is particularly advantageous in all those cases where. Pressures of about 350 kPa are used. as well as organic liquids. Ultrasonic cleaning is also used to remove pitch and polishing-agent residues from glass surface. Ultrasonic Cleaning Ultrasonic cleaning provides a valuable method of removing stronger adherent contaminants. Glass is chiefly cleaned at frequencies between 20 and 40 kHz. 1. However. This process produces an intense physical cleaning action and is therefore a very effective technique for breaking loose contaminants that are strongly bonded to a surface. depending on the temperature. High-pressure liquid spraying is a very powerful and effective method to remove particles as small as 5 µm. Increasing the pressure and the corresponding liquid velocity results in an increase in cleaning efficiency. the influence of partial pressure on desorption is negligible.2. Spray Cleaning The spray-cleaning process uses the shearing forces exerted by a moving fluid on small particles to break the adhesion forces holding the particles to the surface [27]. This sometimes makes such heat treatments problematical. are used. as a consequence of heating. Heating the glass surfaces causes a more or less strong desorption of adsorbed water and various hydrocarbon molecules. treatment with high-temperature flames. In some cases also. the same types of liquids that are used for immersion cleaning can also be used for spray cleaning. The cleaning is performed in a stainless steel tank containing the cleaning fluid and equipped with transducers on the bottom or at the sidewalls. In general.2. The effectiveness of this process also depends on how long the substrates remain in the vacuum and on the temperature as well as on the type of contaminant and on the substrate material. These transducers convert an oscillating electrical input into a vibratory mechanical output [66]. basic. But. because of desired special film properties. High values are typical for clean surfaces [67]. Therefore.7. and neutral cleaning fluids. Under high-vacuum conditions at ambient temperature. Inorganic acidic. shows good results. polymerization of some hydrocarbons to larger aggregates and decomposition to carbonaceous residues may also occur. This can be prevented either by using a surrounding nitrogen atmosphere or using a water spray. although the surface temperature .

A glass surface immersed in the plasma of a glow discharge is bombarded by electrons. type of material to be cleaned. mainly positive ions and activated atoms and molecules. that mild cleaning is effective only when oxygen is present. the lacquer film is stripped off.2. performed in a laminar flow box to prevent recontamination. In a subsequent operation. ionized particles strike the surface of the parts to be cleaned. type of gas and gas pressure.2. duration of treatment. . The basic cleaning procedure is quite simple. however. According to this model. which are positioned near the substrates. The substrates are immersed into the plasma. shape and arrangement of electrodes.2. and N2 . In a flame. Therefore.2. 1. one of the Discharge most efficient methods of cleaning a glass surface is to immerse it in a glow discharge. Particle bombardment and surface recombination of ions will liberate heat and may in this way also help to desorb contaminant molecules.7. 69] are present. without being a part of the glow-discharge circuit. The thick lacquer coating is applied to the precleaned surface with a brush or by dipping. Exposure times of about 15 h in air produced clean glass surfaces [70]. This clearly demonstrates that the presence of ozone increases the cleaning speed. Typical discharge voltages are in the range between 500 and 5000 V. It is assumed that the excited contaminant molecules and the free radicals. 1.4 Cleaning in an Electrical Undoubtedly. it is known that the contaminant molecules are excited and/or dissociated under the influence of UV. As for the cleaning mechanism. clean surfaces are produced in even less than one minute [71]. various kinds of ions as well as impurities and molecules of high thermal energy [68. Only precleaned substrates are treated. Another technique for cleaning surfaces is the use of ultraviolet (UV) radiation to decompose hydrocarbons. Generally. the cleaning action of a glow discharge is very complex.3 Cleaning by Stripping Lacquer Coatings The use of strippable adhesive or lacquer coatings to remove dust particles from a surface is a very special and somewhat unconventional cleaning technique. CO2 .266 1 Preparation of Monolayer Modified Electrodes in such a process reaches only about 100 ◦ C. It seems. aluminum electrodes. the discharge burns between two. which impart their energy to the adsorbed contaminants. react with atomic oxygen and form simpler and volatile molecules like H2 O. and much of work on this subject has been reviewed by Holland [2. produced by the dissociation of the contaminant. Oxygen and sometimes argon are normally used to form the necessary gas atmosphere. it is also known that the production and the presence of ozone produce highly reactive atomic oxygen. Furthermore. If properly precleaned surfaces are placed within a few millimeters of an ozone-producing UV source. 67]. It is assumed [67] that the cleaning action of a flame is similar to that of a glow discharge in which highly energetic. only negligibly sputtered. Attempts to strip off the film in vacuum prior to thin-film deposition were only partly successful because of the difficulty in detecting surface residues inside the evacuated system [27]. the current density. removal of material from a glass surface in a flame may occur because of the high-energy particles. The most important parameters in glow-discharge cleaning are the type of applied voltage (AC or DC). the value of discharge voltage.7. The parts are then allowed to dry completely.

generally. combinations of the various cleaning methods must be used. The change from aqueous solutions to organic fluids always requires an intermediate treatment with a mixable co-solvent such as alcohol or special dewatering fluids. metal. offer interesting possibilities not only in cleaning but also in polishing and machining of optical surfaces. The last steps in a cleaning cycle must be performed extremely carefully. In a cleaning operation. low cost. A change from acidic solutions to caustic solutions requires rinsing with plain water in between. it is important that cleaned surfaces are not left unprotected. cleaning means that the surface must be modified in 1. wiping.2. The plasma energy can be much higher than that achieved thermally and still not damage surfaces because of the low thermal flux. It is important to get the parts dry without allowing solution sediment to remain on the surface because it is often hard to remove later [27]. has all the desired features of simplicity. However. the final rinsing fluid used must be as pure as possible and. Mattox [72] discussed the types and origins of various contaminants and reviewed the cleaning processes for oxide. Proper storage and handing before further treatment by film deposition are stringent requirements. Heating is useful up to the temperature limits of the surfaces to be cleaned.1. and so on. Plasma treatment provides a cleaning method where contaminant bond strengths exceed the temperature limits of the system.7. Cleaning of Organic Glass Cleaning of organic glass and plastic materials requires special techniques and handling because of their low thermal and mechanical stability. Ion-beam technologies.5 Cleaning Cycles Surface cleaning is performed by various methods. stripping. particularly where the solvents themselves are contaminants. Finally. Each has its range of applicability. such as washing with solvents. the sequence of cleaning liquids must be chemically compatible and mixable without precipitation at all stages. antistatic films. assisted by rubbing. With organic polymers. Precleaning of glass parts usually starts with immersion cleaning in detergent solutions. Organic glass surfaces may be covered with low molecular weight fractions. No one method. as well as for modifying the optical constants of subsurface layers [27]. heating. and plasma treatment. There is no universal approach to cleaning cycles. In a wet operation.6 . Most of the contaminants can be removed by an aqueous detergent wash or by other solvent cleaning possibly associated with mild liquid etching.7 Chemically Modified Oxide Electrodes 267 and position of the parts to be cleaned. care must be taken with cleaning fluids because they may be adsorbed into the polymer structure causing it to swell and possibly to craze on drying. Solvent cleaning has the greatest range of utility but is inadequate in many cases. however. and organic surfaces and the mechanisms of adhesion to these surfaces. fingerprints. however. Substrate cleaning in high vacuum by bombardment with ions generated in special ion guns is seldom used for industrial coating processes. 1.2.2.2. There are.7. some general guidelines to follow when establishing cleaning sequences. surface oils. or ultrasonic agitation. however. followed by rinsing in demineralized water and/or alcohol. To achieve optimum cleanliness of substrate surfaces. and effectiveness. it should be as volatile as is practical.

especially different atomization techniques. The hydrolysis of chlorides [4] is normally involved.268 1 Preparation of Monolayer Modified Electrodes such a way that it does not represent an area of insufficient adhesion at the interface substrate surface/film formed after film deposition. was presented [12]. the atomizer test and the water-break test [27]. Surface cleaning and recontamination of glass was monitored by contact angle measurements using distilled water [67]. which is generally high on clean glass surfaces. frequent cleaning of plastics may simply mean the modification of the surface so that the contaminant initially present is afterward no longer considered as a contaminant. dip-coating heated hot vitreous substrate in the solution containing SnCl4 [33]. The critical operations for the spray pyrolysis technique are (1) preparation of uniform and fine droplets and (2) the controlled thermal decomposition of these droplets in terms of environment. The cleaned parts should be mounted into the substrate holders immediately after cleaning and the whole device should be placed carefully and quickly in the coating systems.7. 1. Many variants have been tried to grow the films but the basic technique used by all the workers is similar to that described in Ref. spray rate. Therefore. The thermal decomposition takes place on the hot substrate surface giving rise to a continuous film. and pyrolytic decomposition of SnCl4 [36. such films have been prepared by blowing fumes of SnCl2 onto heated glass [75].2. Vigui´ and Spitz [74] have clase sified chemical spray deposition process according to the type of reaction. 8. The proper treatment in glow discharge plasma is very effective for that purpose since. namely substrate temperature. Thin films of SnO2 .3 Chemical Methods of Film Deposition 1. is to avoid long intervals between cleaning and film deposition. location. There are many cheaper cleanliness tests such as inspection of the breath figure. concentration of solution. based on spraying the hot glass with a solution of InCl3 [37] or introducing it into an airstream containing SnCl4 [76]. There are also some patents in the literature. in addition to micro roughening. Proper cleaning fluids and short cleaning time as well as carefully established energy limits and proper doses in particle bombardment or in radiation treatment are important for optimum results. and so on [9]. a solution of SnCl4 or InCl3 in a mixture of alcohol and water is sprayed onto heated substrates. 39]. For example. All of these qualitative tests are based on the wettability. beside cleanliness of operator and environment.2. Since the production of the first thin films of SnO2 by oxidation of a metallic Sn film in air [31].1 Spraying Pyrolysis Many studies have been done over about five decades on spray pyrolysis (thermal decomposition) for preparation of TCO films. it also causes chemical activation and crosslinking [72].7. The contact angle of water droplets and droplets of other materials on a surface can even be a quantitative measure of wettability [73]. A most recent survey on thin-film materials prepared by spray pyrolysis and advances in the field.3. The best precaution for preventing recontamination. The prime requisite for obtaining good quality thin films is the optimization of preparative conditions. Some review articles pertaining to spray pyrolysis processing and the range of thin films deposited by this technique for various applications have appeared in the literature. and time.

and ZnO:Tb [106] have been deposited by the pyrolytic decomposition using alcoholic solutions of ZnCl2 or Zn(CH3 COO)2 . stoichiometry. HCl [92]. Films of ZnO [49. SnO2 :Sb [85–89]. SnBr4 [82]. or tetrabutyltin [82]. ITO [90. Similarly. SbCl5 has also been tried as the dopant of Sn. ZnO:In [51]. Alcoholic solvents were the most preferred because of their low surface tension and viscosity facilitates the formation of small spray droplets while its low boiling point enables it to be efficiently removed from the deposition chamber in the vapor phase. and above this temperature have a structure of anatase. 78–85].3. propanol [85]. namely good durability and chemical resistance. and SnO2 :F [89–92] have been deposited by spraying alcoholic solution usually of SnCl4 and sometimes of SnCl2 [88. 92]. 90]. Various dopants were added to above precursor solutions in the form of chlorides. InCl3 is used as a source of indium in In2 O3 [93. It can be prepared by means of oxidative pyrolysis of various Cd-alkyls [115].2. Cd2 SnO4 [116] films have been deposited by spraying appropriate combinations of SnCl4 −CdCl2 . The solutions are made usually by dissolving SnCl4 or InCl3 in some solvents such as ethanol [83. TCO films using undoped ZnO by spray pyrolysis were reported by Aranovich and coworkers [49] in 1979. the films were cloudy and contained both rutile and anatase phase [114]. 37.2 . and at higher temperatures (above 450 ◦ C). The anatase thin films of TiO2 with good crystallinity and large area were obtained from the spray pyrolysis technique [110–113]. A simple and effective method for preparing of TiO2 films by decomposing TiCl4 with atmospheric water vapor was first proposed by Cartwright and Turner in 1939 [32] and further developed by Tanner and Lockhart [107]. 98–101]. or In2 O3 :F [97] films. Chemical Vapor Deposition Films with high demands for purity. Tin doping is achieved by adding SnCl4 . methanol [92]. 36. Antimony doping is achieved by adding SbCl3 to the spray solution. 39].7. Banning [108]. Cd2 SnO4 is another transparent conductor having desirable properties. Fluorine doping is achieved by adding NH4 F and sometimes trifluoroacetic acid [90] or HF [91]. Banning [108] found that the hardness and refractive index of TiO2 films were increased by raising the glass temperature to 200 ◦ C and maintaining the liquid tetrachloride at 60 ◦ C. 94]. Their techniques consisted of spraying a solution of stannic chloride and water onto a glass surface heated to 550–650 ◦ C so that a layer of SnO2 was formed [33. TCO thin films of SnO2 [31. butyl acetate [93]. The solvent is made slightly acidic with HCl (or HF for fluoride doping) [91. 39]. 94–96].7 Chemically Modified Oxide Electrodes 269 are most commonly produced by thermal decomposition of aqueous acidified SnCl4 sprayed onto a hot glass substrate [36. ZnO:Li [105]. Hass [109] reported that TiO2 films formed by the vapor reaction process on substrates at temperatures below 280 ◦ C are amorphous. and structural perfection 1. nitrates as well as acetates and acetylacetonates [11]. and Hass [109]. and H2 O [84]. CdO was the first material reported to be semitransparent to visible light and at the same time electrically conducting. Earlier reviews were written by Bauer [31] and Fischer [77]. Films made near 325 ◦ C substrate temperature contained only the anatase phase with 75% optical transmittance.1. ZnO:Al [102–104]. Cd2 SnO4 films have been used as electrodes in photogalvanic cells [26]. 89]. The porosity of the films increased with increasing substrate temperature. sulfates.

the sol-gel process is used as a phenomenological term to describe the conversion of colloid suspensions from a liquid (sols) into a solid (gel). and so on. Kane and coworkers [119] have grown SnO2 films using dibutyl tin diacetate as the organometallic compound. ITO [125. This was for a while only a matter for chemists. ZnO [124. Significant achievements have also been made to obtain low-resistivity and textured ZnO films using CVD [50. and TiO2 [130. In general. The substrate was kept at a temperature of about 420 ◦ C. or argon are generally used as carrier gases. The principle of CVD preparation of oxide films was described in detail [26]. Ghandhi and coworkers [121] have extended their work to grow SnO2 films by adopting the CVD technique to use radio frequency (RF) plasma-activated oxygen as the reagent. the majority of TCO films are currently produced in this way. Thin films of SnO2 [74. CVD consists of a surface reaction on a solid surface. This technique could offer also economic advances of relatively low equipment cost and simple processing. either a liquid (wet gel) or a gas (xerogel). produced by the Schott Company in Germany [138]. Pioneering work was done in the Schott Glass Company in Germany. and oxygen as the reagent gas. 134–137. zinc. The main advantage of this technique is that it allows the growth of high-quality films at room temperature. who was the first to prepare a metal alkoxide from SiCl4 and alcohol. which led to the first products in the 1960s. involving one or more gaseous reacting species. They suggested using alkoxides for the preparation of optical oxide films. 120]. 131] have been deposited by CVD. and he found that the compound gelled on exposure to the atmosphere. The oxidizing agents used are usually O2 . 127–129].7. 117–122]. 124]. 56–59].3. 126]. The most important technologies used to deposit sol-gel films technically are dip and spin coating [28]. nitrogen as the carrier gas. indium. H2 O.270 1 Preparation of Monolayer Modified Electrodes could be obtained by chemical vapor deposition (CVD) methods [3]. CVD is based on the use of volatile organometallic compounds of tin. titanium. or H2 O2 [117. 54. The tin or indium compounds may be evaporated at relatively low temperature (∼100 ◦ C) when organometallic compounds [123] are used or at higher temperatures when chlorides are used [120]. chemical vapor deposition has been widely adopted in the continuous production of with F-doped SnO2 (SnO2 :F) [13]. . SnO2 :Sb films were also fabricated [123] under similar conditions. which allow deposition near thermodynamic equilibrium conditions. O2 . sputtering has become the preferred mode for its production. 53. The material aspect appeared in the 1930s in the work of Geffcken and Berger [133]. N2 . The gel consists then of two phases: a solid network penetrated by a second phase. using the sol-gel techniques and subsequent heat-treatment at a temperature of 450–500 ◦ C [139–145]. 1. Since the 1980s. By far. In2 O3 [74. A smooth and dense TiO2 anatase film was prepared. SnO2 :Sb [123]. Although ITO was first made by spray pyrolysis. Transition metal sol-gel chemistry has successfully been applied since more than 30 years in the form of titania coating on architectural glass.3 Sol-gel Process The first appearance of sol-gel reactions was observed by Ebelmen [132].2. The process development and the resulting film properties were reviewed in Refs.

146]. The technique has been used to deposit excellent quality TCO films of ITO [154. 166] have been deposited by thermal [158–161]. and the anode that is conveniently 1. Sputtering Every sputtering process involves the creation of gas plasma (usually in argon) in a low pressure chamber (from 5 × 10−1 to 10−4 mbar) between a cathode. substrate temperature.2 Evaporation Vacuum and also reactive evaporation using metallic or oxide sources have been employed to deposit various TCO films.7 Chemically Modified Oxide Electrodes 271 1.2. The important control parameters are the evaporation rate. The reduced TiOx films can be converted to TiO2 by anodic oxidation [2. A technique for preparing TiO2 film is to deposit a layer of Ti. Reactive Evaporation Reactive evaporation of SnO2 [152]. electron beam [162–164]. 2–16. They are applied.7. and TiO2 [34. which is then oxidized by baking at 400 ◦ C in air. 156] and SnO2 :Sb [157].2.1 Postoxidation of Metal Films Thin films of SnO2 [31. and TiO2 [155] thin films has been achieved by the vacuum evaporation of the corresponding metal or alloy in an oxygen atmosphere onto substrates heated to . In2 O3 [147]. TCOs are hence obtained either by the postoxidation of lower oxide films [167] or by the introduction of oxygen [158–162] during evaporation. Ohnishi and coworkers [151] found that ZnO films can be made successfully at a low temperature by the oxidation of vacuum deposited ZnSe films without the direct sublimation of ZnO powder or crystals. In Refs. In2 O3 [159–161].7. ZnO [35. Owing to its high melting point. Hamberg and Granqvist [10] reviewed work on ITO films prepared by reactive evaporation of In2 O3 with up to 9 mol % SnO2 onto heated glass. Direct Evaporation Thin films of SnO2 [158]. and oxygen partial pressure. the reaction between the evaporated species and the gas is activated by establishing thermionically assisted plasma in the reactive zone. Activated Reactive Evaporation In the activated reactive evaporation method. Dense plasma is generated in the reaction zone by employing a thoriated tungsten emitter and a lowvoltage anode assembly. 147–149]. ZnO [164. dependent on particular requirements of the production technology. ITO [161–163]. and TiO2 [2.1. 24–30. SnO2 has been deposited by electron beam [167] and flash [168] evaporation methods. or arc plasma [165] evaporated of oxide sources. these techniques will be classified and described in detail. Obviously. ITO [154]. they reduce and form opaque films of lower oxides.7.4.4. In2 O3 [153]. ˚ about 400 ◦ C at rates of about 100–300 A min−1 . 150] have been prepared by the oxidation of the respective metal films. This method has been used by Hammer [34] and was developed in Germany.4 Physical Methods of Film Deposition Physical vapor deposition encompasses sputtering and evaporation. source-tosubstrate distance. When pure or mixed oxides are evaporated. 109. they have their specific advantages and simultaneously introduce given limitations. 1.2. the target holder. 109]. 165].

N2 −O2 . Ar−O2 . 176]. Highly transparent and conducting films of SnO2 [185. SnO2 :Sb [187–189]. 196. 178]. 186]. Both reactive and nonreactive forms of DC and RF sputtering and magnetron and ion beam sputtering have been used. Under the optimum sputtering conditions. The control of film stoichiometry has been found to be easier with oxide targets. 197].3 Pa [193]. The anode was a Sn sheet and the cathode was either an Al sheet or a Pt cylinder. 42.272 1 Preparation of Monolayer Modified Electrodes used as the substrate holder [6]. so the effect . This sputtering technique was investigated by Holland and Siddall in details [42. a new set of problems are encountered with oxide targets. 169–171]. Sputtering of Oxide Targets (Direct Sputtering) Sputtering from oxide targets to form TCO films is significantly different from reactive sputtering of metal targets. which was varied by adding water. Reactive Sputtering of Metallic Targets Subsequent to McMaster’s work with chemically prepared SnO2 films. The sputtering by ions generated in the glow discharge (plasma sputtering) is the mainly used method of thin-film deposition for industrial and laboratory purposes. 194] or 1. There are two basics: DC and radio frequency (RF) diode sputtering systems and their numerous modifications in use. and Cd2 SnO4 [18. there are no problems with diffusion in mixed oxide targets of SnO2 −Sb2 O3 or In2 O3 −SnO2 . 191–195]. Since ion beam sputtering unlike RF sputtering. ITO [187. Target fabrication is quite difficult [4]. 177. TiO2 [2]. 191] have sputtered targets of In2 O3 + 20 mole% SnO2 in pure Ar. The anodizing voltage was 50 V d. SnO2 :Sb [175. ITO [43. Excellent ITO films were obtained using argon [192. involves minimal intrinsic heating and electron bombardment. and Cd2 SnO4 [183] have been reactively sputtered. 172–175]. or O2 are generally used as the sputtering gas. the films were anion deficient and very highly conducting as deposited. 193] or oxygen [194] as working gas with pressures of about 0. Vossen and coworkers [187. Yamanaka and Oohashi [185] have prepared sputtered SnO2 films using the cathode in the form of a tin oxide disk sintered from SnO2 powder at 1770 K in air. In2 O3 [42.c. Ion Beam Sputtering Ion beam sputtering differs from conventional plasma sputtering in that the projectiles bombarding the target are generated in external ion sources that are separated from the deposition chamber by pressure stages [198]. it was found by Preston [38] that partially oxidized Sn or Cd films deposited by cathodic sputtering in an oxygen-containing atmosphere (this technique being termed reactive sputtering) also formed TCO layers when heated in air. 42. The general technique and ideas involved in reactive sputtering have been well described by Holland [2]. Reactive sputtering process was extensively studied experimentally as well as theoretically [26]. ZnO:Ga [55]. producing a current density of 10 mA cm−2 . 179–182]. ZnO [44. 176. Thin films of CdO [38. Furthermore. The electrolyte used was an ammonium pentaborate in ethylene glycol. SnO2 [38. 47] have been deposited by this technique. thus obviating the need for high temperature. However. Giani and Kelly [173] have also prepared SnO2 thin films by a high-voltage anodizing method.66 Pa [192. 184]. The distance between the cathode and substrate was 6 cm and the sputtering voltage was 4. In2 O3 [190].5 kV. postdeposition annealing.

the heating effect is substantially reduced and the plasma is intensified. 200] prepared excellent ITO films from cold-pressed In2 O3 −SnO2 powder target in an oxygen partial pressure of 1. Film preparation of TCO films have been tried by magnetron sputtering [195. Applying this technique Dubow and coworkers [199. The substrate temperature was kept ∼730 ◦ C and the rate of deposition was ∼16 nm min−1 . 201] at deposition temperatures less than 100 ◦ C. Fan [201] has used an argon-ion beam source with a typical value of current of 50 mA. 211] such as Al.3 Reactive Ion Plating The production of low resistivity coatings normally requires elevated temperatures of the order of 400–500 ◦ C. For the purpose of improving stability at high temperatures.7 Chemically Modified Oxide Electrodes 273 on the substrate is minimized. ZnO [209. a few workers have used other techniques. Buchanan and coworkers [195] have grown films of indium–tin oxide of resistivity as low as 5 × 10−4 ohm cm and transmittance of ∼85%. . ZnO films [210] were prepared by impurity doping with a Group III element [15. and indium–zinc oxide [217] films have been prepared by DC. and Mylar. 206].1. quartz. The process where these particles are provided from a discharge running in the residual gas in the vacuum chamber has become to be known as ion-plating.and RF-magnetron sputtering.4. and B. High-quality films of TCOs have been fabricated by ion beam sputtering from oxide targets [173. They were able to deposit these films onto a variety of substrates including Pyrex. By employing a magnetic field to confine these electrons to a region close to the target surface. An alternative to the supply of energy to the condensing molecules by heating the substrates is to provide it by the simultaneous bombardment of the surface with high-energy active molecules.3 × 10−3 Pa. and it can be introduced into almost all the sputtering processes.5 × 10−4 cm were prepared by RFmagnetron sputtering in 1982 [207]. Magnetron Sputtering Conventional sputtering sources suffer mainly from two disadvantages: (1) the deposition rate is very low and (2) there is a substantial heating due to target secondary electron bombardment of the substrate [8].7. Ga. Impurity-doped ZnO films such as ZnO:In prepared by spray pyrolysis were reported by Chopra and coworkers [51] in 1984. ITO [216]. and the Pyrosol process [203]. In2 O3 [215]. TCO films using ZnO:Al prepared by RF-magnetron sputtering were reported by Wasa and coworkers [46] in 1971. Although undoped ZnO films with a resistivity of 4. In addition to these sputtering techniques. they were found to be unstable in temperatures above about 150 ◦ C [208]. In. 205. 1. leading to greatly increased deposition rates. Minami and coworkers [209] reported in 1984 that ZnO:Al films prepared by RF-magnetron sputtering were stable in use at temperatures as high as 400 ◦ C. 52. this process can be used to coat in plastic materials. for example. 213] and zinc–tin oxide [214] films were also prepared by RF-magnetron sputtering on glass substrates. But these processes have not been widely used. Since the substrate temperatures involved are very low.2. glow discharge [202]. or a Group IV element [212] such as Si substituted to a Zn atom site. Reactive magnetron sputtering process of thin films was reviewed by Safi [204] and references cited in it. and then reactive processes can be encouraged on the substrate surface [8].

Fe2 O3 .5 The Properties of Transparent Conducting Oxide Electrode Surfaces The methods of preparation of TCO thin films have been described in previous sections of this chapter. The structural. There have been reports of screenprinted [229] or doctor-bladed [230. The electrochemical and surface characteristics of doped SnO2 and In2 O3 film electrodes [242] were discussed and compared to those of Pt and Au film electrodes [242. The major problem with these processes is the roughness of the surface produced. and SnO2 ) [9].274 1 Preparation of Monolayer Modified Electrodes Reactive ion plating technique has been employed to deposit films of SnO2 [218]. There has been considerable interest in the fundamental electrochemical properties of SnO2 semiconducting electrodes deposited on glass or quartz substrate [236–241].2. ZnO. under certain conditions. Recently. well known for chalcogenide films.4. Some of these processes are borrowed from ceramic fabrication and metallization. Crystalline erbium (Er)doped ZnO thin films have been grown by PLD [226]. because it is one of the most kinetic methods for deposition. that is. In this form. soft solution electrochemical processes for the fabrication of oxide materials such as ZnO. Thin films were also prepared by anodization for SnO2 [173]. as the fundamental electrodeposition mechanisms were reviewed [234]. 225]. This deposition technique is well suited for these studies. 243]. so they will not be described in detail. has been extended to the deposition of oxide films (Mn2 O3 . None of these appear to be in wide use. form solid phases of hydroxides M(OH)n or hydrous oxides (M2 On · xH2 O). ITO thin films were grown on glass substrates by PLD without postdeposition annealing [228]. The mechanisms of electrical conduction and optical transmission are very much interdependent [4].5 . Howson and coworkers [218. and optical properties of TCO thin films in pure and doped forms have been reviewed [3–16]. electrical. The major parameters that control the deposition process are the composition of the deposition bath. and TiN [219] at temperatures as low as room temperature. 220] have used a reactive ion plating process to grow coatings of the oxides of indium and indium–tin alloys staring from the metal sources. its pH. electrodes have been prepared that can be used to observe electroactive species near the electrodesolution interface by internal reflectance spectroscopy in the visible region of the spectrum [237–239]. 1.7. 1. SrTiO3 thin films were grown using PLD from a single-crystal SrTiO3 target [227].4. In2 O3 :F [223]. Other Techniques Several other processes have been described for the deposition of TCO films.2. 231] techniques of In2 O3 and In2 O3 :Sn. which on heating yield the corresponding metal oxides. and its temperature.7. coprecipitation from appropriate mixture solutions for SnO2 :Sb [232] and liquid phase deposition method for SrTiO3 [233]. ITO [220–222]. In2 O3 [218–220]. A new optical approach was demonstrated by Kuwana and coworkers [235] in 1964. The chemical solution growth technique.7. the use of TCO electrode in which the product of an electrochemical reaction is monitored spectroscopically. TiO2 . ZnO:Al and ZnO:Ga films with resistivities of the order 1 × 10−4 cm were prepared by pulsed laser deposition (PLD) [224. and SrTiO3 as well 1.2. Metal ions in aqueous solution.4 Pulsed Laser Deposition Recently.

1. had been paid until the early 1970s to an application of these effects for energy conversion. 260]. Kuwana [246] has reviewed some earlier studies of the effect of light irradiation on electrochemical cells and also others in which light emission is a consequence of an electrochemical process. The material properties of In2 O3 are generally described by a high optical transparency for visible light and a high electrical conductivity [10]. several new TCO electrodes have been characterized. In2 O3 [177. therefore. The bandgaps of these n-type semiconductors correspond to the energy photons in the UV region. it is generally doped with Sn. SnO2 [259]. The preparation and characterization of nanoporous nanocrystalline TiO2 films have been described in detail [253–255]. The conductivity of ITO films can be as high as 0. using a TCO electrode whose surface was modified by the chemical binding of sensitizing dyes. Little attention. Unfortunately. 14]. a The use of these films with the addition of dye molecules has been shown to improve solar cells [253]. as it was caused by electron transfer from or to excited molecules [248]. Spectral photosensitization was also discussed from an electrochemical point of view. Another photoelectrochemical cell for energy conversion has been discussed by Tributsch [256] and by Calvin [257] using the sensitization of photocurrents by dyes that are adsorbed on semiconductor electrodes. To increase the conductivity of In2 O3 . and ZnO [247]. such as TiO2 [258]. be used effectively by these electrodes [249]. have been mainly studied to elucidate the mechanism of spectral sensitization. Gerischer [247–250] has discussed the photoeffects in electrochemical systems under illumination associated with semiconductor electrodes. Most of the useful TCOs with a wide bandgap (≥ 3 eV) studied up to now have been chemically inert conductive oxides. Fujishima and Honda [251] have discussed an electrochemical photocell based on an n-type TiO2 electrode in contact with an aqueous electrolyte and with platinum as counter electrode. significant developments in absorption spectroelectrochemistry have occurred under semi-infinite diffusion conditions and in optically transparent thin-layer electrochemistry. and the indirect coulometric titration technique has been developed and applied to biological systems [245]. The photoreaction in their system is the decomposition of water due to an oxygen evolution at the irradiated TiO2 electrode and a hydrogen evolution at the Pt electrode.5–1. High-surfacearea TiO2 films deposited on a conducting glass sheet from colloidal suspensions was reported by O’Regan and Gr¨tzel [253]. a spectrum distribution in the longer wavelength range and cannot. Since 1974. Solar energy reaching the Earth’s surface has. 261–264] is shown in Fig. including TiO2 [251] and SnO2 [252]. The solar cells developed by Gr¨tzel and his coworker a [253] described earlier are in this category. the electrochemical spectral sensitization works for various electrode materials. TiO2 has a low quantum yield for the photochemical conversion of solar energy. however.1.0 × 104 S cm−1 [10. Spectral sensitization would solve this problem. Since Gerischer [247] started using ZnO. however. In ITO . Osa and Fujihira [265] have developed a new type of electrochemical photocell. which is known as ITO (or In2 O3 :Sn).7 Chemically Modified Oxide Electrodes 275 Developments in spectroelectrochemistry based on TCO electrodes under semi-infinite diffusion conditions were reviewed by Kuwana and Winograd in 1974 [244]. Schematic band diagram of these oxides [254.

8 eV 7.8–4. 266 267 263.0 Energy [eV] 3. For wide-bandgap n-type semiconductors. 268 263.276 1 Preparation of Monolayer Modified Electrodes 0 Vacuum level 4. and chemical properties as well as physical properties of TCO materials can be controlled by altering their chemical compositions [15].5 3. 2 Bandgap energy and work function for some n-type transparent conductive pure or doped semiconductor oxides Material Bandgap [eV] 3. The conductivity increases with the product of concentration of free electrons and mobility.4 4.8 – 3.4–4. 262].4 Work function [eV] 4. 241. 3. the maximum number of electronically active dopant atoms that can be placed in the lattice determines the free-electron concentration.2 3.0–3.0 3. 263].4 4. optical.8 4.7 4. 242].0 References SnO2 SnO2 :F In2 O3 In2 O3 :Sn ZnO ZnO:F ZnO:Al TiO2 SrTiO3 254. The maximum electron concentration and the maximum conductivity in TCOs generally are found to increase in the following order: ZnO:F<SnO2 :F<ZnO:Al<In2 O3 :Sn< Ag or Cu [14]. 269 264. 274 films.2–4.0 Fig. In2 O3 [177.0 CB TiO2 SnO2 In2O3 ZnO 5. and ZnO [264]. 270 14 271 261.4 eV Tab.2 4. Their unique characteristics as transparent electrodes have led to the exclusive utilization of ITO films in flat-panel displays and solar cells. the electron concentration of ITO is ∼1021 cm−3 [10.4 ± 0. SnO2 [254. The electrical. with optical transparency still surviving.75 3.3 4.9 3. .3 4.0 VB 8. 1 Schematic diagram illustrating the energy levels of conduction band (CB) and valence band (VB) of some n-type undoped semiconductor oxides such as TiO2 [261].4 – 3.75 eV 3. 272 273.1 4.2 eV 6.

7 Chemically Modified Oxide Electrodes 277 The physical properties shown in Table 2 are the bandgap energy and work function for various types of pure and doped TCO semiconductors [14. work function. This is actually a well-known effect. Values for the work function (φ0 ) are defined. How to bind molecules on electrode surfaces has been studied extensively among electrochemists since mid1970s. 279–281]. sheet resistance. The work function of TCO electrodes can be controlled after chemical modification [277]. 1. 263].1. The studies of various surface treatments for ITO were summarized in Ref. silver.7. Friend and coworkers [278] have reported a detailed study of the characterization of different surface treatments on TCO electrodes such as ITO in terms of morphology. and oxides have been studied extensively and are called self-assembled monolayers (SAMs) [286–289]. 269] of TCO electrode surfaces also depend upon cleaning method. chemisorbed ordered organic monolayers on gold. and is called chemical modification of electrode surfaces [283–285].1 Self-assembled monolayer Y Y Y Y Y Y Y YY Y Y Y Y Y Y Y Y Y Y Y Y Molecules in solution Y Substrate X X X Y Y Solution Alkyl chain/p-system Immersion time seconds to hours Fig. surface energy and polarity. 276]. The work function [267. which has been reported for heavily doped n-type semiconductors based on In2 O3 [9. treatments are oxygen plasma and UV-ozone [269. 263]. 261–274]. The presence of dipoles or electrical charges on the surface determines the effective work function (φeff ) [275. Bandgap widening associated with doping has been observed in earlier work on doped In2 O3 films [10. and chemical composition. SAMs are 1. The optical data [10] indicated that a gradual shift of the bandgap was toward higher energy as the electron density was increased. 277. 2 Schematic drawing of self-assembled monolayers formed by simply immersing a solid substrate into a solution containing surface-active organic molecules. 254. More recently.3. The most commonly used. as the minimum energy required for an electron to escape into vacuum from the Fermi level.7. 10. carrier concentration and mobility. X Y X Y X Y X X X X X X X XX X X X X X X X X X X X X Terminal groups Y Binding groups X .3 Electrode Modification General Formation of monolayers by self-assembly at electrode surfaces has been widely used in recent years. N¨ esch and u coworkers [282] have studied acid and base treatments of the surface (the surface was cleaned with oxygen plasma prior to acid treatment).

292]. The latter was more reactive [292]. 2). Several examples of organic chemical treatments used for surface modifications of various TCO wide bandgap n-type electrodes are summarized. It was found later that −COOH is selectively chemisorbed on various oxides and −SH on Au and Ag [289. This chapter describes chemical modification of various n-type TCO electrode surfaces with various organic molecules in which one end is a binding group (X−). Kuwana and coworkers discussed the silanization of SnO2 in detail [242]. we found that a SnO2 surface could be modified with functional groups such as −COOH and −COCl. SnO2 In our previous studies [291. the silanization has been used more widely for chemical modification of electrode surfaces [283–285]. 2.7. and these two ends are linked by groups of alkyl chain and π-system as shown schematically in Fig. Organosilanes have been used for chemical modification and as coupling agents since the first reports by Murray and coworkers [290] in the mid-1970s. 3. Since the first reports. 3 Scheme for chemical modification of SnO2 electrodes with RhB−COOH and TPP(COCl)4 [291. This simple process makes SAMs inherently manufacturable and thus technologically attractive for building superlattices and for surface engineering. Fujihira and coworkers [291. 292] carried out pioneering work on covalently attaching organic molecules with functional groups such as −COOH and −COCl onto SnO2 surface. permanent dipole moment) (−Y).2 Fig. dehydrative coupling of a carboxyl group of rhodamine B (RhB−COOH) with a surface hydroxyl group of untreated SnO2 electrodes was tried using dicyclohexylcarbodiimide (DCC) as a dehydrating agent [291]. Studies for formation of various organic monolayers with carboxylic and phosphonic acids as well as organosilanes on these oxide electrodes are reviewed and discussed comprehensively in this chapter. 293–295]. Among the best 1.278 1 Preparation of Monolayer Modified Electrodes ordered molecular assemblies formed by the adsorption of molecules with a surfaceactive binding group on a solid surface (see Fig. the other end is a terminal group with a different functionality (e. 292]. one week at room temperature. As shown in Fig. – – O Sn–OH + (ClOC)4–TPP (Py) Sn–O–C–TPP(COCl)3 – – O Sn–OH + HOOC–RhB (DCC) Sn–O–C–RhB . in the presence and absence of pyridine (Py) as a catalyst for the condensation reaction [292]. SAMs can be built from a variety of molecules having surface-specific functional groups. Chemical modification of SnO2 electrode with tetra-(p-chlorocarbonylphenyl) porphyrin (TPP(COCl)4 ) was carried out by dipping the untreated SnO2 in TPP(COCl)4 methylene chloride solution for ca.g.3.

The grafting of phosphonic acid–derived stilbazole (4-(2-pyridin-4-ylvinyl)-benzylphosphonic acid) on SnO2 or TiO2 was examined as listed in Table 3 [299]. Br-. trichloromethyl-.7 Chemically Modified Oxide Electrodes Tab. 17) References 291. N -dialkanoic acids (n = 2.6 -dicarboxylic acid 8-Hydroxyquinoline-5-carboxylic acid 2-Chloroethyl-. Cl-. 296–298].4 -diphosphonic acid)2+ Alkanecarboxylic acids CH3 -(CH2 )n COOH (n = 16. Another class of self-assembling systems takes advantage of strong chemisorption of carboxylates and phosphonates on various oxide surfaces [289.4 -dicarboxylic acid)2+ Ru(bpy)2 (bpy-4-CH3 -4’-carboxylic acid)2+ Ru(terpy)(bpy-4.4 -dimethylphosphonic acid)2 2+ Eicosylcarboxylic acid and eicosylphosphonic acid 12-Ferrocenyldodecanoic and perfluorodecanoic acids 6-Ferrocenylhexylphosphonic acid Oligo(para-phenylene)-functionalized carboxylic acid p-(H-.4 -dicarboxylic acid)2+ Ru(terpy)(H2 O)(bpy-4. 309 308 309 310. The surface was modified for 3 days. Solid state 31 P NMR spectroscopic data indicated that the phosphonic group has reacted at the surface of SnO2 with formation of P−O−Sn bonds [299]. and aminomethylphosphonic acids (4-Nitrophenyl)phosphonic acid p-(H-. NO2 -. or 10) N. with the phosphonic acid derivative dissolved in H2 O at 100 ◦ C. 313 312 313 314–316 307. 18) and bifunctional SH-(CH2 )15 COOH 1. Cl-)phenylphosphoryl dichlorides n-Nonanoyl chloride and n-palmitoyl chloride Ferrocene dicarboxylic acid and 3-thiophene acetic acid Ru(bpy)2 (bpy-4. Transparent porous SnO2 films have ˚ been prepared from 30 to 50 A diameter colloids. 3 Examples of organic chemical treatments used for surface modifications of n-type semiconductors of SnO2 and ITO 279 Semiconductor SnO2 SnO2 or TiO2 SnO2 :Sb SnO2 :Sb or ITO SnO2 :Sb or TiO2 SnO2 :F or TiO2 ITO Chemical modification RhB-COOH and TPP(COCl)4 4-(2-Pyridin-4-yl-vinyl)-benzylphosphonic acid Ru(bpy)2 (bpy-4. 5. CH3 O-)benzoic acids Bicarbazyl-N. 321 322 ITO or SnO2 :F ITO or ZnO:In characterized systems are alkanethiolates on Au [289. 292 299 300–303 303 303 303 304 305 298 298 306 307.4 -dicarboxylic acid)2+ (PTZ-COOH) and [MV-COOH](PF6 )2 Ru(4-(1 -ethyl-(bpy))(bpy-4. 293–295].3 -bicarbazyl-6. 311 311 312. 308 317 318 319 320.12-dodecanedicarboxylic acid 12-Phosphonododecanoic acid Alkanephosphonic acids CH3 -(CH2 )n PO3 H2 (n = 15. CF3 -)benzenesulfonyl and benzoyl chlorides p-(H-. N -Dioctyl-3. 308 308. CN-. Stilbazole derivatives and π-conjugated compounds with a pyridine unit have been extensively studied for a wide range of applications. These types of films strongly adsorb organic dye-sensitizer . NO2 -.1.

a majority by chelating carboxylate modes and a minority by ester-like linkage. or Al2 O3 films was immersed in an ethanol solution (typically 2 × 10−4 mol dm−3 . These findings and associated insights may find practical applications in the area of optical information storage. solutions of eicosylcarboxylic acid (CH3 (CH2 )19 CO2 H. The structures of monolayers of longchain aliphatic acids deposited on SnO2 :F and TiO2 using Langmuir–Blodgett (LB) techniques have been studied [305]. has been demonstrated [304]. Meyer and coworkers [303] described the surface attachment and photophysical properties of Ru(bpy)2 (dcbpy)2+ and carboxylic acid derivatives of phenothiazine (PTZ-COOH) or methyl viologen [MV-COOH](PF6 )2 on metal oxides (SnO2 . The resulting heterosupramolecular assemblies were washed thoroughly with ethanol and stored in a darkened vacuum desiccator until required for use. TiO2 . 1 mM) and eicosylphosphonic acid (CH3 (CH2 )19 PO3 H2 . metal oxide electrodes were etched in 10% HNO3 /H2 O (v/v) and rinsed thoroughly in nanopure H2 O before attachment.5 mM) were prepared in chloroform. In addition. ITO. The smaller organic compounds. 0. involving electrode-solution interfaces with TCOs. porous films consisting of SnO2 and ZnO colloids were also modified with similar Ru(bpy)2 (dcbpy)2+ derivative by boiling the plate in the solution (2 × 10−4 M in ethanol) for 3 min [302]. This method can be applied widely for the study of a variety of interfaces in situ.280 1 Preparation of Monolayer Modified Electrodes molecules.4 -dimethylphosphonic acid)2 2+ (RP VC4 ) for 2 h [304]. TiO2 . SnO2 electrodes modified with bis(2. PTZ-COOH. The .0) of ruthenium complexes such as Ru(4-(1 -ethyl-(bpy))(bpy4. The change in the Raman intensity as a function of electrode potential was also studied. For SiO2 . pH 3. For MV2+/+ -COOH couple was observed the worst surface stability [303]. The mono(carboxylic acid) salt (Ru(bpy)2 (bpy4-CH3 -4 -carboxylic acid)2+ ) was also attached to SnO2 with a maximum surface coverage of ∼1 × 10−10 mol cm−2 [303]. Covalent organization of these hetersupermolecules yields the heterosupramolecular assembly TiO2 −RP VC4 for which the associated hetersupramolecular function.2 -bipyridine4. the mixed surfaces were prepared by either sequential or competitive binding. and MV-COOH](PF6 )2 displayed similar surface coverages. two modes of binding were suggested. For most experiments.2 -bipyridine)2 (2. Fujihira and Osa [323] were the first to demonstrate that resonance Raman spectroscopy has bright prospects in the studies of adsorbed dye (methylene blue) layers at SnO2 electrode–aqueous solution interface. A transparent nanostructured SnO2 :Sb. or SiO2 ) and the application of resonance Raman spectroscopy to the elucidation of surface binding. In addition. long-lived light-induced charge separation. and TiO2 was via an ester link or H-bonding to the surface [303]. In2 O3 . Resonance Raman measurements [303] on surfaces containing the Ru complexes implied that attachment to SnO2 . SnO2 :Sb. Preparation of the complex Ru(bpy)2 (dcbpy)2+ was reported in the literature [301]. The cleaned electrodes were then soaked in solutions that were 10−4 M in Ru complex or carboxylic acid derivative in CH3 CN or CH2 Cl2 with an equal amount of DCC overnight in a dry box.4 -dicarboxylic acid)ruthenium(II) perchlorate (Ru(bpy)2 (dcbpy)2+ ) exhibit excellent photoelectrochemical response in the visible spectral region with a power conversion efficiency of ∼1% at 470 nm [300]. In2 O3 . Briefly.

ITO Table 3 presents several examples of organic chemical treatments used to modify ITO surface electronic properties.3 benzoic acids [307. The effects of pH. This selective surface-attachment chemistry is termed orthogonal self-assembly (OSA) and can be used to direct the spontaneous assembly of molecular reagents onto ITO and Au microstructures. or 4-nitrophenylphosphonic acid (1 × 10−4 M) [310.3 × 1018 and 3. For device fabrication. They found that phosphonic acids bind to ITO more aggressively than carboxylic acids. After the grafting process. 309] are all in the order of 1018 molecules m−2 . dissolved ions. Chemical structures of carboxylated and phosphonated ruthenium complexes and their derivatives are not shown in Fig. 308].1. the ITO was again briefly rinsed in pure ethanol and dried. different conditions. 308]. 4. trichloromethyl-. with the exception of aminomethylphosphonic acid for which an aqueous solution was used. Bicarbazyl-N. typically for a period of . Without leaving the glove box. trichloromethyl-. Willis and coworkers demonstrated that ITO electrode modification with 2-chloroethyl[310]. ITO was also immersed in ethanol solution containing 10−4 M of carboxylated Ru(bpy)2 (dcbpy)2+ complex [307. The Langmuir isotherms were measured in solution and yielded a maximum surface density of 1. p-substituted 1. most notably by reduction of turn-on voltages. aminomethyl-. ITO substrates were cleaned by sonication and subsequent Ar+ ion bombardment (plasma cleaning) at low power [306–309]. based on the observed coverage ratios (1 or 2) on ITO [298]. 4. and 4-nitrophenylphosphonic acids [311] greatly enhanced the OLED device performance. 311] were prepared in 30% methanol in chloroform. and different substrate materials on the structures of deposited monolayers have been examined.7 Chemically Modified Oxide Electrodes 281 substrates were mounted in the dipped position in the LB trough. respectively [307]. The findings will be used to optimize nanocrystalline solar cells and electrochromic windows based on metal oxide films modified by molecules adsorbed at the surface using phosphonic acid linker groups [305].3. The OSA has been achieved for ITO and Au substrates simultaneously exposed for 30 min to solutions (1 × 10−4 M in each molecule with 5% ethanol in isooctane) of (1) carboxylic acid and thiol or (2) phosphonic acid and thiol.0 × 1017 molecules m−2 for p-nitrobenzoic acid and Ru(bpy)2 (dcbpy)2+ . the substrates were briefly rinsed in pure THF and dried [306–308]. Chemical structures of these organic materials used to modifiy ITO electrode surfaces are also shown in Fig. Solutions of each 2-chloroethyl-. N dialkanoic acids [308]. Wrighton and coworkers [298] took advantage of the selective surface attachment of carboxylic or phosphonic acid to ITO electrode and thiol to Au electrode.7. ITO substrates were derivatized with a SAM by immersion in a solution of the appropriate phosphonic acid. Before grafting. they were transferred into a 10−3 M PPP-func and p-substituted benzoic acid solutions in tetrahydrofurane (THF). and 8-hydroxyquinoline-5-carboxylic acid [309] monolayers grafted to ITO electrode. After several hours of grafting. bicarbazyl-N. N -dialkanoic acids and p-substituted benzoic acids [308. Using a similar approach. Zuppiroli and coworkers [306–309] observed improved performance in the organic light-emitting diodes (OLEDs) using poly(para-phenylene)-functionalized carboxylic acid (PPP-func) [306].

Br. 313].282 1 Preparation of Monolayer Modified Electrodes O C HO O C HO O C HO n F16 CF3 Fe OH HO P O HO Ref. The presence of each phosphonic acid on ITO surface was confirmed by measuring the advanced contact angle relative to bare ITO of triply distilled water on the surface. 314-316 Ref. 309 O Y C HO OH O C HO P O OH 5 O C HO (Y = H. 4 Chemical structures of carboxylic acid and phosphonic acid derivatives used for the surface modification of ITO. 298 OH NH2 HO P O CI CI HO CI O P NO2 CI Sec-butyl HO P O HO C O HO O P O O Ref. 322 Fig. 312. By the use of acid chlorides [312. CI. 320. ITO electrodes were removed from solution and rinsed thoroughly with fresh solvent [311]. 308 O C HO O C HO Ref. NO2. 16 h. CH3O) Refs. 318 Y O C HO O C HO S Refs. 313 Ref. 5. SH) Refs. 306 N O C n N n O Refs. and 10 Ref. CN. 319 Ref. 311 n = 2. 307. 316 OH P O CH3 7 or 9 N OH (Y = CH3. After derivatization. 308 5 HO HO O C O C CI O N CI P CI O Y CI Y O O S CI O CH3 5 or 12 Y N 5 (Y = H. 298 Fe Ref. CF3) Refs. ITO surfaces were modified quickly and the fine and wide change in ITO . 308 O C OH HO C O Fe OH O C HO Ref. 310. 321 Ref.

7 Chemically Modified Oxide Electrodes 283 work function was realized. Chemisorbed small molecules on ITO will provide for better direct contact of added conducting polymer layers and/or hole transport layers (HTLs) in the devices [316]. Adsorption of small redox-active molecules (e. 325] closely followed the procedure described in Ref. Close-packed and ordered monolayers of 12-phosphonododecanoic acid (12-PDA) were recently observed to form on ITO .4 -diphosphonic acid)2+ (tpy is 2. it desorbs within 10 min. for each pretreatment condition [314].1. At pH >10.2 . Monolayers were self-assembled by immersion of ITO in 5 mM 1. The solutions were kept for 24 h at 30 ◦ C during ITO sample immersion. To ensure reproducibility.0) onto ITO.5 mM ethanol solution at room temperature. the adsorption of Fc(COOH)2 on pretreated ITO was repeated a minimum of three times on three separate ITO samples. HS(CH2 )15 COOH molecules can be utilized to generate a thiol-terminated SAM on ITO [318]. the samples were rinsed with hexane and blown dry with N2 . 2 -terpyridine) and kinetic evidence that surface oxidation of RuIII −OH2+ to RuIV −O2+ involves proton-coupled electron transfer. n-Nonanoyl chloride and n-palmitoyl chloride were also used [313]. the ITO substrates were immersed for 5 min in dichloromethane solutions containing 1 mM of p-substituted benzenesulfonyl chloride. Napier and Thorp [319] developed a nucleic acid detection system based on the catalytic oxidation of guanine residues by a Ru(bpy)3 2+ mediator. At pH 7. These modified substrates were rinsed in pure dichloromethane to remove excess unbound molecules and then vacuum dried for 1 h. The electrodes were thoroughly rinsed with hexane to remove any physically adsorbed molecules. Bifunctional HS(CH2 )15 COOH was adsorbed from 0. the complex desorbs from the surface with a half-time of ∼30 min. Stearic and archidic acid [318] solutions were made by dissolution in hexadecane at 40 ◦ C. After the solutions cooled to ambient temperature. The monolayers were relatively stable for several hours at pH 1.12-dodecanedicarboxylic acid in hexadecane for 36–48 h. A few studies investigate the coating ITO with organic monolayers of amphiphilic molecules [318–322]. The activation of surface carboxylates was performed by placing 40 mL of a freshly prepared 10 mM water-soluble carbodiimide in 20 mM sodium phosphate buffer (pH 7. After cleaning with acetone and isopropanol. benzoylchloride. Adsorption of ferrocene dicarboxylic acid (Fc(COOH)2 ) and 3-thiophene acetic acid (3-TAA) onto ITO was achieved by soaking ITO in a 1 mM solution of these small molecules in pure ethanol for 10 min and then rinsing briefly with acetonitrile [314–316]. These molecules were found to form stable and ordered monolayers on ITO.1 × 10−5 to 2 × 10−4 M) concentrations of metal complex in water at pH 3. ferrocene [326]) on ITO can be used to probe changes in electrochemical activity of ITO surface as a function of surface pretreatment [314].g. 312. Meyer and coworkers [317] reported the preparation of surface structures based on Ru(tpy)(H2 O)(bpy-4. with ∼10% of the electroactive coverage lost in the first hour of exposure. The carbodiimide was allowed to dry on ITO surface. Nucleic acids were then coupled to the activated ITO surface [319]. or phenylphosphoryl dichloride [312]. SAM modification of ITO substrates [324. Stable surface coatings of the Ru complex on ITO were prepared by exposing electrodes to various (0.

and H2 O [321].2-µm PTFE Acrodisc syringe filter. the stamp was pressed onto cleaned ITO and removed after a few seconds. To maximize electrontransfer between Ru(bpy)3 2+ and ITO. p-type doped thin films [351–354] and plasma polymerized fluorocarbon films [355]. Schwartz and coworkers reported that bonding of carboxylic acids [341. The printed samples were etched in an aqueous oxalic acid solution (0. a surfacebound alkoxyzirconium species is first formed. Other useful alkanediphosphonic acids were possibly synthesized by Michaelis–Arbuzov reaction [327. In addition. left for 1 min. Phosphonic acid functional groups were found to preferentially interact with ITO surface relative to carboxylic acid groups. In this process. Typical etching times were ˚ ∼5 min for 500 A films [322]. 342] or phenols [343] to surface hydroxyl (−OH) groups of ITO could be stabilized using zirconium alkoxide complex-derived interface. The work function of ITO may be changed by electrostatically controlled self-assembled polymer layers [344–349]. PDMS stamps were inked in either flooding method or spraying method [322]. electrocatalytic detection of surface-immobilized nucleic acid probes using the Ru(bpy)3 2+ mediator is highly dependent upon the preparation of ITO surface [321]. After drying under N2 flow. ITO work function can be changed by treatment with UV-ozone [269. 2-Propanol evaporated from the stamp surface as the ink was sprayed. Recently.05 M). The stamp is immersed for 2 min in a 3 × 10−3 M solution of TBOH in ethanol or water. 340] using organotin (or zirconium) alkoxides [341–343]. 1 M NaCl. 312. ITO electrodes were removed from solution and washed with successive 10 min rinses of H2 O. There are many other studies of ITO surface modification [277] for the purpose of enhanced hole injection.5 h. leaving a film of neat alkanephosphonic acid. ITO and SnO2 :F were cleaned via 20 min of UV-ozone to yield a clean hydrophilic surface. Inked stamps were placed on ITO or ZnO:In surface using tweezers. A 5 mM solution of ODPA or HDPA in 2-propanol was filtered through a 0. and charge transfer [338] as well as by binding dipolar molecules [339. Then the electrodes were rinsed with H2 O followed by drying the electrodes with N2 . and then removed. Breen and coworkers [322] described patterning of ITO and ZnO:In films using microcontact printing (µCP) of either hexadecylphosphonic acid (HDPA) or octadecylphosphonic acid (ODPA) and wet etching. and subsequent ligand exchange . 331]. 330. TBOH reacts with the surface of ITO to form a double ionic layer that drastically inhibits the ability to inject holes in the device [329].284 1 Preparation of Monolayer Modified Electrodes and SnO2 :F through phosphonate-indium bonding interaction [320]. The hole injection was also enhanced by electrochemically prepared thin films [350]. Elastomeric stamp patterning of ITO using tetrabutyl-ammonium hydroxide (TBOH) was demonstrated [329]. with mild agitation. the charge at ITO needs to be negative. ITO or ZnO:In films were cleaned by UV-ozone for 30 min. plasma [332–334]. Phosphonated SAM was allowed to form on ITO by immersing the electrode in solution of 1 mM 12-phosphonododecanoic acid in 50% DMSO/50% H2 O for 16. 328]. acids or bases [335–337]. The cleaned electrodes were immersed for 16 h in deposition solution of 10 mM 12-PDA in 50% dimethyl sulfoxide (DMSO)/50% H2 O. Prior to µCP. in which etch resistance depends on thickness and uniformity of printed alkanephosphonic multilayers.

Hagfeldt and coworkers [359–362] recently obtained a high overall efficiency from 2% up to 5% of Ru(NCS)2 (dcbpy)2 2+ adsorbed on ZnO. some oxides such as SnO2 [300].1. Treated ITO substrates [341] were also dipped in a 10−3 M solution of ferrocenecarboxylic acid (FcCOOH) in dry diethyl ether under an inert atmosphere for 30 min and then rinsed [342]. one may find ZnO to be a candidate as a nanostructured material in efficient solar cells [362]. For ZnO.3. 10−2 Torr to remove any physisorbed molecules [341].5 mM ethanol dye solution of Ru(NCS)2 (dcbpy)2 2+ . cells based on ZnO have shown lower efficiencies compared to cells based on TiO2 . In 1994 Gr¨tzel and coworkers [358] obtained overa all solar-to-energy conversion efficiency of 0. removed. 254]. 340. a 1 mM solution of FcCOOH in diethyl ether was sprayed onto treated ITO using N2 . 343].4% when using Ru(NCS)2 (dcbpy)2 2+ on nanocrystalline ZnO films. Alternatively. ZnO [357]. Several groups have shown that ZnO can be electrodeposited from aqueous solutions in both nonporous [445.4 crystallite sizes than those for typical TiO2 films [357]. at present. and dried in vacuo to give surface-bound zirconium carboxycopolymer. However.7 Chemically Modified Oxide Electrodes 285 or metathesis with carboxylic acid generates a covalently bound alkanecarboxyzirconium surface complex species [341]. followed by evacuation for 60 min at ca. In a typical procedure. The electrodes were sintered at 450 ◦ C for 30 min in airflow to form nanostructured film electrodes [360].7. 446] . Systems based on dye sensitizer such as Ru(NCS)2 (dcbpy)2 2+ adsorbed on TiO2 are the most extensively studied and. Carboxyl groups are the commonly used anchoring groups for chemisorption of dye molecules onto TCO electrode surfaces [291]. the most efficient for dye-sensitized solar cells [356]. The still warm electrode (about 80 ◦ C) was immersed into a 0. Therefore. it is similar in bandgap and band edge position to TiO2 (shown in Table 2) with similar (10–20 nm in diameter) or smaller (5 nm) 1. a substrate was treated tetra(tertbutoxy)zirconium vapor at ca. Nanocrystalline ZnO electrodes were prepared by deposition of a colloidal ZnO solution on TCO substrates (usually SnO2 :F or ITO). The film remained in the above solution for up to 7 days. Treated ITO substrates were then dipped in a saturated ethereal solution of acrylic acid for 30 min. ZnO Dye-sensitized TiO2 electrodes have been investigated due to their potential use in solar cells [253. rinsed with copious amounts of diethyl ether. Prior to sensitization freshly prepared ZnO films were heated at their firing temperature for 20 min to activate the film surface by removing adsorbed water. The sensitized film was stored in ethanol until required for use [358–362]. and SrTiO3 [261] have also been studied for photoelectric conversion. Several attempts [358–362] have been made to use ZnO in photoelectrochemical solar cells. Such surface modification does not constitute an insulating barrier between ITO and a third material near the interface [339. 10−2 Torr for 45 min. SrTiO3 offers the possibility of higher open-circuit voltages through closer alignment of sensitizer excited state levels with conduction band edge [261]. By improving the interfacial contact between dyes and ZnO particles in the film. Table 4 summarizes examples of surface treatments used for chemical modifications of wide bandgap semiconductors such as ZnO and TiO2 . The solvent was then removed by evacuation. Besides TiO2 .

TPP(COCl)4 and ZnTPP(COOH)4 Benzene derivatives benzoic. OH−or CH3 (CH2 )11 OPO(OH)2 Reference 358–363 364–366 367 368 369 370 371 253.2 :6 .4 -dicarboxylic acid)2 2+ (X=Cl−. H-terminated in the benzene ring) [Ru(bpy)2 (CN)2 ]2 Ru(bpy-4. 20) and HO(CH2 )11or15 CO2 H HOOC(CH2 )n PO3 H2 (n = 2.10-perylene tetracarboxylic acid diimide Ru(NCS)(Me2 bpy)(2.2 -terpy-4.4 .9. 292. 376–378 379 356. CNS−) Ru(CNS)3 (2. 3. C2 H5 −.9. 391 392 393 291. NH2 (CH2 )11 COOH Alkane(R)−PO3 H2 (R = CH3 −.2 : 6 . phthalic or salicylic acid Carboxylate-terminated dimeric viologen Mc2 merocyanine acid 3. C6 H5 −) Stearic (octadecanoic) acid.4 -CH2 PO(OCH2 CH3 )2 )3 2+ Ru(Me2 bpy)2 -Rh(bpy-4. Ru(bpy)2 (ina)2 2+ Ru(Me2 bpy)2 (bpy-4-CH3 -4 -(3-propyl)carboxylic acid)2+ Ru(X)2 (bpy-4. 398 399–422 408. and C2 H5 COOH Benzoic acid (C6 H5 COOH) Bi-isonicotinic acid (bpy-4.4 -dicarboxylic acid)3 2+ Ru(bpy)2 (bpy-4. 13–18. CN−. OCH3 −. CN−. CH3 O−) benzoic acids CH3 (CH2 )n CO2 H (n = 9. CH3 COOH. 380–385 386. CH3 (CH2 )17 OPO(OH)2 Dodecanephosphoric acid. CF3 −.4 -dicarboxylic acid)2+ .4 -dicarboxylic acid)3 RhB-COOH. 374 394.23-tetrasulfophthalocyanines Riboflavin 5 -phosphate N. CH3 (CH2 )16 COOH Octadecanephosphonic acid. 387 377 388–390 304.2 :6 .286 1 Preparation of Monolayer Modified Electrodes Tab. CH3 −. 11.4 -dimethylphosphonic acid)2 2+ Ru(bpy-4.4. N -Bis(ethylenesulfate)-3.4 -diphosphonic acid)2+ Ru(CNS)(Me2 bpy)(H2. 2 -terpy-4-phosphonic acid)2+ Ru(4-(1 -ethyl-(bpy))(bpy-4.4 -tricarboxylic acid)2+ Ru(bpy)2 (bpy-4.4 -dicarboxylic acid)2 2+ Ru(bpy-4.16. n-C4 H9 −. 395 396 397 377.5-Bis(phosphonomethyl)benzoic acid derivatives HCOOH. 423 424–426 427 428 429 430 431 432 433 434 435 435–440 441 442–444 TiO2 TiO2 or ZrO2 TiO2 or ZrO2 TiO2 or SrTiO3 TiO2 or ZrO2 TiO2 or ITO TiO2 or ZnO ZrO2 TiO2 or ZrO2 TiO2 TiO2 or ZrO2 TiO2 or ZrO2 TiO2 or ZrO2 TiO2 TiO2 or ZrO2 . NO2 −. 4 Examples of organic chemical treatments used for surface modifications of n-type semiconductors of ZnO and TiO2 as well as ZrO2 Semiconductor ZnO Chemical modification Ru(NCS)2 (bpy-4. CH3 (CH2 )17 PO3 H2 Octadecanephosphoric acid.4 -dicarboxylic acid) Oxalic acid (HOOC−COOH) Glycine (NH2 CH2 COOH) Maleic anhydride (C4 H2 O3 ) p-(H−. Br−. 15) 11-Aminoundecanoic acid.4 -dicarboxylic acid)2 2+ Metal complexes of 2. 372 373–375 303.2 -terpy-4-phosphonic acid)2+ Fullerence (C60 ) carboxylic acid derivatives Succinic acid derivatives (p-CN−.

whereas the carboxyl group was found to be protonated when binding to ZnO [361. Nanoporous ZnO thin films have been applied to dye sensitization with metal complexes of 2. Adsorption on oxide surfaces has also been addressed by computational methods [448]. which is also found to be the most stable adsorption mode [449]. and a deeper understanding of the binding kinetics and bonding nature is therefore important [291. N. Al3+ or Si4+ [OH]2 ) [364–366].2 :6 . electrolysis was carried out under the same conditions as described in Ref. N bis(ethylenesulfate)-3. 366].1 M Zn(NO3 )2 aqueous solution maintained at 70 ◦ C [445]. Phosphonic acid groups bind strongly to ZnO. 365].2 -terpy-4-phosphonic acid)2+ complex was adsorbed onto the ZnO from ethanol/DMSO (70%/30%) [369].9 V (vs. 448]. and Ru(NCS)(Me2 bpy)(2. dried in air at room temperature and subjected to further analysis. Ms=Zn2+ . Thus. thus opening up a new synthetic route to photoactive materials in dye-sensitized solar cells [363. Ru(NCS)2 (dcbpy)2 2+ [363]. theoretical studies of the adsorption of HCOOH on ZnO surface energetically favor a bridging structure. Adsorption was 90% complete within 12 h. while cooling from a second 30 min heating to 380 ◦ C. The deposited films were rinsed by water. Carboxylic acid groups are by far the most popular binding groups in dyesensitized solar cells. Gr¨tzel a and coworkers [369] have recently developed a nonaqueous electrodeposition route to very high surface area ZnO films with a wide range of morphologies.1. 445.9.10-perylenetetra carboxylic acid diimide (SO3 EtPTCDI) [368]. the results also indicate that the bonding mode of HCOOH on ZnO is sensitive to the . Deposited dyemodified ZnO films have been found to perform as sensitized photoelectrodes. Other phosphonated Ru polypyridyl dyes gave similar results [369]. The electrodes were placed into 5 mL of ∼10−4 M dye solution when they reacted at 120 ◦ C. 450]. Formation of the Ti−OSO2 −Pc bond was found by FTIR analysis of TiO2 /TSPcCo composite [447].7 or −0.7 Chemically Modified Oxide Electrodes 287 and porous [363–368] forms. 292]. The deposition of ZnO/dye films was achieved simply by adding typically 50 µM TSPcMs [364. The electrodeposition of ZnO was carried out potentiostatically at −0.23tetrasulfophthalocyanines (TSPcMs.4. Photoelectron spectroscopic measurements of carboxylated Ru complexes adsorbed onto ZnO and TiO2 indicate a bridge bonding (the carboxyl group is deprotonated and each oxygen atom interacts with a separate surface metal atom) in the case of TiO2 . Three structures have been suggested for the formate anion adsorbed on metal oxide surfaces: bridging. Phosphonated dyes have recently been found effective especially for solid-state dye-sensitized solar cells using electrodeposited nanoporous nanocrystalline ZnO [367]. The anchoring of TSPcMs to ZnO is expected to occur through the coordination of sulfonic acid group to the surface Zn2+ of ZnO. SCE) for 60 min in a 0. 5.2 -terpy-4-phosphonic acid)2+ [369]. riboflavin 5 -phosphate (R5-P) [367]. In the case of SO3 EtPTCDI [368].9. and unidentate structures as shown in Fig. A monolayer of Ru(NCS)(Me2 bpy) (2.16. bidentate.2 :6 . However. Quantum chemical calculations have mostly been limited to small adsorbates such as formic acid (HCOOH) on different ZnO surfaces [449. The energy difference between bridging structure and unidentate structure in interactions with the surface OH species was calculated to be very small [449]. R5-P [367] and SO3 EtPTCDI [368] into the zinc nitrate bath.

371]. Charge transport in . ‘‘black dye’’ complex achieved a record 10.3. which bind strongly to TiO2 by coordination of surface Ti ions [453–455].5 surfaces was reviewed in Ref. succinic acid derivatives with p-substituents (CN−.288 1 Preparation of Monolayer Modified Electrodes H C H H C O Fig. 5 C O O O M O M O M (c) Unidentate type Three possible geometries for formate anions adsorbed on metal oxide surfaces. many other complexes have been synthesized and tested [372–393]. M (a) Bridging type (b) Bidentate type surface coverage [361. 456.5. 452]. They used the same system but with. as semiconductor. 372. 450]. In addition. 372–393.1 Polypyridyl Ru Complexes and Organic Dyes as Sensitizers The preparation and characterization of n-type nanocrystalline TiO2 for dye-sensitization studies of Ru complexes containing carboxylate and phosphonate polypyridyl ligands [253–255. Thus. and H−) in the benzene ring were adsorbed onto ZnO into roughly one monolayer by overnight immersion in a 2. Br−. In addition. ZnO. molecularly modified ZnO-based diodes open up possibilities for using light-sensitive molecules to study molecule-semiconductor charge transfer in a solid-state device structure [371]. With ZnO. 386].5 mM acetonitrile solution [371].55. However. 1. Molecular control over the effective barrier height was more effective with ZnO than with GaAs. Transition metal complexes or organic dyes as sensitizers are grafted on semiconductors through anchoring groups such as carboxylate or phosphonate. TiO2 and ZrO2 The adsorption of a wide variety of inorganic and organic molecules on TiO2 1. Fullerene (C60 ) carboxylic acid derivatives were easily adsorbed from solution as monolayers on ZnO and modify the semiconductor work function [370]. SCN−) [356]. CH3 O−. Moreover. the adsorption of small organic molecules is briefly described in this section.3. 356. It is therefore likely that several bonding modes may be involved in the adsorbate interaction with ZnO surface. CH3 −. 23. a much more ionic solid than GaAs [370. 453–455] have been discussed in detail [456]. The carboxylate and phosphonate functionality as an anchoring group to immobilize the complex on nanocrystalline TiO2 films have also been discussed in Ref. CF3 −.7.7. CN−. Since the first systematic study of complexes of the RuX2 (dcbpy)2 2+ (X=Cl−. five times that was of GaAs. I−. the adsorption is a dynamic process allowing translational mobility of adsorbate on the surface. the interface index found to be 0.4% solar to power conversion efficiency in full sunlight [387]. Cahen and coworkers showed that current density-voltage (I−V) characteristics of Au−GaAs and Au−SiOx /Si diodes could be modified by adsorbing a monolayer of dipolar molecules onto the semiconductor or metal surface [451. in 2001. The best photovoltaic performance in terms of both conversion yield and long-term stability has so far been achieved with Ru complexes [356. Several examples of chemical modifications of TiO2 with various organic molecules are listed in Table 4.

Incorporation of phosphonic acid groups creates a basis . Finnie and coworkers [385] suggested a bidentate or bridging coordination to TiO2 surface via carboxylate groups per dye molecule. porous TiO2 ) [14. 356. 253] conductors has recently been investigated by transient and spectral photovoltaic techniques [458]. and [Ru(bpy)2 (CN)2 ]2 Ru(dcbpy)2 2+ have unambiguously shown the utility of carboxylate as an efficient anchoring group [253. 381] in TiO2 have been discussed [254. 380. Fujihira and coworkers [291. Ru(NCS)2 (dcbpy)2 2+ . 385]. 378. A disadvantage of carboxylate group binding to TiO2 is the fragility of the resulting surface link toward hydrolysis. an asymmetric C−O stretch consistent with carboxylate binding modes (bidentate or bridging) has been reported [378. CuI. The nature of linkage between a sensitizer and a semiconductor surface can influence excited state and interfacial electron-transfer behavior as well as the redox potentials. 378–387. 389–392]. 388–392] suggested that much higher surface stabilities could be achieved by the utilization of phosphonated derivatives and phosphonate surface binding. 385].7 Chemically Modified Oxide Electrodes 289 nanocrystalline TiO2 films has been under intense investigation [453] and has been best described by a random walk model [457]. 376. Qu and Meyer [378] demonstrated that high surface proton concentrations favor ‘‘carboxylic acid’’ type linkage where low proton concentrations favor ‘‘carboxylate’’ type binding modes for complexes. 376]. Evidence for ester linkages and H-bonded network have also been reported [303. Studies on dye adsorption showed that the adsorption is much better for P-terpy complex as compared to the analogous dcbpy complex [388]. 382]. Ru(bpy)2 (dcbpy)2+ . the electrode was withdrawn from the solution under a stream of dry air or argon. The charge injection from the dye Ru(SCN)2 (dcbpy)2+ into transpar2 ent hole (CuSCN. 372–374. Earlier studies based on Ru(dcbpy)3 2+ . Nanocrystalline TiO2 films were prepared by spreading a viscous dispersion of colloidal TiO2 particles on conducting glass support with heating under air for 30 min at 450 ◦ C [253. 292] were the first to report on organic dyes containing functional groups such as −CO2 H and −COCl bind to SnO2 or TiO2 electrode surface using ester-like linkage. Coating of the TiO2 surface with dye was carried out by soaking the film for at least 3 h in a 3 × 10−4 M solution of the Ru complex in dry ethanol. In most vibrational studies. with subsequent binding of two or more carboxylate groups on the surface. Recent reports [377. that is.1. After completion of the dye adsorption. Gr¨tzel and coworkers [388. 375. 80 ◦ C. a more efficient electron injection was obtained in the cells. The dye coating was done immediately after the high-temperature annealing. its temperature was ca. 356. 389] a reported the results of their studies involving Ru complexes with one or more of phosphonated terpyridine (P-terpy) as a key ligand. 384. charge injection. and charge transfer from molecular excited states to the empty states [378. CuAlO2 ) [19–22] and electron (SnO2 :F. Possible modes of coordination of the carboxylate are shown in Fig. Fillinger and Parkinson [383] found that the initial binding involves one carboxylate. 387]. Therefore. 255. 380–382. 6. 393]. 303. Several studies have addressed how carboxylated Ru complexes interact with TiO2 surface [303. Charge separation. It was stored in dry ethanol or immediately wetted with redox electrolyte solution for testing [303. The electrode was dipped into the dye solution while it was still hot.

4'-(CO2H)2)2+ −H2O Ti−O−C−4'-((CO2H)bpy)Ru(bpy)2+ (a) O Ti−OH + Ru(bpy)2(bpy-4. The reduced form . phthalic acid. 388. and then the surface linkage strategy is a success [377]. 388–392]. Gr¨tzel and coworkers [456] also a described the difference in binding properties of complexes containing carboxylate. The dramatic rate enhancement of interfacial electron transfer by bidentate benzene derivatives on TiO2 was observed. Nanocrystalline TiO2 (or ZrO2 ) films on ITO substrates and TiO2 (or ZrO2 ) colloids were prepared by a method described in Refs. 379. 10−4 M in phosphonated complexes in ethanol solution for 16 h.4'-(CO2H)2)2+ Ti−OH (c) Fig. (b) bidentate chelating. the electrodes were rinsed with ethanol and stored in a fresh ethanol until use [377. 395]. The second acceptor of the heterotriad.290 1 Preparation of Monolayer Modified Electrodes O Ti−OH + Ru(bpy)2(bpy-4. Viologens form a group of redox indicators that undergo drastic changes upon oxidation/reduction. and (c) bridging. and phosphonate binding groups might stem from the differences in the pKa values of the ligands. that is. The complexation of these acids by TiO2 surface dramatically accelerates the rates of interfacial electron transfer to acceptors in the solution. antraquinone. is linked to methylviologen [394. After derivatization. Surface complexation of colloidal TiO2 by benzene derivatives. 6 Ti−O −H2O C-4'-((CO2H)bpy)Ru(bpy)2+ Ti−O Three possible carboxylate coordination modes to TiO2 surfaces: (a) unidentate. benzoic acid. or by desorbing the complexes with 2 M NaOH solution. Surface coverages were determined by spectroscopic measurement of the amount of complex in ∼10−4 M ethanol solution before and after the attachment. cooled and immersed in solutions ca. Attachment of a methylviologen to the above spacers has been studied. The films were heated to 400 ◦ C for 30 min. and salicylic acid was investigated and was found to obey the Langmuir isotherm [394].4'-(CO2H)2)2+ −H2O Ti O C-4'-((CO2H)bpy)Ru(bpy)2+ (b) Ti−OH + Ru(bpy)2(bpy-4. for stable surface adsorption. These acids chemisorbed at TiO2 by chelation to surface Ti4+ atoms are used as a spacer.

acetic acid. The absorption spectroscopic studies [407–413] concluded that that there is a minority species present. two phosphonate groups on the same molecular anchor should bind much tighter to a metal oxide surface than one phosphonate group. acrylic acid. Generally. 459].5 × 10−10 mol cm−2 and 4. the adsorption and reaction of HCOOH was recently discussed in some detail in Ref. for example. HCOOH dissociates at TiO2 to give formate: HCOOHgas + Olattice = HCOOads − + Olattice Hads (1) Here the H atom forms a hydroxyl with a surface atom Olattice . Organic phosphonates and phosphates bind to metal oxide surfaces much more tightly than carboxylic acid [392. a single-crystalline ZnO [399–402]. The majority of HCOO− are adsorbed in a bidentate fashion.5-bis(phosphonomethyl)benzoic acid. Quantitative information about the adsorption sites.2 Short-chain Alkanoic and Benzoic Acids Formic acid is one of the best investigated organic systems on TiO2 and ZnO surfaces. 398] described the synthesis of a protected diphosphonate anchor of 3. Because many of other carboxylic acids follow the behavior of formic acid. is deep blue. and ZrO2 ) substrates with a hydroxide salt. Intercalated solvent molecules stabilize the structure. benzoic acid.1. which is the dye studied [397]. the dye molecules are oriented. Surface coverages of 1. Gr¨tzel and coworkers [397] successfully a applied this method to induce J. with the molecular plane oriented parallel to the (110) direction. 3. while the oxidized form is colorless. The best candidate for organic solar cells have been derivatives of merocyanine 3-acetyl-5-(2-(3-ethyl-2benzothiazolidinylidene)ethylidene)-rhodanine (Mc2). Meyer and coworkers [377. Al2 O3 . In addition. . Thereby. and lateral interaction between formats and hydroxyls were obtained (see below). and glycine) were investigated by several groups [399–423]. bi-isonicotinic acid. 23. its coupling of its carboxylate group to an amino group of a proline-chromophore. its deprotection. The polar group (carboxylic group) of Mc2 points toward the salt solution and pairs with a hydrated metal cation. The adsorption occurs via reaction (1) with no further details on the adsorption geometry given. geometry. Moreover. and ZrO2 [410] surfaces were used for adsorption of formic acid and acetic acid.5bis(dimethoxyphosphinylmethyl)benzoic acid was converted to an amino derivative by attaching a diamino butane linker [398].and Haggregation of carboxylated merocyanine dyes by impregnating highly porous metal oxide (TiO2 . 1. and finally its demonstration as an anchor on nanocrystalline TiO2 . Efficient reduction of anchored viologen compounds by conduction band electrons of TiO2 can be used for the amplification of an optical signal [396].7. propanic acid. TiO2 [401–408]. respectively. SnO2 [409]. which assists the formation of the appropriate aggregate geometry. In early adsorption studies. ZrO2 . oxalic acid. A large number of the adsorption and reaction processes of carboxylic acids (formic acid. and ITO. with the oxygen atoms bridge-bonded between two fivefold coordinated Ti atoms and molecular plane oriented in (001) direction [411].5.3. Formic and acetic acid adsorption and reaction on rutile TiO2 surfaces were investigated by different groups [401–408].9 × 10−11 mol cm−2 are at TiO2 and ITO electrodes.7 Chemically Modified Oxide Electrodes 291 of methylviologen.

404]. Two main decomposition products such as methyl ketene (CH3 HC=CO) and diethyl ketone (CH3 CH2 COCH2 CH3 ) as well as divinyl ketone (CH2 =CHCOCH=CH2 ) were formed at elevated temperatures [404]. Atom-resolved images of TiO2 surfaces with single formate ions [416–418] are also consistent with the adsorption site at Ti atoms reported in Refs. indicating a bond geometry essentially independent of alkyl chain length [412]. A neat format monolayer was made by exposing the substrate to formic acid vapor at room temperature for 3 Langmuirs (1 L = 1 × 10−6 Torr s) [416]. Scanning probe techniques have also contributed to the understanding of this adsorption reaction. This agrees well with theoretical calculations [415. The adsorption of acetic acid and propanoic acid generally follows the same trends found for formic acid [400–404. and propanate are formed on TiO2 (110) by dissociative adsorption of the corresponding acid. while the total (formate + acetate) coverage was maintained at the saturation [415. TiO2 (110) [405. It is possible to distinguish . Iwasawa and coworkers [420] directly observed the decomposition of acetic acid with scanning tunneling microscopy (STM). 406]. The decomposition of formic acid has been studied on rutile TiO2 (001) [403. The amount of adsorbed acetate could be controlled by the exposure amount to acetic acid. Accurate and reproducible gas exposures were obtained by means of a micron-sized pinhole [417]. surface atoms are incorporated in reaction products. 418].1 A and the O−C−O bond angle was estimated 126 ± 4◦ [414]. The number of bright spots on the surface decreased exponentially with time. 417].292 1 Preparation of Monolayer Modified Electrodes This species is probably adsorbed at the vacancies in the bridging oxygen rows. 416]. Iwasawa and coworkers reported the first example of noncontact atomic force microscopy (NC-AFM) images of oxide surfaces with oxygen point defects on TiO2 (110) [421]. The twist angles probably arise from averaging of majority and minority species. 450]. acetate. Formate. This agreed well with a rate law deduced from a thermal desorption study [404]. It is now clear that the substrate plays a very active role in formic acid decomposition and reaction processes. 412. 449. the separation of ν(C=O)–ν(CO) was observed at 282 cm−1 . The vertical Ti−O distance ˚ was determined as 2. This was assigned as a unimolecular decomposition of acetate to release ketene. 411–413. 407. These angles out of the azimuths vary from 26 ± 5◦ to 39 ± 10◦ . In all cases the carboxylate plane is almost perpendicular to the surface and apparently twisted out of the principle azimuths. with hydroxyl species also being formed [404–407. the formate-covered surface was then exposed to acetic acid vapor. acetate. and propanate in their 2 × 1 overlayers on TiO2 (110) at 300 K. Thornton and coworkers [412] examined the orientation of formate. Both reactions were observed upon formic acid exposure on TiO2 (110) [406]. Formic acid was dosed on TiO2 through a translatable directional dozer. and TiO2 (100) [419]. and the substrate itself is reoxidized upon formate decomposition [23]. An exchange reaction occurred between adsorbed and gas-phase molecules. STM images after a temperature jump to 580 K were analyzed. To prepare mixed monolayer. which is closer to the value expected for monodentate bonding [413]. Dehydrogenation (HCOOH → CO2 + H2 ) and dehydration (HCOOH → CO + H2 O) are two main reaction mechanisms of HCOOH on TiO2 . In addition.

leads to the rutile structure. adsorbed on TiO2 (110). Small coverages on TiO2 surface indicated dissociative adsorption where most of the amino group is released into the gas phase. Benzoate dimerizes along the (001) direction through the interaction between hydrogen of aromatic ring and π orbital [423]. which seems to be the most stable form of oxalic acid on TiO2 surfaces. butene. 425].7 Chemically Modified Oxide Electrodes 293 between coadsorbed formate and acetate molecules with NC-AFM [417. The remaining layer is formed by C. These pathways are undoubtedly related to the conjugated nature of the adsorbate because they are absent in the case of propanoic acid decomposition [404].4 -dicarboxylic acid) on TiO2 (110) in X-ray photoelectron spectroscopy (XPS) and near edge X-ray absorption fine structure (NEXAFS) studies [424. combined with quantum chemical calculations [424–426]. Minot and coworkers [427] performed theoretical investigation of oxalic acid (HOOC−COOH) on rutile and anatase TiO2 . ethyne. once a decarboxylation has occurred. it may behave similarly. in dye-sensitization of solar cells [253]. In addition. 2) and OH hydroxyl species. The calculations suggested that oxalic acid undergoes dissociative adsorption leading to the oxalate (C2 O4 2− ) bonded to two adjacent Ti atoms. These products included ethene. The adsorption is dissociative. were studied with synchrotron radiation-based UV light [428]. N1s NEXAFS spectra were modeled successfully using this adsorption geometry in a cluster model [424. Understanding the molecule-surface linkages in these systems is an important step in developing such molecular devices [379]. The reactions of acrylic acid (CH2 =CHCOOH) over TiO2 provide a clear example of the complexity of the chemistry of conjugated molecules [422]. Multilayers of glycine. The reactions of C4 H2 O3 have been investigated on TiO2 (001) by . 418]. 425]. the molecules stand up with a 25◦ tilt angle and have a preferred azimuthally orientation of 44◦ with respect to the (001) direction in excellent agreement with calculated values [425. NHx (x = 1. and is connected via the rings along the (110) direction. Williams and coworkers [408. The adsorption of more complex acids was extended to bi-isonicotinic acid (2. forming benzoate and surface hydroxyl. Ultraviolet photoemission spectroscopy (UPS) and XPS data showed the multilayers as formed by glycine molecules in polar zwitterionic form (NH3 + CH2 COO− ). and butadiene. a range of products due to the olefin fragment is seen. It was proposed that rotation of the phenyl ring takes place. 426]. However. The adsorption is stronger on the anatase than on the rutile and thus crystal growth of TiO2 .2 -bipyridine-4. 423] demonstrated the adsorption of benzoic acid on TiO2 (110) using STM. There was little evidence that CH2 =CH− (olefin) side chain affected binding of acrylic acid to the surface. allowing the formation of dimers of benzoate at the surface [408]. Although maleic anhydride (C4 H2 O3 ) is not a carboxylic acid. electron-stimulated desorption ion angular distribution (ESDIAD) and low energy electron diffraction (LEED) at room temperature.1. The adsorption of large organic molecules on TiO2 is rapidly gaining in technological importance. Photon induced damage of multilayers occurs fast (produces a first order desorption of zwitterionic molecules with total cross section). in the presence of oxalic acid. The molecules bind to two neighboring Ti rows in a bidentate mode through the dehydroxylated O atoms. for example.

Composite multilayers made of 11aminoundecanoic acid (NH2 (CH2 )10 CO2 H) capped-TiO2 nanoparticles (63 ± ˚ ˚ 2 A total diameter and 20–24 A core diameter) and charged polyelectrolytes were prepared by layer-by-layer self-assembly .3 relatively few studies have been carried out compared to others systems. which have been studied to a much lesser extent than thiols on gold. A longer chain length to promote extended chain structures may be required when the additional polar functionality also has a strong affinity for a particular metal oxide as in the case of carboxylic acids and ZrO2 . HO2 C(CH2 )n PO3 H2 (n = 2. 435] and alkanephosphonic [432. 433.7.294 1 Preparation of Monolayer Modified Electrodes temperature programed desorption (TPD) [429]. 460]. Moreover. The surface bonding. semiempirical calculations of C4 H2 O3 over a relaxed Ti13 O45 H38 rutile clusters were conducted. Nanocrystalline TiO2 layers were treated a 1 mM solution of benzoic acid in CH3 CN at room temperature. Although the adsorption of long-chain carboxylic acids on metal oxides produced the first SAMs [296.3. Looping structures were reported for HO(CH2 )15 CO2 H adsorbed on Al2 O3 [295]. The model was suggested where one C−O−C bond was broken and bonded to one Ti. Long-chain Organic Acids Organic monolayers of amphiphilic alkanoic acids [431. 30. Amphiphilic organic acids on metal oxides are a class of SAMs. and mobility were characterized by 13 C and 31 P solid-state NMR and IR. 434–440] or alkanephosphoric acids [441–444] onto TiO2 and ZrO2 surfaces by adsorption from solution have been studied in the past few years (see Table 4). The results have been shown to be consistent with the variation in the work function of modified TiO2 . and 5 nm. both acid groups can interact with metal oxide surface. chain conformation. They attributed this effect to a change in band bending at TiO2 /HTL interface induced by the dipole moment of adsorbed benzoic acid. These indicated that −PO3 H2 binds selectively to the surface producing a monolayer of HOOCterminated chains. and 15). To investigate the influence of chain length and particle size. The likelihood of such bridging structures increases with increasing chain length and decreasing particle size. Sample preparations as well as the measurements were carried out under an atmosphere of argon. measured on the free surface. were deposited on nonporous TiO2 and ZrO2 powders and nanocrystalline ZrO2 with average particle diameters of 21. but the same surfactant forms densely packed. The average chain conformation depends on the substrate in addition to the chain length. 297. 3. The dissociated mode of adsorption is more favored than the nondissociated mode by 0.5. all-trans chains on ZrO2 due to the formation of zirconium carboxylate bonds [431].5 eV. respectively [432]. The chain length is an important variable in regard to whether extended versus looping structures will form. a series of diacids. Two modes of adsorption were considered. and particle–particle interactions may include bridging structures in which a surfactant molecule binds to two particles. Gr¨tzel and coworkers [430] demona strated that modification of parafunctionalized benzoic acids on TiO2 can be used to systematically improve the I−V characteristics of solid-state dye-sensitized solar cells. In the case of carboxyalkylphosphonic acids. 1. 11. TPD results indicated breaking of C=C bond and formation of ketene with an H atom that could either come from more complete dissociation of C4 H2 O3 or as an impurity from the bulk.

7 Chemically Modified Oxide Electrodes 295 [433]. and then lightly rinsed with appropriate solvent. For long-chain phosphonic acids. This symmetry can be achieved with a tridentate chelating bonding mode (a) or a tridentate bridging mode (b). octadecanephosphonic [435–440]. IR data suggested that phosphate and alkanephosphonates are bounded to metal oxide surfaces in the same C3ν symmetry. These were left for 4 h in 0. TiO2 and ZrO2 surfaces were coated with dodecanephosphoric acid monolayers by immersion of the substrates into aqueous solutions [442–444]. The composite film coated by a layer of gold has been shown to function as a Schottky diode. a fivefold excess of the acid relative to the moles for a full surface coverage on the oxide was dissolved in 1000 mL of 3 : 1 methanol-water mixed solvent. ZrO2 appeared to be the best substrate for the formation of ordered monolayers [436. In addition. In a typical preparation. The adsorption modes were characterized by direct analysis using infrared spectroscopy (IR). It should be emphasized that this method of layering can be potentially extended to any oxide particles capable of interacting with carboxyl group of any amino acid. The resulting suspension was held at 100 ◦ C for 3 days with stirring. Fig. as illustrated in Fig. and octadecanephosphoric acids [441] for surface modification of TiO2 and ZrO2 has also been reported. The alkyl chain (R) is perpendicular to the surface. 7 O M O M O M (b) Tridentate bridging . A suspension of 2 g of metal oxide in 200 mL of deionized water was added dropwise to the acid solution. Modifications of TiO2 and ZrO2 membranes and powders with phosphoric acid and short-chain alkanephosphonic acids for separations in biotechnology have been studied [434].1 M acid solution. The solid was washed and centrifuged with 200 mL of methanol seven times to remove any physisorbed acid and then dried under vacuum at room temperature [436]. Reven and coworkers [436–438] have employed solid-state NMR technique for characterizing the surface bond and chain dynamics in SAMs of octadecanephosphonic acid on both planar and particle surfaces of TiO2 and ZrO2 as well as Al2 O3 . Fadeev and coworkers [439] have reported the comparative study of the reactions of octadecanesilanes with different headgroups and of octadecanephosphonic acid for the surface modification of TiO2 R P R P Alkanephosphonic (or O O O alkanephosphoric) acid bonding modes on metal oxide surfaces M such as TiO2 and ZrO2 : (a) thridentate chelating and (a) Tridentate chelating (b) tridentate bridging. 7. The use of octodecanoic [435]. 437].1. Monolayers of octadecanoic acid and octadecanephosphonic acid were formed from solutions in either isooctane or ethanol with concentrations of 1 mM in adsorbate. Whitesides and coworkers [435] have examined the preparation and properties of SAMs obtained by adsorption of longchain alkanoic acids and alkanephosphonic acids as well as alkanehydroxamic acids onto metal oxide surfaces such as TiO2 and ZrO2 . The membranes and powders were dried at 70 ◦ C before immersion in the acid solutions.

05. kinetics. 443] have described results on both pure and mixed SAMs of CH3 –and OH-terminated dodecanephosphoric acids deposited on TiO2 and ZrO2 as well as other oxides (Al2 O3 . SAMs were formed by immersion of the substrates in the solution for up to 48 h. which results in a stronger bonding of phosphonic acids [440]. and mechanism of the growth of the monolayers derived from different surface coupling agents on TiO2 . The preparation of well-ordered SAMs from heptane/propan-2-ol is applicable to various oxide substrates covered by alkanephosphates. and XPS (coverage and orientation of molecules) [443]. SAMs were characterized by water contactangle (wettability). 10 mL of solution of C18 H37 PO(OH)2 in toluene was injected into the vials using a syringe. and then dried in an oven at 60 ◦ C overnight [439. Fadeev and coworkers [440] have also reported the results on hydrolytic stability of different C18 -monolayers supported on TiO2 and ZrO2 surfaces. Following immersion. At 65 ◦ C. and Nb from an organic solvent.05–0. the substrates were removed from the solution and rinsed with propan-2-ol. The work was focused on the structure. After a given time (1–240 h).15–0. H¨hner and coworkers [441] have dea scribed the preparation and characterization of SAMs of long-chain alkanephosphoric acid esters on oxide surfaces of Ti. The u samples were subsequently washed with toluene. each being rinsed with 10 mL of high-purity water and finally blown dry with N2 .15 for ZrO2 and ∼0. The monolayers of C18 H37 PO(OH)2 demonstrated the best hydrolytic stability among the studied surfaces. the following range of reactivity was established: C18 H37 SiCl3 >> C18 H37 PO(OH)2 > C18 H37 Si(CH3 )2 Cl > C18 H37 Si(OCH3 )3 > C18 H37 SiH3 . blow-dried with N2 . Octadecanephosphoric acid was dissolved in n-heptane/propan2-ol (100 : 0. They have focused on a direct determination of the orientation and order of acid monolayers on the surface. and acetone. the reactions were quenched by filtering on a B¨ chner funnel with a fritted disk. microdroplet density measurements (condensation figures to judge homogeneity). 440]. Upon addition of solution. which corresponded approximately to a threefold excess in respect to the complete monolayer coverage of the surface with alkyl groups (∼5 group/nm2 ).2 for TiO2 -supported surfaces [440]. Al. The surface of ZrO2 is more basic (isoelectric points (IEP) ∼7–11) than that of TiO2 (IEP ∼4–7). The solutions contained 25 µmol of modifier per each square meter of TiO2 . The substrates were immersed for 48 h in the acid solution and removed.02–0. the presence of a functional group has been showed to influence the order of the adsorbed monolayer [444]. High stability of these monolayers is explained because of strong specific interactions of phosphonic acid group with the surfaces of metal oxides.296 1 Preparation of Monolayer Modified Electrodes (anatase).5 mM concentration. then dried on the filter to a dry state. On the basis of the kinetics measurements. This might open up the possibility of chemically tailoring many technologically important oxide surfaces via self-assembly. the values of θHYDROLYZED were ∼0. acetone. SAM formation did not occur on SiO2 surface under the same conditions [442]. the reaction vessels were left at room temperature. and stored in air until analysis. However. Ta2 O5 . The .4 (v/v)) solvent mixture at 0. and Nb2 O5 ) from aqueous solution. water-acetone (1 : 1). Spencer and coworkers [442. The extent of hydrolysis (θHYDROLYZED ) at 25 ◦ C for TiO2 and ZrO2 supported surfaces was ∼0.

8 eV) [461]. which places the conduction band edge above the excited state potential of most dyes (Fig. Allara and Nuzzo [296.0 VB Fig. Other large bandgap oxides are discussed in this section.0 e− 4. parameters that played a pivotal role for the preparation of organic surfaces with tailored properties [444]. . 460. Other Oxides Much research has been focused on the self-assembly of various organic molecules on wide bandgap n-type TCO substrates as described earlier.7.0 CB Energy [eV] TiO2 S+/S* ZnO e− 5.6 0 adsorption of organic monolayers on ZrO2 is described in the previous section and also summarized in Table 4. The metal oxides with a large bandgap such as ZrO2 (Eg = 5.or CH2 =CH-terminated alkanoic (C19 ) acids Vacuum level ZrO2 3. are ruled out by a low electron affinity.3. 462–490] is listed in Table 5 as described in the following.1. 8 Schematic energy band diagram of suitable and unsuitable metal oxides for organic dyes as sensitizers. 8).0 3. The chemical surface modification of large bandgap oxides with organic monolayers [295–297.4 eV Dye 7.8 eV 5. 264]. Most studies of the adsorption of carboxylic acids on metals have involved surfaces exposed to air prior to adsorption and thus largely refer to adsorption on native oxide overlayers.2 eV 6. Election injection from the dye-excited state to the energy level of conduction band (CB) is energetically favorable for wide bandgap oxides such as TiO2 and ZnO [261.0 S+/S 3. but forbidden for large bandgap oxides such as ZrO2 [461]. for example. The 1.7 Chemically Modified Oxide Electrodes 297 synchrotron-based technique gave direct information on the average orientation of molecules and the amount of defects. 297] studied the adsorption of n-alkanoic (C6 −C24 ) acids and CH≡C.

the . 4-CH3 (C=O)OC6 H4 COOH Zr (or Sn) alkoxide-mediated bonding carboxylic acids Octadecanephosphonic acid.4-cyclohexanedicarboxylic. 475. CH3 (CH2 )17 PO3 H2 R−PO3 H2 (R = n-C8 H17 . Al substrates were prepared by the evaporation of Al from resistively heated W boats onto Si wafer.22 COOH 4-Acetoxybenzoic acid. OH-. 474 462.and trans-1.10 COOH) acids Cl-. aliphatic dicarboxylic (HOOC(CH2 )3 – 8. 297 460 Substrate Al2 O3 295 435. (POCl3 ) Octadecanephosphonic acid. CH3 (CH2 )n COOH (n = 2–20. 471 472. isophthalic. 478–480 442 303 481 482 436 483–489 490 SiO2 Zirconated SiO2 SiO2 or Mica CaHAP on oxidized Al2 O3 . CH3 (CH2 )17 PO3 H2 Alkanephosphonic and alkanebisphosphonic acids Alkanephosphoric acids.or bithienylhexanphosphonic acids Octadecanephosphoric acid. 397. CH3 (CH2 )2 – 18.4 -dicarboxylic acid)2+ Stearic acid. CH3 (CH2 )16 COOH Phosphorus oxychloride. 462–466 467 468–470 435. 1. CH3 (CH2 )15 – 17 COOH and CF3 (CF2 )8 COOH n-Alkanoic acids.10 ) dicarboxylic acids on γ -Al2 O3 powders. OH−or CH3 (CH2 )11. n-C18 H37 . Ogawa and coworkers [460] studied the adsorption of tere.298 1 Preparation of Monolayer Modified Electrodes Tab. CH3 (CH2 )17 PO3 H2 Octadecanephosphonic acid. F-.and isophthalic acids. 473 441. OH−or CH3 (CH2 )11 OPO(OH)2 Ru(bpy)2 (bpy-4. 476 464 Al2 O3 or CuO AgO or CuO Steel or Brass Steel Nb2 O5 or Ta2 O5 473 477 441. 436. nC8 F17 F−(CH2 )2 ) References 296. benzoic. cis. 22) 4-alkoxybiphenyl-4 -carboxylic and 6-alkoxy-2-naphthoic acid derivatives with aliphatic long-chains (n = 15–19) Alkanephosphonic and alkanebisphosphonic acids Thienyl.17 OPO(OH)2 Polypyridyl Ru complexes and organic dyes n-Alkanoic acids. and aliphatic (C3 – 8. In addition.4-cyclohexanedicarboxylic acids. 442 304. 5 Examples of organic chemical treatments used for surface modifications of large bandgap Al2 O3 and various other oxide substrates Chemical modification n-Alkanoic acids and CH≡C−or CH2 =CH(CH2 )19 COOH Tere-. CH3 (CH2 )17 OPO(OH)2 Dodecanephosphoric acid. 464.

Octadecanephosphonic acids are air stable compounds that are known to form stable. 297]. 435]. Observations made by Allara and Nuzzo [296. Whitesides and coworkers [295] demonstrated the formation of orthogonal SAMs obtained by adsorption of alkanethiol on Au and alkanoic acids on Al2 O3 . 472.78 A. each ∼ 1 µm. Whitesides and coworkers [471] showed that octadecanephosphonic acid can be patterned on Al2 O3 /Al by µCP and that patterned structures are electrically similar to samples prepared by conventional photolithography and lift-off. The plane that bisects the methylene groups is twisted with respect to the plane of the carboxylate group. IR studies by Tao suggested that monolayers on AgO are more ordered than their counterparts on Al2 O3 . the carboxylate two oxygen atoms bind to the surface nearly symmetrically. However.or naphthyl-containing alkanoic acids on the surfaces of Ag and Cu. Polarized IR external reflection spectroscopy studies confirm this structure [462. It was found that on AgO surfaces. 475].1. and separated patterns are electrically isolated. and binding strength. and are tilted at 26. the carboxylate binds asymmetrically to the surface displaying tilt angles close to zero. with interchain spac˚ ing of 5. easily displaced adsorbate [296.7◦ from the surface normal toward the nearest neighbor. 462–466] and AgO or CuO [435. ordered monolayers on metal oxide surfaces [298. Tao and coworkers [464] also reported the self-assembly of biphenyl. and Sondag and coworkers [467] indicated that stearic acid adsorbs to AgO and Al2 O3 in slightly different orientations. 473] and copper or iron [435. The area per chain within the ˚ SAMs is 28. Tao [462] has showed that the chemisorption of alkanoic acids on amorphous metal oxide surfaces is not unique. in isooctane for 24 h. Schwartz and Bernasek [468–470] developed a method to increase the binding of SAMs of carboxylic acids on a hydroxide terminated Al2 O3 /Al surface by first priming the metal hydroxide surface with Zr alkoxide. binding geometry. Using µCP. which was then removed from solution and washed with hexanes. Schottky diodes of aluminum have been prepared on p-type Si(100).8 A2 [476]. This technique provides control over the scale of the dimensions reached by the microlithograpically generated features. but this interaction results in a weakly bound. among other factors. 297]. Thompson and Pemberton [463]. SAMs were formed by exposing the clean grid to a mixture of CF3 (CF2 )8 CO2 H and Cl(CH2 )8 SH. Aluminum is commonly used as a metallization layer in the microelectronics industry. SAMs on the native oxides of aluminum [435. 473] have been formed from alkanephosphonic acids. while on surfaces Al2 O3 and CuO. Different behavior observed on Ag and Cu has been attributed to site specificity. Alkanecarboxylic acids adsorb on Al2 O3 / Al as the carboxylate anion. A stable monolayer assembly can be formed on Ag by the spontaneous adsorption of arachidic acid (CH3 (CH2 )18 COOH) from hexadecane [475]. The patterned structures resulting from etching are continuous and electrically conductive within each pattern. 475] surfaces has also been investigated.7 Chemically Modified Oxide Electrodes 299 adsorption of alkanoic acids on natively oxidized Al2 O3 [435. 464. This study . Surface X-ray diffraction of docosanoic acid (CH3 (CH2 )20 COOH) monolayers on Ag(111) surface showed that the carboxylate anion adsorbs in a p(2 × 2) overlayer structure. The alkyl chains are in all-trans extended configuration.

The surface bonding and conformational order of octadecanephosphonic acids adsorbed onto Al2 O3 . Equally clearly. The results show that octadecanephosphonic acid reacts strongly with Al2 O3 to form a bulk (aluminoalkyl)phosphonate [436]. First attempts to apply SAMs for corrosion protection were made with the use of alkanethiols on iron and copper [491]. 478–480]. TiO2 . performed in ultrahigh vacuum.and diphosphonates were applied successfully to form well-oriented SAMs on aluminum [435. as evidenced by the experimental observation of a reorganization of layers and a formation of rodlike structures on bilayer surfaces at room temperature. The monolayer films of metal phosphate have been fabricated with divalent (Ca2+ ) and tetravalent (Zr4+ ) metal ions on the phosphoric acid (PA) modified substrates [482].and bidentate binding of the phosphate group thus enabling the formation of a close-packed layer. and iron or steel [473. Transparent nanoporous nanocrystalline Al2 O3 films (4-µm thick. and zirconated silica were characterized by solid-state NMR and IR spectroscopy. copper or brass [473]. 472. Octadecanephosphoric acid (CH3 (CH2 )17 OPO(OH)2 ) and dodecanephosphoric acid (OH−or CH3 (CH2 )11 OPO (OH)2 ) have been shown to form SAMs on Ta2 O5 and Nb2 O5 [441. Furthermore. 397]. however. the molecular structure of these adlayers has been demonstrated to be similar to thiols on ˚ gold with an intermolecular spacing of 5 A ˚ (corresponding to 21 A2 per molecule) and a tilt angle of the molecular axis of 30–35◦ relative to the surface normal [479]. and the reactivity of Zr alkoxides may limit its application to monolayers formed in solution. Self-assembled octadecanephosphonic acid layers were also prepared on a Si substrate by a solution spreading method and studied using AFM [483]. TiO2 . highly ordered monolayers can be prepared by the adsorption of octadecanephosphonic acid onto nonporous ZrO2 . While Zr4+ ions combined with PA monolayer maintain the positive charge as Zr2+ . 442. irradiation with the blue output of an Arion laser (200 mW cm−2 ) for 15 s does not lead to a measurable change in the optical absorption spectrum of Al2 O3 -RVs. Immobilized molecules are able to act as adhesion promoters and corrosion inhibitors. V = viologen) are not significantly different from those of Al2 O3 -RVs in solution [304]. 473]. ZrO2 . since the bandgap of Al2 O3 is so large (about 9 eV) that are no conduction band states isoenergetic with the electronically excited state of the Ru component of Al2 O3 -RVs [304. These findings. Al2 O3 . Dense.300 1 Preparation of Monolayer Modified Electrodes was. Octadecanephosphonic acid molecules were found to be highly mobile. no visible emission is detected from Al2 O3 -RVs. Using a combination of dedicated surface characterization techniques. 14-nm diameter nanocrystals) supported on a microscope glass slide were prepared as described by Gr¨tzel and coworkers a [397]. Alkane mono. 477]. The absorption spectra of Al2 O3 -RVs (R = phosphonated Ru complexes. p-Type Si(100) wafers were used as a substrate . and zirconated silica [436]. Ca2+ combined with PA monolayers forms a neutral surface. The binding of the phosphate head group to the surface is believed to be through direct coordination between phosphate and metal cation and arguments have been given for the presence of both mono. however. These investigations have shown that the phosphonic acid group is one of the best anchor groups for building stable SAMs on passivated iron [477]. are not unexpected.

two of which have been studied. The monolayers on a mica substrate is very stable upon heating at temperatures up to 80 ◦ C [488]. undoped single crystal of α-Al2 O3 . semiconductors. Solutions of low concentration (∼5–10 mM or less) yielded covalently attached monolayers supported on CaHAP. the major mineral component of hard tissues (teeth and bones). while a 2-mM solution was used for formation on the mica surface [483].5 mM aqueous solution of Zr4+ or Ca2+ ions for 20 min to bind metal ions. at room temperature. An Si wafer and a cleaved mica substrate were used as the support for preparing CH3 (CH2 )17 PO3 H2 samples. Sapphire. The cleaned Si substrates were immersed for 12 h at 70 ◦ C in a fresh 1 : 1 mixed solution of 10 mM phosphorus oxychloride (POCl3 ) and 10 mM 2.7 Chemically Modified Oxide Electrodes 301 for the SAMs. calcium hydroxyapatite (Ca10 (PO4 )6 (OH)2 or CaHAP). there have been reports of the use of octadecanephosphonic acid (CH3 (CH2 )17 PO3 H2 ) molecules to form monolayers on Si [483]. Recently. When a diluted solution of CH3 (CH2 )17 PO3 H2 was used to wet the mica substrate. mica [484–488]. Schwartz and coworkers [486] studied the growth kinetics of CH3 (CH2 )17 PO3 H2 on mica by examining films removed from solution before completion. for example. is widely used as a substrate for thin-film deposition of metals. These data were compared to two models for diffusion-limited and adsorption-limited (Langmuir) kinetics.4. Fadeev and coworkers [490] studied the surface modification of CaHAP with organophosphonic acids (R−PO3 H2 ). sapphire [489]. A concentration of 5 mM CH3 (CH2 )17 PO3 H2 solution in ethanol was used for preparing CH3 (CH2 )17 PO3 H2 samples on the Si surface. the major products . resulting in a monolayer having a great potential for application as an ordered surface providing hydrophobic chemistry [484–487]. C-face (1000) and Rface (1102). The solution-phase reactions of R−PO3 H2 (R = n-C8 H17 . Schwartz and coworkers [489] also extended their CH3 (CH2 )17 PO3 H2 SAM studies to a new substrate as sapphire (corundum). and Ca hydroxyapatite [490] surfaces. indicating that the interaction between the hydrophilic headgroup and the mica surface is quite strong. such as that of inorganic phosphates. Nanometer-scale patterning on the self-assembled metal phosphate films has been achieved using AFM. According to FTIR spectroscopy. The headgroup of CH3 (CH2 )17 PO3 H2 molecules is found to be bonded to the mica surface. namely. Different growth kinetics were observed for the two crystal orientations.1. Russell and coworkers [487] studied the dynamics of self-healing of scratches made on CH3 (CH2 )17 PO3 H2 monolayers employing AFM as the experimental tool. for samples prepared by the drip coating and crystal melting methods. ranging from partial to complete was observed on drip-coated samples. Surface coverage of submonolayer islands was extracted from AFM images as a function of immersion time for solution concentrations from 0. or insulators. These substrates were dipped into a 0. and n-C8 F17 F-(CH2 )2 ) were studied with two types of CaHAP substrates: high surface area powder and thin films supported on Ti/Si wafers. a monolayer of CH3 (CH2 )17 PO3 H2 was observed using AFM. Several crystallographic faces of sapphire are available. which could be related to the surface energetics [489]. n-C18 H37 . Very little is known about surface modification of nonoxide surfaces. Scratch morphological evolution was followed as a function of time.02 to 2 mM. Self-healing.6-collidine in acetonitrile.

4-F.7 CH3 . X4−n −Si−Rn X3 −Si−R. 265]. aryl amine Ru(bpy)2 (β-(4-trichlorosilylethyl-4 -CH3 -bpy)2+ Cl3 −Si−R. or immobilize large functional groups such as biomolecules on surfaces [23. CH3 O.1. (CH2 )3 NH2 .7. Cl. Al2 O3 [498. 4-Cl. 498 499 SnO2 or Fe2 O3 TiO2 TiO2 or ZrO2 TiO2 . alkoxide. R = (CH2 )3 NH2 . 573–575] (see Table 6). (CH3 )3 −Si−CH2 Ph-R. HfO2 . C2 H5 C5 H4 N (C2 H5 O)3 −Si−(CH2 )3 −R.1 Tab. 291 492 493 494 495–497 439. or alkyl group. R = SiH3 . Examples of chemical modification of organosilane derivatives on various oxide surfaces Organosilanemolecule. 440. (C2 H5 O)3 −Si−CH=CH. 492–494]. 3-CH3 . 265. where R = 3-CH3 O. X = H. and SiO2 [533–575] as well as other oxide surfaces [440. the functional groups R are chosen to form protective layers. C18 H37 . (CH2 )2 C6 F13 (CH3 O)3 −Si−(CH2 )2 (CF2 )7 CF3 (HO)3 −Si−R. 4-CH3 . SAMs of organosilane derivatives require hydroxylated substrate surfaces for their monolayer formation. NiO. R = (CH2 )3 NH2 . 290. (CH3 O)3 −Si−(CH2 )17 CH3 (C2 H5 O)2 −Si(C2 H5 )2 . 506–529]. (CH2 )3 N(CH3 )3 + Octachlorotrisiloxane. Si3 O2 Cl8 N(p-C6 H4 (CH2 )3 SiCl3 )3 and TPD-((CH2 )3 SiCl3 )2 References 290 Substrate SnO2 242. 501–503. C8 H17 . (CH2 )3 NHC2 H5 NH2 . or 3-CF3 ) (CH3 O)3 −Si−(CH2 )3 NHC6 H5 H3 −Si−R. ITO [347. Modified surfaces showed good hydrolytic and thermal stability [490]. ZrO2 . a reactive leaving group that attaches the Si to the surface. X4−n −Si−Rn (where X represents a halide.4. X is a hydrolyzable. (CH3 O)3 −Si−(CH2 )2 CF3 . 6 between organic and inorganic layers. 530–532]. 265.2-tetrahydrooctyl Octadecyltrimethoxysilane. 283–289].4 Organosilanization General Silanes with the general formula. (CH2 )2 CHCl2 . modified electrodes. TiO2 [439. (CH2 )3 SH (CH3 O)3 −Si−(CH2 )3 NH2 (CH3 O)3 −Si−R. and (C2 H5 O)4 −Si X3 −Si−C18 H37 .302 1 Preparation of Monolayer Modified Electrodes of the reaction were organophosphonic groups bound to the surface via PS −O−P bonds. CH3 O. Organosilanes can act as a bridge 1. 493. and R an organofunctionality). X = C2 H5 O. R = (CH2 )3. R = 4-arylazo-1-naphtol NH2 . have been used for chemical modification and as coupling agents since the first reports by Murray and coworkers [290] and others [242. 440. 1. 495–503]. Cl. Al2 O3 ZnO 500 501–503 504 505 506–508 347 509–511 512–516 ITO ITO or SiO2 . 3-Cl.2.7. (CH2 )6 CH=CH2 . Substrates on which these monolayers have been prepared include SnO2 [242. R = tridecafluoro-1. (CH3 )2 Cl Benzyltrimethylsilanes. ZnO. ZnO [503–505].

6.or18 Cl3 −Si−(CH2 )3 -3-(pyridine-4-methyl)-urea Cl3 −Si−(CH2 )12 −R. X = CH3 O.7 CF3 . CH2 Br. 519 520 521 522 523 524–526 527. di-. [(CH3 )3 −Si]2 −NH2 . (CH2 )3 NH(CH2 )6 NH2 (C2 H5 O)3 −Si−(CH2 )3 NH2 4-Aminobutyl-dimethyl-monomethoxysilane (3-Bromopropyl)trichlorosilane Mono-. retinal. (CH2 )3 OCF(CF3 )2 . 4-Cl. R = phenyl. (CH3 O)3 −Si−(CH2 )17 CH3 Docosyltrichlorosilane.8.4. . 4-SO2 Cl). Cl3 −Si−(CH2 )3. Cl3 −Si−(CH2 )17 CH3 Octadecyltrichlorosilane. 533–541 463. The Si 2p band was most intense for SnO2 treated with Cl3 SiCH3 . (CH3 O)3 −Si(CH2 )3 O2 CCH3 =CH2 References 517 518. 562 563–566 567 568 569 570. X4−n −Si−Rn (C2 H5 O)3 −Si−(CH2 )3 NHCO2 -TPA (triphenylamine) 3-[N-CH3 -N-4-(4-nitrophenylazo)phenyl-amino]propylmethyldiethoxysilane (Dichloromethyl)dimethylchlorosilane (CH3 O)3 −Si−R. CO2 CH2 -R .1 SnO2 It is known from chromatographic [576] and other studies that the order of reactivity of halosilanes with silica is X3 SiR > X2 SiR2 > XSiR3 .or10 SH p-Aminophenyltrimethoxysilane Phenyltrichlorosilane.7 CH3 . R = ethyl. This relationship was also observed with SnO2 surfaces in a series of reactions where X = Cl and R = methyl. TiO2 SiO2 SiO2 .7.12. Cl3 −Si−CH2 (CH2 )20 CH3 Cl3 −Si−(CH2 )7. 531. Cl3 −SiR. Cl3 −Si−C6 H5 Cl3 −Si−(CH2 )11 −O−C6 H5 (CH3 O)3 −Si−R. Cl-SiMe2 R.2. R = (CH2 )5.1. 532 527. 543 544–548 Substrate ITO or SiO2 ITO or SiO2 Al2 O3 Al2 O3 . and CH=CH2 (CH3 O or Cl)3 −Si−(CH2 )3. 1-propanthiol Octyltrimethoxysilane. 6 303 (continued) Organosilanemolecule. SiO2 . Al2 O3 . and least for ClSi(CH3 )3 [290]. Cl. Cl3 −Si−(CH2 )17 CH3 Octadecyltrichlorosilane. (CH3 O)3 −Si−(CH2 )7 CH3 Cl3 −Si−(CH2 )2 (CF2 )7 CF3 Octadecyltrimethoxysilane. Cl3 −Si−(CH2 )17 CH3 X3 −Si−R. (CH2 )6 CH=CH2 . C6 –C8 . Cl3 −Si−(CH2 )2 C6 H5 R (R = 4-H. pyrene). (CH2 )17 CH3 .17 CH3 . R = C1 –C4 .21 CH3 10-undecenyl. CF3 ).17. 542. R = (CH2 )2 (CF2 )5. allyl. 3-(2-aminoethyl)-aminopropyl Cl3 −Si−(CH2 )2 (CF3 )5 CF3 . Cl2 −SiMeR. 560 561.4. Si3 N4 549–551 552 553–555 556–558 SiO2 or Al2 O3 559.7. 571 572 CaHAP 573–575 1. C10.or 18-nonadecenyltrichlorosilanes Octadecyltrichlorosilane. Cl3 −Si−(CH2 )3 R (R=CH2 Cl.2 Wide Bandgap Transparent Conducting Oxide Electrodes 1. R = carbazole. 528 529 530 498. and trichloroalkylsilanes.7 Chemically Modified Oxide Electrodes Tab.

the sensitizers should be bound as close to the electrode surfaces as possible in order to increase the efficiency of spectral sensitization [291]. Ghosh and Spiro [492] have used this approach to covalently attach Ru(bpy)3 2+ to n-type SnO2 via condensation of surface hydroxyl groups with Ru(bpy)2 (β-(4trichlorosilylethyl-4 -CH3 -bpy)2+ and have studied electrochemistry and photochemistry of the coated electrodes. At low coverages. Such thermal lithographic method is a new approach to patterning surfaces [494]. TiO2 and ZrO2 A series of silanes on clean and water-dosed TiO2 (110) surfaces were investigated by Campbell and coworkers [495–497].2. under nitrogen. for several hours with trichlorsilanes to several days with triethoxysilanes. Surface bonding depends on reactions of organosilane reagents with hydroxyl groups on SnO2 . Organosilanes spontaneously react with hydroxylated surfaces to form films of specific chemical functionality for a variety of applications. consists of a central Si atom bound to four ethoxy (EtO) groups. Fujihira and coworkers [265. 10% solution of refluxing silane.2 Sn–OH + (C2H5O)3Si(CH2)3NH2 Sn–O– Si(CH2)3NH2 (1) Sn–O–Si(CH2)3NH2 + (ClOC)4–TPP (Py) Sn–O– Si(CH2)3NHC–TPP(COCl)3 (2) O Amide linked Schematic presentation for formation of aminopropyl-modified SnO2 electrodes with organic dyes such as TPP(COCl)4 [292]. the cleaned SnO2 or TiO2 electrodes were treated with γ -aminopropyltrichloroethoxysilane.304 1 Preparation of Monolayer Modified Electrodes Silanization reactions were carried out in dry deaerated benzene or xylene. Fig. 292] have tried to increase the surface coverage of the amide-linked organic dyes such as RhB−COOH or TPP(COOH)4 and ultimately to increase the sensitized photocurrent by improving yields of the silanization reaction. in toluene to form the aminopropyl-modified SnO2 electrodes [292] by the method developed by Murray and coworkers [290]. If the chemical modification of electrode surfaces are applied to the solar cells. For example. 291. (C2 H5 O)3 Si(CH2 )3 NH2 . it readily dissociates. the utility of the thermally generated organosilane masks was demonstrated through selected area deposition of sol-gel derived materials such as SnO2 [493]. the surface attachment of electroactive molecules to modify electrode properties has been studied very extensively and chemicals with various properties have been immobilized [284]. Since the mid-1970s. As shown in Fig. the solution was decanted and the specimens were washed under nitrogen with several portions of fresh solvent [290]. tetraethoxysilane (TEOS). 9 . After reaction. On the average. two of the four −COOH groups of TPP(COOH)4 might be bound to SnO2 [292]. For the amide-linked electrode. 9. Electrode specimens were reacted under 50 ml of a ca. Multilayers form at high dosages at low temperatures 1.7.4. The simplest molecule. splitting off one or several EtO groups.

1. Wettability studies revealed that the surface of the as-prepared thin films showed a contact angle (CA) for water of 128. The prepared thin films were treated with a methanol solution of hydrolyzed (heptadecafluorodecyl)trimethoxysilane (CH3 O)3 Si(CH2 )2 (CF2 )7 CF3 .4. PANI was able to sensitize TiO2 efficiently in the presence of SAM.7. many mechanistic details have been collected about this TiO2 -sensitized photooxidative process starting with benzylic derivatives such as alcohols and silanes) in CH3 CN [499].2. and the surface modified by a (fluoroalkyl)silane showed superhydrophobic properties.3 ZnO A simple method of electrochemical deposition was adopted to prepare conductive hydrophobic ZnO thin films [504]. 4-CH3 . Kornherr and coworkers [505] have compared a model of a reconstructed surface with a model of ideal bulk terminated surface.3 ± 1.0 wt %) for 3 h and subsequently heated at 100 ◦ C for 1 h.7 Chemically Modified Oxide Electrodes 305 [495]. They also studied the reactions of different endfunctional organosilicon hydrides (H3 SiR.1. These ZnO films were fabricated by overpotential electrochemical deposition at room temperature. and HfO2 as well as other metal oxides (groups II–VIII) [501. and thiolpropyltrihydroxysilane) with the polar ZnO(0001) surface [505].and diethyldiethoxysilanes also dissociate on TiO2 surface in the absence of water by splitting off two EtO groups [496]. 3-CF3 ) were used. (CH3 )3 SiCH2 PhR. where R = 3-CH3 O. 1. 3-CH3 . 503]. Spectroscopic data showed that these bind to exposed Ti sites. CH3 O) with surfaces of TiO2 and ZrO2 . According to the rate constants [439]. 501]. C8 H17 . (CH2 )6 CH= CH2 . ZrO2 . Benzyltrimethylsilanes. 3-Cl. butyltrihydroxysilane. All the SAMs good thermal stability and no mass loss were observed below ∼200 ◦ C in air [439. Surface morphology is shown to have little effect . whereas the superhydrophobic surface with a water CA of 152. According to the rate constants. In addition. Methoxysilanes are more reactive with TiO2 (110) than ethoxysilanes [497]. the following range of reactivity was established: C18 H37 SiCl3 >> C18 H37 PO(OH)2 > C18 H37 Si(CH3 )2 Cl > C18 H37 Si(OCH3 )3 > C18 H37 SiH3 . (CH3 O)3 −Si−(CH2 )2 CF3 turned out to be more reactive than ethoxysilanes considered. X = H. the following range of reactivity was established: H3 Si(CH2 )8 SiH3 > H3 Si(CH2 )2 C6 F13 ≈ H3 SiC8 H17 > H3 SiC18 H37 [501]. 440] have studied the reactions of octadecylsilanes with different head groups (X3 SiC18 H37 . Cl. R = (SiH3 .0◦ was obtained by (fluoroalkyl)silane modification [504]. Vinyl. 503]. The structure of the monolayers and the reaction mechanisms were discussed in detail [501. C18 H37 ) with TiO2 . 4-Cl. molecular dynamics simulations at 298 K were used to study the interaction of adsorbed silane molecules (octyltrihydroxysilane. An organic solvent free heterojunction of n-TiO2 /p-polyaniline (PANI) with enhanced photovoltaic properties could be constructed by chemical polymerization of aniline followed by covalent grafting via (CH3 O)3 −Si−(CH2 )3 NHC6 H5 compound [500]. (CH2 )2 C6 F13 .7◦ . and that the Si in the remaining (CH3 O−Si−(CH2 )2 CF3 ) complex binds to two lattice oxygens (two bridging oxygen atoms in the proposed model) [497]. In recent years. aminopropyltrihydroxysilane.0 ± 2. This molecule also adsorbs dissociatively by splitting off −OCH3 groups. Fadeev and coworkers [439. (C2 H5 O)3 Si(CH2 )3 NH2 (with a (CH2 )3 −NH2 group substituting one EtO in TEOS) does not dissociate on TiO2 in any measurable quantity [496]. 4-F.

Fukuzumi and coworkers [507.21 CH3 and Cl3 −Si−(CF2 )5 CF3 -based SAMs on ITO that modulate the luminescence of OLEDs [528. and high current efficiencies (∼8 cd/A) [516]. 511] have reported the use of layer-by-layer. 529] have described ‘‘hot microcontact printing’’ to form patterned Cl3 −Si−(CH2 )7.4. Marks and coworkers [528. Patterning ITO electrode is conventionally achieved via photolithography. These substrates were then alternatively immersed in a polyanion and then a polycation solution. Other methods of patterning ITO have been explored as cost-efficient alternatives. such as (CH3 O)3 Si(CH2 )3 NH2 .4. have been patterned on Al2 O3 and TiO2 as well as SiO2 surfaces by µCP [498. The general conclusion of these studies is that the formation of densely packed defect-free SAMs on ITO is difficult due to the high surface roughness and low hydroxyl coverage. Silanization of ITO using shortchain alkylsilanes [520. The ease of preparation of these monolayers. low turn-on voltages (∼4 V). Large Bandgap Oxide Electrodes Octadecyltrichlorosilane. They have also reported that chemically tuning the interface structure represents an effective approach to studying nanoscale injection layers and yields with high efficiency (∼70 000 cd m−2 ).306 1 Preparation of Monolayer Modified Electrodes on the orientation of silane adsorbates (except thiolpropyltrihydroxysilane). selflimiting chemisorptive octachlorotrisiloxane (Si3 O2 Cl8 ) self-assembly techniques to introduce robust. this lowering is not as large as expected from a naive estimate.17. 521] was reported and shown to be anchor with a good stability on ITO. conformal. microstructurally/electronically well-defined charge injection dielectric layers at ITO/HTL interface of OLEDs. which is due to the fact that the dipoles are not densely packed and do not stand perfectly perpendicular to the electrode surface. 1. 529]. The grafting of molecular dipoles at the surface of ITO anode has been found to lead to a significant lowering of the injection barrier [518]. In addition. The ITO surface was first derivatized to form a positively charged layer of pH-insensitive and redox-inactive −CH2 CH2 CH2 N(CH3 )3 + groups by silylation [347].20.3 . have been used mainly for attaching dye molecules such as triphenylamine [517] and azobenzene derivatives [518. Functionalized alkylsilanes. with adsorption energy being correlated with the surface polarity.2. Marks and coworkers [512–515] have demonstrated that a spincoated. However. Cl3 Si(CH2 )17 CH3 . N(p-C6 H4 (CH2 )3 SiCl3 )3 and TPD((CH2 )3 SiCl3 )2 derived adhesion/injection interlayers at ITO/HTL interface of the devices.7. 508] have recently reported the first photogeneration by ITO modified chemically with SAMs of porphyrin-C60 linked molecules (H2 P-C60 /ITO) and its zinc complex (ZnP-C60 /ITO). will open the way to their use as commercially important etch resists [523]. ITO Mirkin and coworkers [506] have reported the first SAMs of C60 attached onto 3aminopropyltrimethoxysilane ((CH3 O)3 Si(CH2 )3 NH2 )-modified ITO electrode. Preparation and deposition of self-assembled siloxane dielectric layers were described [509].4 Armstrong and coworkers [510. combined with the ease of patterning and their high etch resistance.7. 1. 519]. only a small number of studies have been reported that aim at attaching alkyl chains onto ITO surfaces via silane chemistry [522–529].

such as Al/Al2 O3 [463.1. and plasma-modified polyimide [531]. 535–539. The oxidized Si samples were immersed into a freshly prepared solution of Cl3 Si(CH2 )17 CH3 in dried toluene at room temperature [534]. ITO.7 Chemically Modified Oxide Electrodes 307 530–532. 530–532. While S−Au bond is mostly charge transfer in nature. 527. One of the most useful classes of SAMs is that formed by alkanesilanes such as Cl3 Si(CH2 )17 CH3 on hydroxylterminated surfaces with a native oxide. the ‘‘headgroup-substrate’’ interaction of the silane and SiO2 surface is quite different. Sugimura and coworkers [545. forming a thin layer of covalently linked polysiloxane at the interface [577]. 40–60 A thick. The Al2 O3 layer formed either by air oxidation or by electrochemical anodization is amorphous and is referred to as α-Al2 O3 . The patterns were transferred into the substrates using both dry and wet etching. 541. Si/SiO2 . chemical properties. which protects the underlying metal [463]. glasses (for example. 543]. but upon heating. Lieber and coworkers [549] have reported systematic force microscopy studies of the interactions between different chemical functional groups covalently . In addition. 533–538. HF-treated silicon nitride surfaces. 557. including thickness. Surface potential images of these microstructures were acquired by Kelvin-probe force microscopy. SAMs have also been patterned on a number of substrates: Al/Al2 O3 . They [546] have also demonstrated nanostructuring of insulator based on current-injecting AFM lithography. After the substrates have been allowed to cool to room temperature. This small polymer interface is much more thermally stable than its RS−Au counterpart. µCP using octadecyltrichlorosilane ink is a convenient and easy way to pattern both metal and nonmetal (Al2 O3 . the samples were rinsed with deionized water and dried in vacuum. Experimental data suggested that the monolayers formed on oxygen-depleted Si3 N4 surfaces are similar to those formed on oxidized Si [537]. Films made from fluorinated alkylsilanes have been studied and they were found to yield well-ordered monolayers on Si substrates with the native oxide [544–548]. and morphology. Trichlorosilane (Cl3 Si(CH2 )17 CH3 ) SAM films having −CH3 and −CH2 Br terminal functionalities were grown on oxidized Si surfaces. and HF-treated Si3 N4 probe tips [537]. water repellency. 548] have studied the relations between the fluoroalkyl chain lengths of the fluoroalkylsilane molecules and properties of the films produced. TiN/TiO2 . The Al and Ti were etched using electron cyclotron resonance plasma source and Si was etched in HF to remove the native oxide. SiO2 ) surfaces without the extended use of photolithography. The oxide overlayer completely covers and is firmly adherent to the underlying metal surface. Cleaned Si(100) wafers are oxidized in a freshly prepared 4 : 1 mixture of 96% sulfuric acid and 30% hydrogen peroxide (piranha solution) at 100 ◦ C [534]. the silane molecules condense with native hydroxyl groups adorning the SiO2 surface. glass microscope slides). 567]. microstructures composed of two types of organosilane SAMs terminated with different functional groups have been constructed on Si substrates covered with native oxide [547]. Al easily passivates in the presence of air forming ˚ a thin Al2 O3 overlayer ca. 542] and Si/SiO2 [288. this form of oxide changes to a harder crystalline form known as γ -Al2 O3 [463]. thus affording greater stability and an extremely robust system. followed by KOH [498]. here.

Si wafers were immersed for 3 h in a 3 mM solution of the organosilane in anhydrous toluene and then cleaned in fresh toluene for 2 min. The structure of alkylsilane SAMs on Si have also been studied [463. and friction. Surface modification can be achieved by binding of different substituted alkylsilanes at the surface. pyrene) [561. organosilanes were applied to the SiO2 gate insulator from solution and form a SAM.10. 572]. 283–285.7. CO2 CH2 R (R = phenyl. the use of organosilanes. adhesion. 563]. thiol [563–566]. ruthenium phthalocyanine (RuPc) [560]. and CH3 ) on the Si(100) substrate [549–551]. When alkyltrichlorosilane is used. 527. Adhesion studies between SAMs which terminate with COOH and CH3 functional groups have shown that the interaction between COOH/COOH > CH3 /CH3 > COOH/CH3 [549]. 570]. Electrochemical studies on chemically modified oxide electrodes have been discussed in details in Refs. 560]. and phenyl [568. and deoxyribonucleic acid (DNA) [566. COOH. Prior to the depositing the organic semiconductors. 265. alkyl (C1 – 4. but also for providing active surfaces for the attachment of molecules with different properties such as polymers [552]. for surface modification of nonoxide surfaces such as CaHAP and Ca phosphate ceramics has been described [573–575]. 533. 290. These electrodes are widely applied in electrochemistry and electrocatalysis. Batlogg and coworkers [572] have more recently reported controllable shift of the threshold voltage and the turn-on voltage in pentacene thin-film transistors and rubrene single crystal field effect transistors (FETs) incorporating nine organosilanes with different functional groups (see Table 6). 549. retinol. This shift is governed by the build-in electric field of the SAM and can be explained using a simple energy level diagram [572]. Recent developments in optoelectronic and photovoltaic device systems require control of the chemical and . 570–572]. 4-chlorosulfonylphenyl [572]. 572]. Surface modification reactions are important not only for engineering of surface energy and interfacial properties such as wetting. they have utilized monolayers of 11mercaptoundecanoic acid on the probe tip and (C2 H5 O)3 −Si−(CH2 )3 R (R = NH2 . SAMs have been reported from alkyltrichlorosilanes with terminal groups of amine [552. halogen [553–555. vinyl [561. 570]. In addition. 572].18 ) [556–558. 562]. 554] have reported that self-assemblies of organosilanes can be used to tune the electronic properties of Si surfaces. In order to study the interactions. 556. 545. 1. 547.5 Potential Applications Starting from the pioneering works of chemical modification of TCO electrodes [242. π-electron moieties [561]. The observed shifts of the transfer characteristics range from −2 to 50 V and can be related to the surface potential of the layer next to the transistor channel. SAMs with low surface free energy have been prepared using partially fluorinated alkylsilanes [544. 3-(pyridine-4-methyl)-urea [559. mostly trialkoxysilanes.12. p-aminophenyl [567]. a lot of application possibilities have been developed.6 – 8. 569. 291].308 1 Preparation of Monolayer Modified Electrodes linked to a probe tip and sample substrate. Si−Cl bonds react with the OH groups present on the surface of the substrate to form a siloxane network. carbazole [561]. 570]. Cahen and coworkers [553. Organosilanes with more than one reactive group have the potential of binding to more than one surface site [556].

the contact potential between the two materials is VCPD = −(φ1 − φ2 )/e. 10(a). 312] in the same way as in chemical adsorption of acids and bases [311. Artificial photosynthetic molecular systems were also studied with various scanning probe microscopes including SSPM [584]. 10(b) and (c). These experiments were carried out to determine the phase-separated structure of a mixed monolayer of FC and HC amphiphiles ion-complexed with a cationic polymer deposited on Si(100) observed by friction force microscopy [582]. The increases in work function due to dipoles of binding and terminal groups are 1 and 2 . 580].7. Similarly. and CF3 −) benzene derivatives leads to enormous increase in ITO work function [312]. The molecular control of work functions of other semiconductors. we prefer π-conjugated systems to alkyl chains as the π-conjugated linkage can reduce the barrier heights for charge injection [291. 316]. CdSe. Campbell and coworkers [585. and −PO2 Cl2 ) of p-substituted (H−. The vector addition of the component dipole moments holds . 292. Selection of bonding modes of molecules with high permanent dipole moments is also important because additional dipole is created through the bonding [277. 324. Binding site and terminal group are linked by n-alkylene or p-phenylene group as shown in Fig. Cl−. SiO2 . Later. Directions of two dipole layers are preferable for enhanced hole injection. 584. such as CdTe. Large surface potential difference was observed between fluorocarbon (FC) and hydrocarbon (HC) covered water surfaces by Vogel and M¨ bius [578]. −COCl. expected energy diagrams are also shown. 325].7 Chemically Modified Oxide Electrodes 309 physical as well as photophysical properties of TCO thin films used as electrodes [254. we reported that the chemical modification of ITO with different binding groups (−SO2 Cl. where φ1 and φ2 are the work functions of the conductors including changes due to the adsorbed layers. electrochemical [314] and photovoltaic (PV) cell studies [308.1.5 eV by changing a surface covering pure monolayer from HC to FC with a terminal group CF3 − [276. and ITO surfaces with scanning surface potential microscopy (SSPM) [276. 586] applied the large work function difference between FC and HC on silver to control Schottky energy barriers in organic electronic devices. In this molecular design. and InP. The work functions can be changed by adsorption of molecules with different dipole moments [276]. The work function of ITO was increased more 1. 255. The following section gives some examples of the applications of chemically modified oxide electrodes for controlling the performance of optoelectronic and photovoltaic devices based on organic materials. 593]. Two dipole layers with large electric dipole moments have been introduced at the surfaces [578–586] via a binding group (X−) and a terminal group (−Y). 335–337. The work function control by alloy formation [588–592] and by the surface modification has been applied to enhanced charge injection at electrodes for OLEDs [306–313. 594]. than ITO were also reported using benzoic acid [587] and dicarboxylic acid derivatives [451].5. o the CPD due to large work function difference was observed between FC and HC covered gold. Recently. Tuning the Work Function of Electrodes Contact potential difference (CPD) for clean metal surfaces is given by the difference in the work functions of the two materials. respectively. 275–277]. 579–584]. GaAs. In a simple model.1 than 0. In Fig.

4 -diamine (TPD) film and an ITO anode chemically modified with various compounds with a binding site (X−) and a terminal group (−Y) linked with (b) p-phenylene or (c) n-butylene. Fig. N -bis(3-methylphenyl)1. It is obvious from the energy diagram that p-phenylene is better than n-butylene because of the lower barrier height for hole injection. φ0 : work function of ITO without dipole layers. N -diphenyl-N. the barrier heights for binding sites and terminal groups are more arbitrarily and schematically drawn because of the variety of these groups studied [292]. The change in work function due to chemical modification of ITO was .3 eV TPD HOMO: 5. In contrast. 10 in general [595].5 eV X =: − COCl − SO2Cl − PO2Cl2 Y =: HClCF3- ITO X Y TPD (b) Y X ITO TPD (c) Schematic illustration of (a) the energy diagram near the interface between a N. φeff : effective work function of ITO after chemical modification [312]. 1 -biphenyl-4. The barrier heights of nalkylene (dashed) and p-phenylene (solid) were estimated from our previous photoelectron spectroscopic data [596. 597].310 1 Preparation of Monolayer Modified Electrodes Vacuum level ∆total ∆2 ∆1 feff f0 ITO (a) +− +− +− +− +− +− +− +− +− +− +− +− +− +− +− +− +− +− +− +− +− +− +− +− +− +− +− +− +− +− +− +− +− +− LumO: 2. total : a shift of a vacuum level at the ITO/TPD interface due to two dipole sheets ( 1 and 2 ) formed by chemical modification of ITO.

In Fig. CPD values observed on ITO chemically modified with −SO2 Cl. and −PO2 Cl2 binding groups of p-chlorobenzene derivatives [312].7 Chemically Modified Oxide Electrodes 311 observed by SSPM [579–581] using gold-coated atomic force microscopy tips derivatized with 1-decanethiol. and UV-ozone treated ITO measured with the same modified tip are also plotted. The modified tips gave reproducible results. - Terminal groups Treated at 120°C Cl 0 −200 CPD [mV] As-cleaned −400 −600 −800 ITO (b) UV-oz. −SO2Cl −COCl −PO2Cl2 X X =: −SO2Cl −COCl −PO2Cl2 Binding groups Fig. Treated at 120°C 0 −200 CPD [mV] −400 −600 −800 ITO (a) 200 C =O Cl H− Cl− − CF3 As-cleaned Y Y =: H− Cl− − CF3 UV-oz. In order to tune the work function of ITO fine. 11(b). The large decrease in CPD down to ∼ −770 mV. that is. the CPDs of as-cleaned. and CF3 –terminal groups in para position are shown. . heat-treated. The CPD decreases with the increase in the 200 work function of ITO [276]. CPD values observed on ITO modified with benzoyl chlorides with H−. Cl−. and −PO2 Cl2 binding groups of p-chlorobenzene derivatives. −COCl. For comparison. In Fig. 11 The change in contact potential difference of modified ITO as a function of (a) benzoyl chlorides with various terminal groups and (b) −SO2 Cl. the work function of ITO increased as the permanent dipole in the para position increased. the effect of binding groups on the work function was also studied. As we would expect. 11(a).1. −COCl.

Various possible origins for interface dipoles formed at the interfaces have been proposed [275. 0. The work function shifts with respect to nontreated ITO were reported to be 0. φe . as shown in Fig. Impressive tests of the dipole layer on electrode surfaces have been conducted with use of SAMs of p-substituted arylthiols on Au [599] or Cu [585].7. Even on the latter modified ITO anodes. 12b). interfaces.1 eV for H3 PO4 . The molecular approach allows for finetuning the work function using organic molecules on ITO depending upon magnitude and direction of the dipole moment [312]. Thus. was observed with −PO2 Cl2 . TiO2 [430].4. 594] as well as both p. With molecules carrying a high dipole moment oriented perpendicular to the surface. since their charge will be sterically separated further away from the protonated positive surface. 331. 12(c). were observed with −COCl and −SO2 Cl. This picture was applied to the difference between HPF6 and HNO3 . In the double ionic surface layer model [335–337]. and HNO3 .5. 312. where the electrical double layer was created by formation of a double ionic surface layer. 598]. we can reduce the work function.and o-substituted phenols on modified ITO with tetra(tert-butoxy)tin [339]. However. the Fermi energy is down) and HOMO energy level in the organic layer is up by adding an electrostatic energy. GaAs [451. that is. Reversing the direction of the dipole. 12. the work function increase (or decrease) is associated with enhanced hole (or electron) injection [312. clean. and 0. while the enormous shift for H3 PO4 was rationalized by specificity of this acid whose two protons at least were considered to bind to the surface thus increasing the adsorbed dipole [335]. and thus the electron injection barrier. the results shown in Fig. Although various inorganic treatments have been shown to change the work function of ITO [330–337]. the work function increase was greater than that on the UV-ozone treated ITO. molecular electronics [593. .e. p-substituted benzoic acids on CdTe. often molecular. respectively. 587].2 Correlation of Device Performance with Changes in the Work Function The increasing level of research and device development activity involving a variety of organic. while the moderate decreased values of CPD.312 1 Preparation of Monolayer Modified Electrodes the increase in the work function of ITO. The work function can be changed when surface dipole is oriented as shown in Fig.and inorganic-induced surface dipoles [275. large counter anions should increase the surface dipoles. which was developed primarily for well-defined. 1. these procedures do not easily lend themselves to adjustable modification of ITO surface. respectively. mostly nonmolecular inorganic surfaces and interfaces [601]. 338]. As a result. and ITO [308. the nature of developments in what are often called organic electronics [602–604]. ∼ −350 and ∼ −270 mV. it has been observed that total interface dipole can be rather easily tuned by changing chemically the magnitude of the molecular dipole moment [598]. CdSe. 276. In addition.7. 600] has tested the fundamental understanding of basic surface energetics. and their modification using organic. 11(b) can be compared with the work function change of ITO treated with various acids [335]. the hole injection barrier φh is reduced (Fig. HPF6 . The effect of the binding group on work function has not been studied systematically so far except the study described in Ref. An interface dipole with its negative end pointing toward the organic layer and its positive site toward the electrode surface increases ITO work function (i.

7 Chemically Modified Oxide Electrodes 313 feff Vacuum level +− +− +− +− +− +− +− +− (SAM) fe fh Enhanced h+ injection Electron energy f0 EF ITO LUMO fe OS Interface dipoles fh HOMO (b) feff (a) −+ −+ −+ −+ −+ −+ −+ −+ (SAM) fe fh Enhanced e− injection (c) Fig. .4–4. Here. has tested the ability to make the ‘‘classical’’ understanding available to specialists from areas other than that of surface science. The values of CPD were reported to be ∼ −60 mV and ∼ −190 mV for as-cleaned and UV-ozone treated ITO.6 eV [612. As-received a bare ITO work function is considered to be in the range 4. 605–607] and dye-sensitized solar cells [253. by SAM formation. including organic molecules on more traditional surfaces [611]. However. respectively.5 ± 0. the interface dipoles with opposite sign are directed toward the ITO surfaces (b) increasing and (c) decreasing the work function of ITO. 608–610]. 613]. 13. 612. (b) and (c) reduction of the hole injection and the electron injection barrier. Schematic energy diagram used for a two-layer organic electroluminescent (EL) device [590] and the range of ITO work functions estimated by CPD values [312] are shown in Fig. the work function of ITO is generally not sufficiently large for the contact to be Ohmic and so there is a barrier to carrier injection. The work function of ITO measured by UPS has a consistent value of 4. 265. In Table 7.1.1 eV. 613]. with H−. 291. we summarize the experimental values of CPDs for ITO modified with various binding groups of p-substituted benzene derivatives [312]. To achieve enhanced hole injection from ITO anode. 12 Schematic energy level diagram of the impact of the formation of an interface dipole at an ITO/organic semiconductor (OS) interface: (a) the barrier in the absence of the dipole layer. We have demonstrated that ITO surface modification. even though originating from different providers [269. its Fermi level must be aligned with the highest occupied molecular orbital (HOMO) of the adjacent organic film. in the presence of the interface dipole layer on the surfaces of ITO. respectively.

21.45 ± 0.45 eV. µ [311].35 ± 0.1 eV HOMO: 5.4 eV (a) Holes. and −PO2 Cl2 binding groups of p-chlorobenzene derivatives estimated from VCPD and the work function of 4.1 5. 7 Work function φ of SAM modified ITO with −SO2 Cl.9 5.01 0.77 ± 0.27 ± 0.85 ± 0.5 ± 0.1 5.95 ± 0. 0. h+ Li:Al hν Barrier to holes HOMO: 5.7 4.1 p-ClC6 H5 −X − SO2 Cl − COCl − PO2 Cl2 VCPD (V) 0.1 Y −C6 H5 COCl H− Cl− CF3 − VCPD (V) 0. where Alq3 is a tris(8-hydroxyquinoline) aluminum) and (b) values of estimated work function for chemically modified ITO from the results of CPD measurements [312].85 ± 0. Cl−.1 4. e− (~3. The .01 0.2 eV C6H5COOLi (2 nm) Terminal groups 4.2 eV) LUMO: 3. Dipole-induced work function change of ITO is related to dipole moment of the assembled molecules.5 Work function [eV] 4.0 eV TPD Alq3 ITO 4. and 0.27 ± 0.21 ± 0.01 0.314 1 Preparation of Monolayer Modified Electrodes Tab.77 ± 0. 035. respectively [312].1 eV for cleaned ITO [312] Terminal groups Binding groups φITO−SAM (eV) 4.5 ± 0.01 LUMO: 2.71 ± 0.3 (b) Fig.3 eV Electrons.01 φITO−SAM (eV) 4. 13 Ascleaned Binding groups UVozone HClCF3- −SO2Cl −COCl −PO2Cl2 (a) Schematic energy level diagram used for a two-layer organic EL device [590] (ITO/TPD/Alq3 /C6 H5 COOLi(2 nm)/Al.1 4. −COCl.01 0.1 4.7 eV Al: 4.35 ± 0. and CF3 –terminated benzoyl chlorides increases its work function by ca.

In terms of EL efficiency shown in Fig. and −PO2 Cl2 binding groups are compared with those of the devices with as-cleaned and UV-ozone treated ITO. In addition to p-terminated benzoyl chlorides. The EL characteristics. If the electron and hole injections are well balanced. In our improved EL devices [277. which directs toward the ITO electrode. 451. 599. the characteristics became better than those with UV-ozone treated ITO. 313]. 14(a). I−V and luminance–current density (L−I) characteristics of the ITO/ TPD(75 nm)/Alq3 (75 nm)/C6 H5 COOLi (2 nm)/Al devices with ITO modified with benzoyl chlorides with various terminal groups in the para position are shown in Fig. 590. however. 591]. as shown in Fig. −SO2 Cl.and n-palmitoyl chlorides were also used for chemical modification of ITO [313]. the intermediate Cl-terminal group gave the highest performance suggesting that the best balance between electron and hole injection [331] was attained on this modified electrode. which were well correlated with the change in work function.7 Chemically Modified Oxide Electrodes 315 order of the magnitude of the permanent dipole moments is expected to be µCF3 – > µCl – > µH− [312. 578.2 D vs. that is. 312. Substitution of benzoic acid in para position with moieties of varying electronwithdrawing or -donating capability is well known to alter both intramolecular dipole moment and acidity of carboxylic acid group [337. the turn-on voltages shift to less bias voltage with the increase in the permanent dipole moment of the terminal group. Among them.3 V for 100 cd m−2 . for −OCH3 functionalization µ = −1. 331. which yield decreased the work function. I−V and L−I characteristics of the EL devices with ITO chemically modified with p-chlorobenzene derivatives with −COCl. holes injected from ITO anode into TPD HTL first reach to the TPD/Alq3 interface and then injected further into Alq3 layer. were dramatically improved by the chemical modification [277. 2. The drive voltage was most effectively reduced when CF3 -terminated benzoyl chloride was used. −PO2 Cl2 exhibited the best I−V characteristics and gave an extremely low operating voltage of 4. 616]. 13a). The binding −COCl group gave slightly better I−V . 312. n-nonanoyl. With ITO modified with Cl-terminated benzoyl chloride having the intermediate dipole moment. those of binding site and terminal group. In Fig. in general. 614]. 15. in particular the drive voltages. 615. µ = +2.1. that is. while electrons injected into the Alq3 layer move toward the TPD/Alq3 interface and are blocked at the interface. [451. Even on the modified ITO with H-terminated benzoyl chloride without any appreciable dipole moment in the para position. Thus. the characteristics were better than those on cleaned ITO.82 D for −CF3 . We have studied the effect of two dipole layers. 617]. 14. All binding groups lowered the drive voltages. 13(a). The optimization of thickness of Li benzoate was examined and when the thickness of Li benzoate was ca. almost all these charges with opposite signs are recombined inside the emission zone near the TPD/Alq3 interface inside the Alq3 layer [331. 14(b). on work function of ITO and EL characteristics using p-phenylene linkage [312]. 618].0 nm the lowest turn-on voltage was observed (Fig. electron-withdrawing substituents lead to increased work function in comparison to benzoic acid treatment and electrondonating substituents. In Fig. The para substitution can be varied to such an extent that the dipole moment of substituted benzene (part of the carboxylic acid) is directionally reversed. 354.

the devices with ITO modified with −COCl and −SO2 Cl exhibited the best EL efficiency (∼5 cd A−1 observed at 250 mA cm−2 ). 14 As-cleaned UV-ozone HClCF3- 5 10 Bias voltage [V] 15 20 As-cleaned UV-ozone HClCF3- 0 50 100 150 Current density [mA cm−2] 200 250 (a) I−V and (b) L−I characteristics of EL devices with ITO chemically modified with benzoyl chlorides with −H. These results suggest that the efficient hole injection into TPD was due to the increase in work function of ITO covered with the two dipole layers introduced by the chemical modification. the results show that the selection of the binding sites is also important to tune the total work function change total in Fig. As shown in Fig. In particular. Too much higher hole injection with −PO2 Cl2 results in the lower EL efficiencies. Our decision which EL device . This can be interpreted again by the best balance between the hole and the electron injection.316 1 Preparation of Monolayer Modified Electrodes 250 200 Current density [mA cm−2] 150 100 50 0 0 (a) 12 500 10 000 Luminance [cd cm−2] 7500 5000 2500 0 (b) Fig. characteristics than −SO2 Cl. and – CF3 terminal groups in the para position having different permanent dipoles. −Cl. 10. 15(b).

independent of surface cleaning methods including UV-ozone treatment [619] or hydrogen peroxide/ammonia [267].7. One important characteristic of SnO2 :F is that the surface is very flat [267].9 eV obtained for ITO cleaned with hydrogen peroxide/ammonia or UV-ozone treatment [267].1 eV. −COCl.3 1. Furthermore.7–4. but lower than the value of 4. 250 As-cleaned UV-ozone −COCl −SO2Cl 200 150 −PO2Cl2 100 50 0 0 5 10 Bias voltage [V] 15 20 (a) 12 500 As-cleaned UV-ozone −COCl −SO2Cl −PO2Cl2 10 000 Luminance [cd cm−2] 7500 5000 2500 0 0 50 (b) 100 150 Current density −2 [mA cm ] 200 250 we should use depends on our choice between the EL efficiency and the power efficiency.5. This value is the same as those obtained for as-received ITO and cleaned ITO with acetone/isopropanol.7.1 Other Possible Applications SnO2 The work function of SnO2 [619] or F-doped SnO2 (SnO2 :F) [267] is about 4. and there is no indium present . and −PO2 Cl2 binding groups of p-chlorobenzene derivatives.3. The fact that neither work function nor chemical composition depends upon the cleaning methods indicates that SnO2 or SnO2 :F is more stable to oxidation than ITO. The device structure is ITO(various treated)/ TPD(75 nm)/Alq3 (75 nm)/C6 H5 COOLi (2 nm)/Al.1.4 ± 0. 1. SnO2 :F is less expensive to produce than ITO. especially when the outermost surface lacks fluorine [267].7 Chemically Modified Oxide Electrodes Fig. 331].5. 15 317 Current density [mA cm−2] (a) I−V and (b) L−I characteristics of EL devices with ITO chemically modified with −SO2 Cl. EL characteristics were strongly correlated with the changes in observed work functions of various treated ITO [312. Therefore.

492. 326]. Eg > 3 eV. and ITO [498. 1. 633]. Its fundamental optical properties near the band edge have been extensively studied over the past few years [634.2 -bipyridyl) dissolved in solution have been employed to sensitize SnO2 electrodes. SnO2 or SnO2 :F is presently used as a transparent back contact where charge extraction is the primary application [621–624]. 629]. doped ZnO.5. thin-film transistors [638]. However. 512. sensors [639]. NHE at pH 1) lies ∼0. Some examples include chlorophyll [625].7.5.3. Wide bandgap TCO semiconductors. and Ru(bpy)3 2+ [262. Ferrocene terminated SAMs (Fc-SAMs) [326] are one of the most studied redox-active two dimensional aggregates on metal surfaces [630].7. 264]. These films can be also used in other applications such as electrochemical cells [357]. 1. 527. the power efficiency in these examples has remained very low (η 0. SnO2 is a stable wide-bandgap semiconductor and has been widely used in a variety of electrochemical and electrooptical devices. µCP is a soft lithographic technique useful in patterning SAMs [632.1%). Over the past few years. However.3. potential applications in optoelectronic devices necessitate better understanding of the factors controlling the structural and electrical properties of ZnO thin films [641–643]. 528]. The modification of ITO surface with electroactive small molecules such as Fc(COOH)2 and 3-TAA provides for better wettability of organic layers to the polar ITO surface and enhanced electrical contact between ITO and copper phthalocyanine (CuPc) layers in multilayer excitonic organic EL and PV technologies [316]. Whitesides and coworkers [632] used low concentrations of thiols in ethanol as the ink to stamp patterns onto Au. do not appreciably absorb visible light. Recently. 1. Printed organosilane SAMs have been used as etch resists to pattern Si/SiO2 . 635].45 V vs.5. 628].2 518] and amines [631] have also been used mainly for attaching organic molecules onto ITO.4 TiO2 To date. . SnO2 is a better electron acceptor since its conduction band (ECB = +0. 637]. functionalized siloxanes [509] or alkylsilanes [347. especially Al-doped ZnO (ZnO:Al) films have been used as a transparent electrode in optoelectronic device applications [636. Compared to TiO2 or ZnO. almost all applications of molecular excited states in sol-gel processed semiconductors such as TiO2 have been for solar energy conversion. and photonic crystals [640]. and the incorporation of molecular chromophores allows efficient solar harvesting [253–255. Many organic dyes and organometallic complexes such as Ru(bpy)3 2+ (bpy = 2. Al/Al2 O3 . and alkanephosphonic acids have been used similarly to pattern Al/Al2 O3 [471]. 523.3. 644. SnO2 was also used as a transparent anode electrode to improve charge balance and device efficiency [620]. ITO Chemisorption of small redox-active molecules on ITO can be used to probe changes in electrochemically activity of ITO surface as a function of surface pretreatment [314–316. Ti/TiO2 .3 ZnO Zinc oxide is a wide bandgap semiconductor material with a large exciton binding energy [9.7. rhodamine [627. croconate violet [626].5 V more positive than that of TiO2 [254].318 1 Preparation of Monolayer Modified Electrodes to possibly diffuse into organic layers in OLEDs [267]. In addition. in PV devices such as TiO2 dye-sensitized solar cells [253].

5 Other Oxides In addition to large bandgap oxides such as ZrO2 [646].1.7. 17 together with the experimental values of their bandgaps and electron affinities. the very large bandgap (∼9 eV) gate oxides such as Al2 O3 and SiO2 and potential barriers for electrons of ∼3 eV at Al/Al2 O3 and Si/SiO2 interfaces have been studied [647]. and their CNLs [650]. While the thicker layer prevents direct tunneling across the oxide. Hence. which have been well reviewed [254. BHSchottky is Schottky barrier height and CNL is the charge neutrality level of Si. A key requirement for the large bandgap gate oxide is that it acts as an insulator–it has a low leakage current. it gives zero offset for SrTiO3 .7 Chemically Modified Oxide Electrodes 319 645]. 1. . The CNLs for the oxides are given in Table 8 and shown schematically in Fig. 255].5 and Vol.2 V above the valence band. which form during the deposition of the material on Si. 6 [456]. For example. interfacing the oxide layers with Si is a major challenge [649]. More details of some applications can be found in the Sect. 16 VB Si Oxide Oxide Schematic illustration of band offsets at a semiconductor heterojunction and metal/semiconductor interface. Therefore. 16). Most robust and efficient sensitizers are based on the metal-to-ligand charge transfer (MLCT) excited states of polypyridyl Ru compounds. Dyesensitized nanocrystalline electrochemical photovoltaic system has recently become a validated and credible competitor to solidstate junction devices for the conversion of solar energy into electricity [453–455]. CB Electron energy BHSchottky CB offset CB EF EF or CNL VB offset VB Metal Fig. Kahn and coworkers [651] extended the concepts of CNL and induced density of interface states and proposed that the energy-level alignment is driven by the alignment of the CNLs. 1. Indeed. The band offsets for various oxides in contact with metal or silicon were found by calculating their Schottky barrier slopes S.5.3. but the CNL of most oxides can be high in their gaps [647].3. The charge neutrality level (CNL) of Si is low in its gap. metal Al is easily ˚ oxidized to form Al2 O3 layer with ∼20 A or more thick under typical conditions [648]. only 0. the alignment of Si and the oxides tends to give small conductionband offsets.5 nm to several nanometers thick. conduction can still occur by excitation of electrons and holes by Schottky emission into the oxide conduction or valence bands (Fig.7. One of the most challenging problems is that of controlling the oxide interfacial layers ranging from ∼0.

4 0.4 4.9 VB offsets Calculated conduction band (CB) and valence band (VB) offsets of various oxides in Si [647.8 3.5 nm will be demanded.1 1. such as Al2 O3 .320 1 Preparation of Monolayer Modified Electrodes Tab. Only a thicker insulator with a dielectric constant higher than that of SiO2 could reduce the leakage current while still keeping the capacitance 5 4 CB offsets 3 2 1 Energy [eV] 0 −1 −2 −3 −4 −5 Fig.3 4.4 Ta2O5 0.05 values.8 4.0 3.5 3. and calculated CNLs and CB offsets on Si for each oxide [647. no one has demonstrated that all of the extraordinary electrical properties of the Si/SiO2 system can be reproduced.0 0. 650] Gap (eV) 1. 650].3 3. SiO2 can no longer be considered as an insulator because the direct tunneling current rises over 1 A cm−2 [652].) −0.5a 3.6 2.8 1. 8 Experimental bandgaps.36 2.3 3. For several candidates. until now.8 6.25 3.9 3.8 5.2 2.4 4.4 TiO2 0.8 EA (eV) 4. and future generations a further reduction below 1.5 (exp.) 2.9 3.5 Si 1.4 5.2 – 5.0 1.1 7.1 9 8.1 3.4 (exp. ε∝ 12 2. High-quality gate insulator surfaces such as Al2 O3 can be prepared by anodization (electrochemical oxidation) of the gate metals [542].9 1. At that moment.3 – 2. . which SiO2 Al2O3 ZrO2 2.1 0 Oxide Si SiO2 Al2 O3 ZrO2 Ta2 O5 Si3 N4 SrTiO3 TiO2 a Estimated To ensure higher gate oxide capacitance.2 CB offset (eV) – 3. ZrO2 .84 3.8 4.9a CNL (eV) 0.4 Si3N4 2. However. operating devices have been fabricated. and electron affinity (EA).8 1. These surfaces possess surface hydroxyl groups.6 3. dielectric constants ε∝ .0a 2. SiO2 layer thickness has been decreased to less than 2 nm. and Ta2 O5 . 17 high.

and Culture of Japan. 464–509. Ann. Jarzebski.6 TCO electrode surfaces with various organic molecules in which one end is a binding group (X−). 4. 1958. 123. the other end is a terminal group with a different permanent dipole moment (−Y). and these two ends are linked by groups of alkyl chains and π-systems (see Fig. 333C. Further studies on the preparation and characterization of chemically modified electrodes will be expanding our understanding and advancement of the science and applications of inorganic and organic electronic materials and devices. L. Organosilane on SiO2 have been of great utility in the photoresist industry. 199C. P. However. 1976. Regarding applications. L. To improve the device performance of organic FETs. the oxide surfaces can be treated either by silanization [542. where the use of well-controlled octadecylphosphate SAMs on optical waveguide chips has been demonstrated to increase both the specificity and selectivity when sensing extremely low quantities of biomolecules using evanescent field and fluorescence techniques. Acknowledgement We would like to gratefully acknowledge and thank financial support of this work provided by the Grant-in-Aid for Creative Scientific Research on ‘‘Devices on molecular and DNA levels’’ (No. Studies for the formation of various organic monolayers with carboxylic acids and phosphonic acids as well as organosilane derivatives on these oxide electrodes were summarized comprehensively in this chapter. We have also presented several examples of organic chemical treatments used for the surface modifications of various wide. 653]. 22. New York. 13GS0017) from the Ministry of Education. We have described the chemical modification of various n-type . long-chain phosphoric (and also phosphonic) acid esters are expected to have potential for applications in areas where the specific surface functionalization of oxides by extremely thin films is essential to the quality of a product [479]. 749. Vacuum Deposition of Thin Films. a 2. Vossen.1. Science. Summary This chapter has highlighted various approaches in which organic monolayers play an important role in chemically modifying the properties of the surface of TCO electrodes. K. 655]. 2). 299C. Thin Films 1977. J. 1. pp. in which their patterning by energetic beams affords structures that can direct the substrates’ topographical etching [577]. 9. D. 3. Sports. the precise mechanism of the mobility enhancement due to surface modification is somewhat controversial. J. J. The information in this chapter may help in choosing the most appropriate TCO electrode materials for a new use.7 Chemically Modified Oxide Electrodes 321 are highly detrimental to carrier mobility. AFM induced formation of SiO2 structures in the electrochemical nanocell was demonstrated [654. 1. References 1.and large-bandgap oxide electrodes. Recently. John Wiley & Sons. Phys. One area where application of octadecylphosphate on tantalum oxide has already proven to be successful is optical biosensor technology. which change the surface wetting properties of the oxides [542]. M. Holland. 543. B¨deker. Z. Physik 1907. Electrochem. Soc. Marton.7.

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