1

Part I
Introduction

Masamichi Fujihira
Tokyo Institute of Technology, Yokohama, Japan

Researches on chemically modified electrodes definition of the electrode surface (or in-
was initiated about three decades ago by terface) including the region (2) ∼ (5) into
Hubbard [1, 2], Murray [3], and Millar [4] the bulk of solution, variation of possible
and their coworkers. The field of the chem- ways to deliberately design the functional
ically modified electrodes diverged sharply electrode surfaces has been expanded.
from the traditional field of adsorption on For example, electrochemistry in micelles,
electrode surfaces [5] in a sense that one de- microemulsions, and related microhetero-
liberately seeks to immobilize a chemical geneous fluids has been studied [7].
on an electrode surface so that the elec- Not only the functional variations but
trode displays the chemical, electrochemical, also the chemical variations of the
optical, and other properties of the immo- chemically modified electrodes have been
bilized molecule(s). After this first review, broadened. Atomically modified electrode
researches in the field in 1986 [6] is sum- surfaces [7] have become popular with
marized and the concept of the chemically the developments in electrochemistry on
modified electrodes is extended from the surfaces of single crystals [8, 9] as well
viewpoint of the broadened definition of as the study of underpotential deposi-
an electrode (system). In the broad sense, tions (UPD) [10]. Introduction of func-
an ionically conductive phase being in con- tions into the region (2)–(4) has been
tact with an electronically conductive phase attained by using polymers [11, 12]. Af-
can be regarded as the electrode (system). ter a pioneering electrochemical study by
Then, a side view of an electrode (system) Taniguchi et al. [13], self-assembled mono-
consists of (1) an electrode phase (the elec- layers (SAMs) of disulfides and thiols on
tronically conductive phase), (2) a transfer gold electrodes [14, 15] have been studied
layer, (3) a diffused double layer, (4) a extensively.
diffusion layer, and (5) a bulk solution. This Volume describes, how to prepare
The region covering (2) and (3) is called monolayer modified electrodes on metals,
an electrical double layer, and the region carbons, silicon, conducting metal oxides,
(2) ∼ (5) together corresponds to the ioni- and chalcogenides; how to prepare film
cally conductive phase. By broadening the 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 8. J. Clavilier, J. Electroanal. Chem. 1980, 107,
ex situ or in situ the modified electrodes, 205–209.
9. A. Hamelin, in Modern Aspect of Electro-
and, finally, functions and applications of
chemistry (Eds.: B. E. Conway, R. H. White,
modified electrodes. J. O. M. Bockris), Plenum, New York, 1985,
pp. 1–101, Vol. 16.
References 10. D. M. Kolb, in Advances in Electrochem-
istry and Electrochemical Engineering (Eds.:
H. Gerischer, C. W. Tobias), John Wiley &
1. R. F. Lane, A. T. Hubbard, J. Phys. Chem.
Sons, New York, 1978, pp. 125–271, Vol. 11.
1973, 77, 1401–1410.
11. R. Murray (Ed.), Molecular Design of Electrode
2. R. F. Lane, A. T. Hubbard, J. Phys. Chem.
Surfaces, in Techniques of Chemistry (Eds.:
1973, 77, 1411–1421.
A. Weissberger, W. H. Saunders Jr.), John
3. P. R. Moses, L. Wier, R. W. Murry, Anal.
Wiley & Sons, New York, 1992, Vol. 22.
Chem. 1975, 47, 1882–1886.
12. G. Inzelt, in Electroanalytical Chemistry (Ed.:
4. B. F. Watkins, J. R. Behling, E. Kariv et al., J.
A. J. Bard), Marcel Dekker, New York, 1994,
Am. Chem. Soc. 1975, 97, 3549–3550. pp. 89–241, Vol. 18.
5. R. W. Murray, in Electroanalytical Chemistry 13. I. Taniguchi, K. Toyosawa, H. Yamaguchi
(Ed.: A. J. Bard), Marcel Dekker, New York, et al., J. Chem. Soc., Chem. Commun. 1982,
1984, pp. 191–368, Vol. 13. 1032–1033.
6. M. Fujihira, in Topics in Organic Electrochem- 14. R. G. Nuzzo, D. L. Allara, J. Am. Chem. Soc.
istry (Eds.: A. J. Fry, W. E. Britton), Plenum, 1983, 105, 4481–4483.
New York, 1986, pp. 255–294. 15. L. H. Dubois, R. G. Nuzzo, Annu. Rev. Phys.
7. J. F. Rusling, in Electroanalytical Chemistry Chem. 1992, 43, 437–463.
(Ed.: A. J. Bard), Marcel Dekker, New York,
1994, pp. 1–88, Vol. 18.

15

1.1 proximity to the electronically active sites
Modification of Transparent Conducting of the metal oxide. Chemical modification
Oxide (TCO) Electrodes through of the TCO surface can be accom-
Silanization and Chemisorption of Small plished through covalent bond formation
Molecules (silanization) or through chemisorption of
molecules containing functional groups
Michael Brumbach and Neal R. Armstrong such as carboxylic acids, phosphonic acids,
University of Arizona, Tucson, Arizona alkanethiols, and amines.
Initial modification strategies were em-
ployed for oxidation of biomolecules,
1.1.1 such as ascorbic acid, neurotransmitters,
Introduction heme proteins, and so forth using var-
ious surface-confined molecules or thin
1.1.1.1 The Metal Oxide Electrode and
films of conducting polymers. Modifica-
Modification Schemes
tion schemes have also been used to attach
Surface modification of transparent con-
photoactive dye molecules, such as ph-
ducting oxide (TCO) thin film electrodes thalocyanines, porphyrins, and a variety
(indium–tin oxide (ITO), SnO2 , TiO2 , of organometallic complexes, to oxide sur-
ZnO, etc.) has traditionally been directed faces to enhance redox processes between
toward enhancement of heterogeneous solution species and semiconducting elec-
electron transfer rates of solution species trodes [2–6]. Chemical modification of
for which the electron transfer process is conducting oxide surfaces has also been
thermodynamically favored but kinetically used to enhance charge injection rates into
inhibited. The surface-confined molecule condensed phase organic thin film devices
is intended to exhibit rapid and reversible (for example, in organic light emitting
electron transfer at the oxide surface to pro- diodes (OLEDs) and organic photovoltaics
vide rapid mediation of electron transfer (OPVs)). There is still some debate as
to a solution species [1]. Surface-confined to whether the enhancement in device
molecules are typically not directly ‘‘wired’’ performance is due to enhancements in
into the conduction or valence band of the wettability of the oxide surface toward the
oxide, but electron transfer rates are often nonpolar molecules used in these devices,
reasonably fast for these species simply to changes in work function of the ox-
because they have been brought into close ide 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]. lattice terminations [19–23]. The structure
Many of the same strategies initially used and electronic properties of several TCO
to enhance solution electron transfer rates films can be summarized as follows:
on these oxide surfaces appear to posi- Indium–Tin Oxide (ITO): ITO has the
tively impact device efficiencies in simple complex unit cell of indium oxide (bixbyite
OLEDs and OPVs [9, 14–18]. lattice) consisting of more than 80 atoms.
Indium oxide has two distinct indium
1.1.1.2 Commonly Encountered TCO
sites in the lattice and as many as four
Electrodes
oxygen species, considering surface hy-
The most commonly encountered TCO
drolysis products and oxygen vacancies
electrodes, typically studied as thin films,
[24]. Oxygen vacancies and electron-rich in-
are antimony-doped tin oxide (ATO) or
terstitial tin dopant sites lie close in energy
fluorine-doped tin oxide (FTO), ITO, ti-
to the conduction band edge so that promo-
tanium oxide (anatase or rutile, TiO2 ),
tion of electrons into the conduction band,
and zinc oxide (ZnO) [19]. There are also
at room temperature, is facile [25]. Figure 2
some recently reported trinary and ternary
shows the proposed band diagram for ITO
oxides based on modifications of ITO, zinc-
indium tin oxide, ZITO or IZTO, for exam- exhibiting the common features that dic-
ple, which may become more popular with tate the electrical properties of many TCO
time as electrodes for solution-based redox materials. The upper portion of the va-
chemistry and as anodes in devices such as lence band arises from filled O(2p) orbitals,
OLEDs and OPVs [7]. These new tailored while the lower part of the conduction band
composition oxides may exhibit higher sta- arises from unfilled metal orbitals (In(5s)
bility, higher work functions, and/or a orbitals in the case of ITO). Oxygen defects
greater variety of surface sites with more are induced into the TCO material during
possibilities for chemical modification. its formation, usually by depositing or an-
An idealized metal oxide surface is nealing the thin film in an oxygen-deficient
shown in Fig. 1, where the metal atoms atmosphere, thus creating electron-rich
are in tetrahedral coordination with four sites within a few kT of the conduction
oxygen atoms. This metal oxide, empirical band edge. An interstitial dopant, tin, is
formula MOx , is stoichiometric, having no often introduced into these In2 O3 lattices
defects or surface hydrolysis products, and at concentrations up to 10% (atomic), pro-
can be considered as a typical platform for ducing additional electron-rich sites within
understanding the modification of most a few kT of the conduction band edge. In
TCO thin film materials of electrochemical ITO, the donor density can be as high as
interest. TCO films are typically deposited 1020 cm−3 with a sheet resistance as low
by sputtering, chemical vapor deposition, as 10  sq−1 . The introduction of oxygen
or pulsed laser deposition, and tend to defect sites and other dopants, however,
be ‘‘microcrystalline’’ whose dominant ex- may also increase the chemical reactivity
posed faces tend to be either 111 or 100 of these oxide surfaces toward hydrolysis

O O O O O O O O
M M M M M M M
Fig. 1 Schematic view of an
O O O O O O O O ideal metal oxide surface.

1.1 Modification of TCO Electrodes through Silanization and Chemisorption of Small Molecules 17

Fig. 2 Schematic view of the energy
levels in ITO showing the components
of the valence band and conduction In: 5p
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). In: 5s 0.03 eV

Energy
and other components of the vacuum de- EF
position system. The reactivity of the oxide
surface has important consequences for V o: s 2 Sn3+: 5s1
their further modification and enhance-
ment of electron transfer rates, which have
been extensively studied as functions of O2−: 2p6
surface pretreatment [8, 24, 26, 27].
Tin Oxide (SnO2 ): Tin oxide has a tetrag- In: 3d10
onal rutile structure with a unit cell of
six atoms. The electrical conductivity of
n-doped SnO2 is due to the presence of oxy- thin film TiO2 electrodes have been quite
gen vacancies, interstitial tin (in excess), or successful [32, 33]. Both anatase and ru-
added dopants such as fluorine, chlorine, tile forms of TiO2 are readily n-doped
or antimony. Carrier concentrations can by creation of oxygen vacancies leaving
electron-rich Ti3+ and Ti2+ states in the
be increased to approximately 1020 cm−3
band gap, with electron energies suffi-
through doping from the intrinsic con-
ciently close to the conduction band edge
centration of approximately 1018 cm−3 for
so as to provide for reasonable room tem-
SnO2 [19].
perature conductivity.
Titanium Oxide (TiO2 ): Titanium oxide
exists in three different crystallographic 1.1.1.3 Variability in TCO Electrodes
structures, rutile, anatase, and brookite. TCO thin films can exhibit tremendous
The most commonly studied material is variability in transparency, microstructure
rutile, being the most stable phase, al- (and surface roughness), surface compo-
though many studies have been conducted sition, conductivity, chemical stability at
on the anatase phase as well [28]. Stoi- high current densities (in OLEDs, OPVs,
chiometric rutile contains Ti4+ in six-fold and chemical sensors), and in their chem-
coordination with oxygen staggered by ical compatibility with contacting organic
Ti4+ in five-fold coordination. Oxygen layers. Variability is often noticeable from
atoms at the surface are often bridging production batch to production batch and
and only two-fold coordinated [23]. The within batches of the same metal oxide
band gap of rutile is 3.0 eV, and 3.2 eV material [34]. Surface pretreatment condi-
for anatase, making titanium oxide a use- tions have also been shown to dramatically
ful material for photocatalysis [29–31]. impact the electrochemical, physical, and
Photoelectrochemical cells based on sin- photophysical properties of metal oxide
tered nanoparticulate arrays of anatase or films [8, 9, 24, 26, 27, 35]. Modification

18 1 Preparation of Monolayer Modified Electrodes

of these surfaces through silanization and observed with oxide electrodes. Hydrolysis
chemisorption would appear to be a means products on ITO remain strongly ph-
for improving the stability of these ox- ysisorbed (precipitated) to the electrode
ide surfaces, enhancing their compatibility surface at greater than monolayer cover-
with nonpolar solvents and condensed age, constituting a primary factor for the
phase materials, and optimizing rates of appearance of electrical ‘‘dead spots’’ on
interfacial electron transfer. the oxide surface [24, 36, 37]. The so-called
‘‘dead spots’’ are regions exhibiting poor
1.1.2 electroactivity or no electroactivity.
Factors that Control the Surface Surface hydrolysis of metal oxide sur-
Composition of the TCO Electrode faces can be examined by comparison to
solution equilibrium constants for hydrol-
The structure shown in Fig. 1, represent- ysis and solubility. Indium oxide has a
ing an ideal metal oxide surface, provides favorable equilibrium constant for hydrol-
a useful platform for understanding metal ysis [38–40]:
oxide surfaces. A further, and more re-
alistic, modification to the model would In2 O3 + 3H2 O ←−→ 2In(OH)3
account for the presence of surface hydrol-
K = 4.3 × 101 (1)
ysis products as shown in Fig. 3. Surface
hydrolysis critically affects the chemical Whereas, the fully hydrolyzed In moiety,
modification of the TCO surface. Mod- In(OH)3 , has a very low solubility product.
erate hydrolysis may only break bridging
oxygen-metal bonds leaving surface hy- In(OH)3 ←−→ In3+ + 3OH−
droxyl groups. More extensive hydrolysis
Ksp = 1.3 × 10−37 (2)
can lead to fully hydroxylated metal species
that may remain physisorbed. The pres- There is also the possibility for incomplete
ence of dopants and/or oxygen vacancies, hydrolysis of an indium surface oxide
as shown in Fig. 4, can also affect the metal creating the intermediate hydroxylated
oxide surface by creating sites that can re- species, InOOH:
act with adventitious impurities present
during, or after, deposition. In2 O3 + H2 O ←−→ 2InOOH (3)
Varying degrees of hydroxylation and
defect density, as well as the preferential This type of surface site may also arise
migration of dopants to the near surface by the nucleophilic attack of water on
region, contribute to the high degree of exposed oxide defects, which serve as sites
heterogeneity in electron transfer rates for dissociative adsorption. In contrast,
and chemical compatibility commonly hydrolysis of tin oxide is significantly less

HO
M OH
HH H H HO HH H H Fig. 3 Schematic view of an oxide
O O O O OO O OO O O O surface that has undergone hydrolysis,
M M M M M M M producing hydroxylated sites, and even
physisorbed metal hydroxide,
O O O O O O O O monomers or polymers.

1.1 Modification of TCO Electrodes through Silanization and Chemisorption of Small Molecules 19

Fig. 4 Schematic view of the O O O O O O O
near surface region of the oxide +n +n
thin film with oxygen vacancies, M M M M D D M
+x +n
producing electron-rich metal O O O O O O O
sites and dopant sites of lower
stoichiometry, and also creating
electron-rich sites.

favored than for indium oxide, at any pH determining the surface coverage of the
[38, 39]: modifier. Rates of electron transfer/charge
injection at the modified oxide surface
SnO2 + 2H2 O ←−→ Sn(OH)4 are subsequently affected. Despite the un-
K = 5.6 × 10−10 (4) certainties in oxide surface composition,
several modification protocols have been
While the solubility of tin hydroxide is developed over the last thirty years, which
higher than for indium hydroxide: yield improved electrochemical perfor-
mance of the TCO thin film. Two strategies
Sn(OH)2 ←−→ Sn2+ + 2(OH− ) have continued to be successful at modi-
fying metal oxide electrodes; silanization,
K = 1.4 × 10−28 (5)
covalent bond formation to metal hydrox-
Sn(OH)4 ←−→ Sn4+ + 4(OH− ) ides, and chemisorption, using functional
groups known to either hydrogen bond to
K = 7.2 × 10−14 (6)
M–OH sites and/or to coordinate to metal
cation sites.
The typical doped SnO2 thin film can
therefore be expected to show monolayer
1.1.3
(but not significantly higher) coverages of
Chemical Modification of TCO Surfaces
hydroxide species. Hydroxide species in Using Silane Chemistries
excess of monolayer coverage would be
expected to be more easily removed from 1.1.3.1 Introduction to Silane Modification
the oxide surface through pretreatment Surface modification of TCO thin films
steps. with monofunctional, difunctional, and
For titanium oxides and zinc oxides, sim- trifunctional organosilanes arose initially
ilar hydrolysis and dissolution processes from protocols developed in modifying
must be considered [39, 41]: silica surfaces [42]. The covalent attach-
ment of functional groups to the oxide
Zn(OH)2 ←−→ Zn2+ + 2OH−
surface through silanization involves the
Ksp = 3 × 10−16 (7) coupling of the functionalized silane to
4+ − the metal oxide at hydroxylated sites,
Ti(OH)4 ←−→ Ti + 4OH through a metal–oxygen–silicon bonded
Ksp = 7.94 × 10−54 (8) network with the release of one or more
‘‘leaving groups’’ as shown in Fig. 5. ‘‘Leav-
Chemical modification of these oxides, ing groups’’ are generally chlorides or
therefore, needs to take into account the alkoxides (methoxide or ethoxide) yield-
routes to formation and loss of surface ing HCl or the corresponding alcohol as
hydroxide species playing a key role in by-products.

20 1 Preparation of Monolayer Modified Electrodes

OMe Schematic view of silane
Fig. 5
modification of an oxide
R–Si(OMe)3 + HO–M R–Si–O–M + MeOH surface, using (as an example) a
tri-methoxy silane. Reaction
OMe with only one surface hydroxide
site is shown, releasing
methanol as the product.
Unreacted hydroxide sites
R R R remain, as do unreacted alkoxy
MeO OMe OMe MeO OMe groups on the silane, which can
Si MeO Si Si further cross-link under
H H H H
appropriate conditions.
O O O O O O O O O O O
M M M M M M M
O O O O O O O O

In the absence of water, silane modifiers viologen, porphyrin, phthalocyanine, etc.)
can form multiple bonds to the surface cre- or can simply be tailored to control the
ating a clawlike multidentate attachment, wettability of the TCO surface.
Fig. 6(a) [43]. Silanes with multiple leaving It is desirable to start with a surface
groups, however, will generally cross-link that has been mildly hydroxylated for
during the surface attachment process, surface modification, as opposed to the
or afterward during storage in high hu- stoichiometric surface shown in Fig. 1,
mid environments, to form a polymeric, so that there are sufficient reactive sites
hydrolytically stable layer, as shown in for silanization. If the redox chemistry of
Fig. 6(b). The functional group (R) can be an attached molecule is to be optimized,
an alkyl or aromatic group terminating it is also desirable to work with mono-
with a redox active molecule (ferrocene, functional silanes. In this case, only one

R R R
MeO OMe
H Si Si Si
H
H
O O O
O O O O O O O O O
M M M M M M M
O O O O O O O O
(a)

R R R R R
O O O O
O OMe
H Si H Si Si Si Si
H H
H H H
O O O O O O O O O O O Schematic view of cross-linking
Fig. 6
O O O
a silane surface modifier as it passes
M M M M M M M through the (a) multidentate/brush
O O O O O phase to the (b) fully cross-linked phase,
O O O
with relatively few unreacted M−OH
(b) 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 brushlike silanized layer with tridentate
the tethered redox group in close proxim- attachment.
ity to the electrode surface and promoting
reasonable rates of electron transfer [1]. 1.1.3.2 Examples of Silane Modification
Control of surface hydroxylation, however, Trimethoxysilane molecules will cova-
given the tendency of oxides to exten- lently attach to ITO following a reflux
sively hydrolyze, is problematic and affects of the electrode in a 10% (silane:toluene)
the coverage of redox active groups that solution for approximately 30 min [37]. Ex-
can be achieved through silanization reac- cess silane can be removed by sonication
tions. Silane formation on SnO2 surfaces, for 10 min in pure toluene. Water con-
where hydrolysis can be more easily con- tact angle measurements on such modified
trolled appears to be a more advantageous surfaces immediately show increased con-
strategy. tact angles, consistent with the addition of
Silanization is generally performed in silane molecules with nonpolar function-
refluxing toluene or benzene with low con- ality to the surface. On ITO, the contact
centrations of the desired silane. Silanes angle can change from less than 30◦ be-
of the form X(R2)2 SiR1 have only one fore modification, to angles higher than
reactive bond and can therefore make 65◦ after modification, and even higher if
only one bond with the metal oxide sur- cross-linking of the silane occurs [37, 46].
face (see Fig. 5). X represents a chloride, X-ray photoelectron spectroscopy (XPS) is
methoxy, ethoxy, or other ‘‘leaving group.’’ also used to verify the presence of silicon
R2 groups are typically small substitutents on the surface. Shepard and Armstrong
such as methyl groups, but can be changed have measured the electrode interfacial ca-
to something larger such as phenyl groups pacitance at tin oxide electrodes modified
to provide steric hindrance and blocking with a series of silanes [47–50]. The ca-
unsilanized surface sites. Large side chains pacitance studies showed the sensitivity of
would, however, also sterically reduce the the electrical properties of modified sur-
number of silane molecules bound to the faces to variations in reaction conditions
oxide. The energy barrier for the surface during silanization, and to the types of
bonded silane to rehydroxylate, and the functional groups attached to these sur-
metal oxide to ‘‘heal,’’ with a bridging oxy- faces.
gen, is extremely low. Therefore, these Untereker et al. used several meth-
brushlike phases are generally unstable ods for creating clawlike brush phase
and nearly all of the brushlike phases silane layers on SnO2 , TiO2 , and
reported in the literature are produced glass [43]. SnO2 was modified with γ -
with triply reactive silanes reacted un- aminopropyl-triethoxysilane, 3-(2-(amino-
der highly controlled dry conditions such ethylamino)propyltrimethoxysilane), and
that multiple bonds can be made with β-trichlorosilyl-2-ethylpyridine by expos-
the surface, as shown in Fig. 6(a). Accord- ing the electrodes to 2–10% organosi-
ing to Kirkov, there are 2.23 × 1015 Sn−O lane solutions in refluxing benzene or
sites cm2 on SnO2 [44, 45], and similar xylene under N2 for up to 12 h. The
site densities can be expected for ITO and electrodes were washed with dry ben-
TiO2 . Since not all sites will be uniformly zene. A similar procedure was used for
reactive, a maximum surface coverage silanizing SnO2 and TiO2 at room tem-
is approximately 10−10 moles cm−2 for a perature with lower silane concentrations.

22 1 Preparation of Monolayer Modified Electrodes

Another brief exposure was performed C60 has been tethered to ITO in
with 1% organosilane in benzene at 6 ◦ C a self-assembled network by exposing
under argon for 10 s. A more aggres- the ITO to basic conditions followed
sive silanization procedure was used to by a reflux in high concentrations of
modify glass with neat organosilane in a (MeO)3 Si(CH2 )3 NH2 in benzene for half
sealed tube at 90 ◦ C for 12 h. The authors a day [52]. The electrodes were then mul-
evaluated their films via XPS to deter- tiply rinsed before refluxing in a 1-mM
mine thickness and approximate surface solution of C60 in benzene for as long as
coverages. 2 days. This scheme resulted in an ITO-
Finklea and Murray accomplished the silane-N-C60 tethered network and allowed
silanization of single crystal TiO2 fol- for the formation of an organized C60
lowing a 5 min exposure of the elec- layer on the ITO surface. Quartz and glass
trodes to 10% silane solutions in ei- were similarly modified for spectroscopic
ther toluene or benzene. Excess silane comparisons. Nearly, all monolayer cover-
was removed with fresh solvent, while age of C60 was determined electrochem-
methanol was found to reduce the silane ically, 1.7 × 10−10 mols cm−2 . Reduction
coverage [51]. The silanes evaluated in of C60 in these films is shifted more
these studies were 3-(2-aminoethylamino)- negatively, indicating a direct interaction
propyltrimethoxysilane, methyltrichlorosi- between the underlying silyl-amine layer
lane, and dimethyl-dichlorosilane. XPS and C60 .
surface analysis showed the presence of
some cross-linking but could not conclu- 1.1.3.3 Silane Modification of Electrodes
sively characterize the homogeneity of the for Use in Devices
modified surface. Their photocurrent re- Perfect cross-linking of silane molecules
sults indicated that the M−O−Si bond is unlikely in most circumstances due to
is oxidatively stable to photo-generated a mismatch in the lattice spacing between
holes and, therefore, may provide a use- the cross-linked silane layer and the un-
ful means of modifying TiO2 particles for derlying metal oxide substrate. A more ac-
use in dye sensitized solar cells DSSCs. Re- curate picture of a silanized surface would
dox active and photoelectrochemically ac- consist of some silane molecules attached
tive metal phthalocyanines were attached via multidentate binding interspersed with
to γ -aminopropyltriethoxysilane-modified cross-linked neighboring silanes as shown
SnO2 . Tetrasulfonated cobalt and copper in Fig. 6(b). Extensive cross-linking of sur-
phthalocyanines (CoTSPc and CuTSPc) face silanes may provide a stable modified
were modified with thionyl chloride, to surface; however, it also appears to impede
provide for attachment to the silanized sur- electron transfer and, for optimization of
face via formation of sulfonamide linkages solution redox processes, may not be de-
[47, 50]. sirable [1, 46].
Phenyl and diphenyl silane-modified Marks and coworkers have shown how
ITO surfaces have been used to im- extensively cross-linked silane monolayers
prove the physical compatibility with Lang- and multilayers can be used to stabilize an
muir–Blodgett thin films of phthalocya- electrode and regulate charge injection in a
nine assemblies, where the direct electron condensed OLED phase [14, 53–55]. Their
transfer of the assembly with the ITO sur- approach has been to start with silanes
face was of concern [46]. 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 biological sensors [56–58]. The authors
groups, which can subsequently be con- found that the ITO electrodes can be ef-
verted to new reactive silanes, to produce fectively blocked from electron transfer by
a layer-by-layer ‘‘self-limiting’’ chemistry. silanization. Silanization results in more
Multilayer formation can be well con- uniform films suitable for the biological
trolled, leading to desired film thicknesses sensor platform, with ionic diffusion oc-
and orientation of the charge transport- curring almost entirely from pinholes in
ing core molecules [14]. In general, these the film. Silanization was accomplished by
modified electrodes show significantly im- sonicating ITO substrates in 5 vol% solu-
proved performance as anodes in OLEDs, tions of the silane in dry toluene with 0.5
apparently due to the fact that hole injec- vol% n-butylamine, followed by 30 min of
tion into the tri-arylamine hole transport incubation. Temperatures were held be-
layer (which is the core molecule being low 293 K for ODTMS and below 280 K
cross-linked by these silanes), is impeded for OTMS. Sonication in dry toluene for
after modification. This allows for a more 2 min removed excess silane. Markovich
balanced injection of both holes and elec- and Mandler also derivatized ITO with
trons in the device and results in the ODTMS but derivatization was performed
emissive state forming in the middle of over a seven-day period [59, 60].
the thin film device [14]. The long alkyl chain length and stability
Chlorosilanes are often used to aid in of cross-linked silanized surfaces also
the extensive cross-linking that is desired allows for their use as masks for patterning
for the modification of anodes for use and etching TCO substrates. ODTMS has
in OLED devices. Chlorosilanes liberate been used as a mask for patterning ITO
HCl as a by-product of silane attachment, [61]. Luscombe et al. have used perfluoro-
which can degrade the TCO surface if low decyltrichlorosilane as a mask for etch
concentrations of base are not added for resists for lithographic processing of ITO
neutralization. No significant etching of surfaces [62].
the TCO anode surface has been noted, and
surface analysis of the modified electrode 1.1.4
generally indicates no entrapped chlorine Modification of TCO Surfaces through
[14, 51–53]. Chemisorption of Small Molecules
Silane modification of ITO and SnO2
electrodes has also been used to create 1.1.4.1 Modification using Small
nearly perfect ‘‘blocking’’ electrodes, such Molecules Containing Carboxylic Acid
as thin films where rates of electron trans- Functionality
fer are intentionally kept low, so as to pro- Modification of electrode surfaces through
vide for measurement in changes in inter- chemisorption has been more in recent re-
facial potential of an additional overlayer, ports than silanization, and its discussion
such as a bilayer lipid membrane, during here is intended to contrast the strategies
ion transport, pH changes, and so forth. used for both types of surface modifica-
Hillebrandt and Tanaka have evaluated the tion. Chemisorption of small molecules
effects of octyltrimethoxysilane (OTMS), to the TCO surface allows for robust
octadecyltrimethoxysilane (ODTMS), and modifications occurring over short dis-
octadecyltrichlorosilane (OTS) on ITO tances and with relatively strong interactive
for applications to lipid-membrane-based forces (H = ca. 200 kJ mol−1 ) through

24 1 Preparation of Monolayer Modified Electrodes

combinations of electrostatic, H-bonding, for ITO and ATO have been determined to
and metal ion coordination. Chemisorp- be as high as 8 × 104 M−1 [34].
tion processes generally have a high ac- Chemisorption is often as successful as
tivation barrier for adsorption, may be silanization at obtaining monolayer cov-
irreversible, and can ‘‘self-limit’’ at mono- erages of small molecule modifiers. As
layer coverage. Owing to the amphoteric an example, Davis and Murray attempted
nature of metal oxide surfaces, chemisorp- to couple iron porphyrins to amine-
tion of Lewis acids such as carboxylic terminated silanized SnO2 surfaces. The
acids, aliphatic and aromatic amines, and authors found that the surface coverage
phosphonic acids are generally successful. was independent of the apparent extent of
Chemisorption typically anchors individ- surface silanization [63]. Silanized and un-
ual molecules in close proximity to metal silanized electrodes were soaked in 5 mM
cationic sites and may also compete for porphyrin dissolved in DMF, THF, or pyri-
sites with surface hydrolysis products. Pre- dine solutions overnight. Porphyrins with
vious work has examined chemisorption pendant carboxylic acid groups produced
to ITO, SnO2 , and TiO2 surfaces, with higher surface coverages (determined
most of the studies reporting adsorption by coulometric analysis of the voltam-
of either carboxylic or phosphonic acids or metry of the surface-confined species)
salts. on bare, unmodified SnO2 than seen
Carboxylate functionalities have been on SnO2 electrodes modified with 3-(2-
used repeatedly and successfully as an aminoethylamino)propyltrimethoxysilane.
anchoring group for molecular chemisorp- Zotti and coworkers adsorbed sev-
tion to oxide electrodes proceeding through eral carboxylated ferrocene deriva-
the formation of an ester linkage to the tives on ITO: ferrocene-carboxylic acid
metal with the loss of water, or through (Fc(COOH)), ferrocene-dicarboxylic acid
hydrogen-bonding interactions to surface (Fc(COOH)2 ), and ferrocenylheptanoic
hydroxyl groups. Possible interactions for acid Fc(CH2 )6 COOH [64]. Fc(COOH) was
carboxylic groups are shown in Fig. 7. adsorbed from 1-mM solutions of the
Binding constants for the carboxylic group molecule in 5/95 ethanol/hexane for as

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

1.1 Modification of TCO Electrodes through Silanization and Chemisorption of Small Molecules 25

long as 16 h, followed by a rinse with in the dipole induced by the derivatized
acetonitrile. Higher solution concentra- modifiers [67].
tions were found to yield higher surface Dye molecules possessing carboxylate
coverage, following a Langmuir adsorption functionalities have been extensively ex-
isotherm, with saturation coverage (ca. 1 × plored as sensitizers of semiconducting
10−10 mols cm−2 ) occurring at approx- oxide electrodes toward visible light in
imately 10 mM solution concentration. photoelectrochemical cells [4, 32, 68]. Dye
The saturation coverage, however, was sensitization was first explored as a means
25% of the expected monolayer coverage of enhancing the photocatalytic properties
(4 × 10−10 mols cm−2 ) based on the geo- of TiO2 [69–72]. Spitler and coworkers
metric area [65]. Fc(COOH)2 was adsorbed investigated dye sensitization of ZnO elec-
from ethanol, while Fc[(CH2 )6 COOH] was trodes using carboxylic acid functionalized
adsorbed from hexane. Adsorption of these dyes [4–6]. The authors found that the pho-
molecules appears to be kinetically lim- tocurrent produced by dye sensitized TiO2
ited. Recent work has shown that time and ZnO crystals closely resembled the ab-
for adsorption is required to remove hy- sorption spectrum of the dye, indicating
drolysis products (e.g. In(OH)3 ) or other that the dye is in close proximity to the
nonelectroactive species adsorbed to the crystal and, upon excitation, injects charge
ITO surface [66]. into the semiconductor from energy levels
Fc(COOH)2 has been used success- that are relatively unperturbed.
fully to increase electron transfer rates The observation of photocurrent from
and for enhancing the performance of dye sensitized planar semiconductors
organic light emitting devices and or- led to the evolution of the DSSC,
ganic photovoltaics [24, 37]. In addition on the basis of extremely high sur-
to modifications of electron transfer rates, face area nanoparticulate oxides, usu-
carboxylic acid-modified small molecules ally TiO2 . The most successful dye for
have been used to introduce dipole fields sensitization, N3, cis-bis(isothiocyanato)
at the surface of TCO substrates. For bis(2,2 -bipyridyl-4,4 dicarboxylato) ruthe-
example, benzoic acid derivatives have nium (II), employs several carboxylic acid
been used to modify the interface dipole groups for adsorption to TiO2 , ZnO, SnO2 ,
at ITO surfaces, attached to the ox- and/or ITO from an ethanol or acetoni-
ide surface via formation of a Lang- trile solution over a several-hour period
muir–Blodgett thin film. Changes in [32]. Electron injection from the excited
work function closely relate to changes state of this dye to the conduction band

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

26 1 Preparation of Monolayer Modified Electrodes

of the oxide is believed to occur on a [77]. A maximum surface coverage was
femtosecond timescale [73, 74]. Binding obtained at 4.2 × 10−10 mols cm−2 , ap-
constants for the carboxylated dyes assum- proximately four times the surface cover-
ing an ester linkage are 8 × 104 M−1 on age obtained with the analogous carboxy-
SnO2 from chloroform [73]. A similar car- lated ferrocene. Cyclic voltammetry (CV)
boxylated ruthenium complex has been of the adsorbed (Fc[(CH2 )6 PO(OH)2 ]) ex-
evaluated on ATO, ITO, TiO2 , and SiO2 hibits a symmetric voltammogram about
[34]. The authors argue for ester linkages the x-axis (applied potential axis). The
on all substrates except silica. On silica, high degree of symmetry suggests fast, re-
adsorption occurs through a chelating car- versible electron transfer at the interface.
boxylato link with a second carboxylate Additionally, the modifying molecules
group hydrogen bonding to the surface. were found to be very robust to CV cycling.
Hydrogen-bonding interactions for proto- An amine derivatized ferrocene
nated carboxylic groups to TCO surfaces molecule, Fc[CH2 N(CH3 )2 ], was used to
can also be envisioned as shown in Fig. 8. modify ITO, although less successfully
Notice that physisorption can occur to than the carboxylic derivatives [64].
metal oxide surfaces, which are not hydrox- Modification with amines tends to create
ylated, by formation of hydrogen bonds to a less robust modification, where the
bridging oxygens. molecules can be easily removed with
solvents. CV cycling can also lead
1.1.4.2 Modification Using Phosphonic to the loss of amine modifiers. This
Acids and Other Chemisorbing phenomenon is clearly a result of the
Functionalities weaker Lewis base characteristics of
Phosphonic acids are known to chemisorb the amine for the Lewis acid sites
strongly to oxides such as ITO and have on the metal oxide surface. Han and
been used to help produce lithograph- coworkers, however, were able to design
ically patterned ITO surfaces [75, 76]. a dense self-assembled monolayer of 1,12-
The schematic view of the adsorption of diaminododecane from methanol onto
such materials is shown in Fig. 9. Adsorp- ITO after 60 h of immersion [78]. The
tion of hexylferrocene phosphonic acid terminating amine group allowed for the
(Fc[(CH2 )6 PO(OH)2 ]) has been investi- subsequent addition of a monolayer of
gated by Vercelli et al. from ethanol to phosphomolybdic acid to provide redox
silanized and unsilanized ITO surfaces active centers. The diaminododecane, at

R R R
–H2O –H2O
HO OH OH
P P
P
OH O O
HO O O O HO O
O O HO O O
O
M M M M M M M M M
O O O O O O O O O O O
O
(a) (b) (c)
Fig. 9 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 electron transfer rates are associated with
for one-third as much redox active a conformational change of the molecule
acid. This protocol may allow for the in the adsorbed state at the electrode sur-
modification of oxide surfaces through face [82, 83]. Above a certain scan rate,
chemisorption to obtain surfaces similar the conformational change can be over-
to those obtained through silanization; come. More recently, Runge and Saavedra
however, the robustness of this platform showed that cyt C forms a sufficiently
was not evaluated. stable adsorbed state such that it can be mi-
Cyanuric chloride has been used to crocontact printed on ITO surfaces, while
modify oxide and graphite electrodes [79]. retaining high electron transfer rates [84].
The linkage, an ether bond through surface
hydroxyls, is short and strong, allowing for 1.1.5
a robust surface and enhanced electron Conclusions
transfer between the surface and the
aromatic terminal group. The modification of TCO surfaces can
Another modification scheme of note is clearly be used to enhance the electro-
the selective addition of tin-phenoxides on chemical performance of oxide electrodes.
an ITO surface, a process developed by There are, however, issues yet to be
Schwartz and coworkers for the modifica- resolved regarding the initial surface com-
tion of the effective work function of ITO position of the oxide, especially for ITO,
surfaces [13, 80]. Because of the low con- which prevent realization of the full elec-
centration of tin sites on such surfaces, trochemical and electronic potential of
this modification scheme, which does not these electrodes. In some cases, the mod-
modify exposed indium sites, places the ification chemistries produce a surface,
functional groups at some distance from which is sufficiently robust to be used
each other, a type of modification not in various sensor platforms or condensed
afforded by other modification schemes phase devices. However, it is not yet
based on covalent bond formation, or clear whether long-term stability can be
chemisorption.
achieved in those cases where the oxide
Heme proteins have also been adsorbed
is exposed to solutions that also promote
to TCO surfaces as ‘‘modifiers’’ of their
the hydrolysis of the oxide unless an ex-
electrochemical properties. These adsorp-
tremely strong covalently bonded network,
tion processes are undoubtedly a combi-
or chemisorption interaction can be pro-
nation of electrostatic forces, H-bonding,
duced. These modification strategies will
and metal ion coordination in the TCO
continue to evolve with the increasing need
surface, and produce reasonably robust
for viable interfaces between electroactive
and active modifying layers. Cytochrome C
materials and the metal oxide electrode.
(cyt C) has been the most extensively stud-
ied adsorbed heme protein. Hawkridge
and coworkers have examined the elec- Acknowledgments
trochemical behavior at gold, platinum,
and metal oxide electrodes [81]. Electron Work cited in this review from our
transfer rates as high as 10−2 cm s−1 laboratories was supported in part by
were obtainable at ITO electrodes. Bowden the National Science Foundation (Chem-
and coworkers have determined that the istry); the Office of Naval Research; the

28 1 Preparation of Monolayer Modified Electrodes

Department of Energy, National Renew- Institute of Physics Publishing, Philadelphia,
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or they are themselves polymer. or liquid. was of crucial importance for the advent of ized on the substrate [1]. a monolayer and can serve as the struc- nous medium. a kind of supported organic monolayers [4. that is. and J.2. 12].Rusling Copyright  2007 Wiley-VCH Verlag GmbH & Co. The thiol substituent is a an ensemble of the component molecules soft binder effective to specific surfaces.F. 5]. Edited by M. tions.ISBN: 978-3-527-30402-8 . organization of the tightly packed mono- face.2 is one of the most popular SAMs for SAMs on Au and Ag Electrodes modifying a silicon surface covered with a naturally grown oxide film [7.1. Bringing together two concepts of sup- acterized: all of the component molecules ported organic monolayers and sponta- are chemically bonded one by one to the neous organization (or self-assembling) substrate. In Encyclopedia of Electrochemistry. are coded by the structural specificity to express their func- 1. 1 [1].1 The essence of these self-organization pro- Preparation of Self-assembled Monolayers cesses is that no external intervention is (SAMs) on Au and Ag necessary to guide the processes once the Uichi Akiba and Masamichi Fujihira assembling processes start [1. 2]. Self-assembled monolayers (SAMs) layer through van der Waals interaction on substrates belong to the latter orga. 10 Modified Electrodes. Stratmann Vol. Tokyo Institute of Technology.1. This looks as if biomolecules in nature. and the other is a system tural unit that enables the spontaneous that organizes at a heterogeneous inter. 1. the code is set in two structural cess in which an organized superstructure parts. that is. 11. KGaA.J. the self-assembling of supported organosulfur compound from the solution organic monolayers had already been stud- or gas phase onto a gold surface [6–10]. 12–19] and also for chemically of the former. they are members of in Fig. Two different types of SAM adsorption 1.2. Weinheim.1. of forming SAM on a substrate is not new.2 Historical Background on SAMs processes on solid substrates are well char. a silane-based SAM monolayer adsorption on substrates. ied using acid/base interaction for the For the latter instance.Rubinstein.1 Introduction as DNAs or proteins. Around principal driving force for assembling the that time. The into two types of organized systems: one alkane chain is a building block to form is a system that organizes in a homoge.30 1 Preparation of Monolayer Modified Electrodes 1. A typical example SAMs [6. In the case of an alkanethiol-based faces Molecular self-assembly is a pro. to which the component liquid or gas phase [1–3].2. We can synthesize various component Japan molecules in which predesigned struc- tures are specifically coded with the rules necessary for the molecular assembly.1. SAM. A schematic of need to be supported by the surfaces of alkanethiol-based SAM structure is shown solid. tion of sulfur–gold coordination as the it was well known in the 1940s. Bard and M. (or hydrophobic interaction in water) be- nized system because these monolayers tween the alkane chains. The structure molecules can be chemically adsorbed of molecular self-assembly can be divided from the solution or gas phase [5]. Yokohama. that are uncorrelated to each other in a such as gold.1. a thiol substituent and an or pattern is spontaneously formed from alkane chain. such 1.1 Molecular Self-assembly at Sur. I.Edited by A. is a thiol-based SAM on modified electrodes [14. The idea gold. 20–29]. which involves the specific interac.Fujihira.2.

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

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

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

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

89]. the cells adherent to the gold surface for 12–24 hours at 300–350 ◦ C in the can effectively function without evidence chamber. with its biocompatibility [102.99% purity modify the surface with SAMs as soon as grade. The commonly first 150 nm of gold film is deposited used evaporation procedure of (111). 150]. 126]. the evaporation. the gold thin films 0. Thin atmosphere owing to its inertness for ionic gold films less than 100 nm in thickness (hard) interaction [5–7. by which the individual domains are cal applications of SAMs chemisorbed on separated from each other [5]. atomic force mi. Thus. 156] for cells and proteins. of importance in biologi. 142–145]. Second. 147]. parameter if one needs a preferable RAS [83. with high speed tends to reduce the size ments. so that the desired gold films of toxicity [9]. at a high rate of 5 nm s−1 . electrochemical-surface plas. gold film surface with widely spreading scanning tunneling microscopy (STM: (111)-oriented terraces [125. unlike other met. et al. finally 120–123. The evaporation rate should be possible. with a large area of atomically flat faces on the surface can be obtained. The gold for the evaporation reannealed before use. Heating the als. evaporation under these conditions. It is recommended that such pressures are required to be 10−8 to a flat gold substrate just prepared. including SPR spectroscopy [82. 141]. followed oriented gold surface on muscovite mica by the second 50-nm gold film at a is as follows [124–127]: Freshly cleaved rather slow rate of 0. QCM gold evaporation is another important [140.2 SAMs on Au and Ag Electrodes 35 etchants [86. 1. After gold gold. IR. evaporation temperature to 150 ◦ C resulted and various electroanalytical techniques in smaller plateaus surrounded by grooves [106. in particular. 10].2 Preparation Method of a Flat Gold an improved procedure for the vapor Surface on Mica One of the most popular deposition of gold onto mica has been techniques for preparing an atomically flat reported. where a two-step deposition gold surface is the epitaxial growth of gold process is performed for the formation onto muscovite mica. In the deposited gold films are annealed fact. The mica mechanical stability enough to be used is baked for 12 or more hours at ∼500 ◦ C in experiments in vacuum and in various before gold evaporation [126]. so that a size have been prepared as a substrate on which of (111)-oriented terraces of more than SAMs are deposited and characterized 100 nm2 can be obtained. 153–155]. in addition. The growth conditions [128]. of 5. of (111)-oriented terraces. 1. Temperature 134–137]. control of the mica substrate during mon resonance (EC-SPR) [138. The thickness of the inated readily even upon exposure to the gold films is usually 100–250 nm. a gold substrate prepared on mica has vacuum evaporation instrument. This feature have a lot of trenches of ∼3-nm deep is.5-nm depth [124]. Recently. 146. 103. is not contam. The smoothness of of atomically flat gold thin films of the gold surface depends largely on the 200-nm thickness on mica [157]. 148].1. 9.05 nm s−1 . The evaporation by a variety of surface-analytical instru. should be used to usually requires at least 99. Chidsey see Itaya) [149. Such mica is set in a chamber of the high. 139]. EQCM [81.1–0. demonstrated that decreasing the croscopy (AFM: see Fujihira) [150–152].0 to 7. ellipsometry [47. The vacuum liquids.2. The deterioration of the widely . gold does not readily form an oxide mica at 300–350 ◦ C is common during surface and.5 nm s−1 or so.2. or 10−9 Torr.

168]. 127. and used by other re.2. This procedure generates large areas icon surface and a gold film. been used so far. the gold film. that more easily to the outer surface of the is. 9. Moreover.2. the application cedures were proposed. One of the problems Another Route for Preparation of Flat Gold is caused by the limited stability against a Substrates This technique.1. and stripping techniques in (3). To improve adhesion between a sil. a silicon wafer and Bard [161]. In the gluing searchers [162].1. This technique was also procedure (2). this preparing a gold thin film. As an alternative to the tita. 165].2. These adhesives give rise to some problems during experiments us- 1. deposition on silicon wafers or glass sub. first reported variety of solvents especially when epoxy by Hegner et al. face. of silicon wafer or glass substrate. of the flatness of the gold surface but also face and the gold film.2.2. termed a template-stripped gold (TSG) sur- 131]. this metal has without loss of quality.. gluing techniques in (2).2.2. after the procedure (2) is performed. where trapped basic idea is to use the first deposited air bubbles and solvent pockets in these gold layer directly in contact with the adhesives are not compatible [169]. It allows not only improvement used as a binder between the silicon sur. usually convenient adhe- applied to the nanotransfer printing sives. 130. The method is based prepared are not used soon. Instead of strates was demonstrated by Majda [160] mica as a template of TSG. a silicon wafer technique is termed a template-stripping covered with a native oxide film has been technique and the obtained gold surface is used widely as a base [5. 2): (1) epitaxial films on mica could be kept in absolute growth of gold on mica (the same pro- ethanol for preserving it from the oxidative cedure as described in Sect. If the fresh gold films in Sect. atmosphere [158.36 1 Preparation of Monolayer Modified Electrodes spreading area of (111)-oriented faces in mica surface rather than the top surface the freshly prepared gold surface can be of the deposited gold film as described followed by STM. The other is improved method for preparing a widely caused by out-gassing problems under ul- flat gold surface on mica [164.7. has been used similarly [167].3 Gold Substrate on Silicon Wafer stripping of the mica down to the freshly As an alternative to mica substrate for appearing gold surface [164]. Rabe .1. 1.2. 159] (see Schneeweiss (2) gluing the fresh gold surface to a piece and Rubinstein). These include the of (3-mercaptopropyl)trimethoxysilane as use of alternatives to the mica substrate in a molecular adhesive in the gold vapor the procedure (1).2. However. 1. Later. it is storage of the mica/gold/silicon multilayer believed that chromium tends to move for a long period after its preparation. has been developed as an is used as an adhesive. a titanium of the smoothest gold surfaces known to or chromium layer of 1–10-nm thick is date [166].2). 1. Thus.4 Template-stripping Technique as ing the TSG substrate. and thus it contaminates the substrate can be stored for several months gold surface. The tra high vacuum (UHV).1.1. and (3) chemical or consecutive mechanical 1.7). various further-improved pro- nium or chromium layer. such as epoxy or ceramic glues have method [163] (see also Sect. these gold on three procedures (Fig.2. and later the pro- a potential toxicity to cells adsorbed to cedure (3) is performed just before use for the SAM in the application of biological modifications with organic materials [167. interface [9].

Glueing onto a glass of silicon wafer 1–2 hours coverslip 3 hours at at 150 °C 80 °C 5. Removing of the mica by soaking in THF by soaking in THF TSG TSG (a) (b) Fig. thus lowering the adhesion be- cold-welding technique. application of TSG substrates to sensors free TSG supported on nickel. which can also tween these two surfaces [166]. re- Blackstock et al. A more solve the conductivity problem of the TSG simple and reliable method for the strip- substrates produced by the conventional ping procedure (3) is demonstrated by technique or Rabe’s method. and coworkers developed an adhesive. Covering with epo-tek 3. Deposition of 200-nm gold by thermal evaporation 3. 170. Covering with epo-tek R377 10 µl cm−2 R301-2 20 µl cm−2 4. Glueing onto a piece 4. Nickel of and electronics [169]. Cleave of muscovite mica 2. 171]. Thiols can interca- without any adhesives in the procedure late between the mica and gold layer of (2) [169]. 2 Typical preparation procedures of template-stripped gold surfaces supported (a) by a piece of silicon wafer and (b) by a glass coverslip [165]. Improvements of the 200-µm thickness was deposited on the procedure (3). This method is based on the gold the TSG. in which mica acter will be extremely important in the can be removed by immersion of the . have been demonstrated cedure (2) described above [167.2 SAMs on Au and Ag Electrodes 37 1. recently demonstrated a ported the utilization of organothiols as new type of template-stripping technique a stripping technique. Removing of the mica 5. 1. stripping step. This char. Ulman et al. by several researchers. Gooding and coworkers. which involves the prob- gold surface on mica by electroplating in lem relating to mechanical stress in the place of a piece of silicon wafer in pro.

and tita. Al- A number of atomically flat and wide lara et al.1 Preparation from Solution Phase are very familiar to electrochemists as the The most outstanding feature of SAMs is so-called Clavilier method or the flame their ease of preparation. plied to the preparation of gold and silver strate for a variety of applications. at present. and inexpensive ishing of a (111) face that is parallel to the method of preparation of a (111)-oriented facet of the bead [196. resulting in clean separation to clean and well-defined low index surfaces leave large atomically flat planes. electrode [189. [189. face for experiments is limited to a small facet (usually less than 0. the try because expensive instruments such most prominent semiconductor alterna- as physical vapor deposition are not re.2.1.5 mm in diame.2. The single-crystal electrodes by Hamelin et al. This annealing method. are observed by STM af. as explained above.2. and can be gold bead [10. and we have to set Alkanethiol-based SAMs on Gold up the experiment to directly use the small facet only. Namely.3 Preparation Techniques of ter) with a (111) face.5 Single Crystal Bead of Gold the single crystal bead by mechanical pol- A handy. 186–192]. one can use a single crystal gold cut nium oxide [185]. suggesting ter flame annealing by a hydrogen torch that the chemical bonds of RS−As (R = just before use. tive to silicon. have 193. gallium arsenide (GaAs). 194]. 190].1. 1. 202]. the application viewpoint [199–203]. Only a gold wire repeatedly used after removing the adsor- (99.99%) with ca 1 mm in diameter and bates and doing flame annealing again. expanded to not only physical chem- istry [173–176] but also biochemistry and 1. These single-crystal techniques 1. Clavilier and cowork- cryogenic stripping method is based on ers first demonstrated with platinum the the difference in contraction between mica effectiveness of a simple preparation of and gold. we can use the (111)-oriented gold sur. If neces- silver [171].3. a Bunsen hydrogen flame is necessary to make a single crystal bead by crystallizing 1. TSG substrates.38 1 Preparation of Monolayer Modified Electrodes sample into liquid nitrogen [172]. which as patterned features without any change was performed by heating the platinum in substrate quality. being rapidly and Motoo et al.2. The crystalliza. the types a single crystal bead itself is not amenable of surfaces fabricated according to this to various measurements that require a TS technique have increased. faces of thiol-based SAMs.2.7 Other Substrates of Interest As the end of the gold wire.1. 184]. Later.2. including larger area of flat gold surface. this method was also ap- been extensively used as a widely flat sub. The cut bead is gold surface is to use a single-crystal usually 3–5 mm in diameter. The cut electrode has an exposed (111)-surface prepared from 1. availability is. SAMs . the area where alkyl chain) form on the surface [199. In addition. However. 200. as well by the flame annealing method. is actively studied from quired for making a single crystal bead. more than could provide well-ordered organic sur- 300 nm in size.1. a new class of substrates for forming thiol- tion needs skill. sary. 195–198]. demonstrated that GaAs (100) terraces of a gold (111) face. platinum [183.2.1. but it is very easy to based SAMs. 198]. timesaving. wire in a Bunsen flame for minutes [186.6 Single Crystal Cut of Gold Such biology [176–182].2.

47. it may depend on the structure of based L (Langmuir) films formed on an the organosulfur compound. 61]. Stratmann kinetics for adsorption of SAM [48]. 52]. Ma and Lennox [208]. and the development of the highly ordered structure have slowed down significantly. but SAMs can be prepared by ing SAM on gold [206]. charged sulfur and the substrate. There. vs Ag/AgCl [207]).1 V toluene [47].2. the SAMs chemical bond between the negatively generated with these solvents show al. When holding the using a variety of solvents. The stud. ethanol (varying between −0. at cathodic po- their characteristics. 205] focusing on the former will compositions otherwise inaccessible us- be described here and. The process of SAM for. The most electrode potentials. peaks observed in cyclic voltammograms mation is determined from energetics and of the SAM on gold [204. it has been found that the period.2 Electrode Potential Control of demonstrating that the electrode poten- SAM Deposition Gold substrates for tial affects the kinetics and mechanisms of chemisorbing SAMs are a kind of elec. so that it may be natural for us to binstein [159]. and compared it with frequently used solvent is ethanol [46. as for the latter. tetrahydrofuran [47. two-component mixed SAMs with various ies [204. usually for few minutes to 1 day. aqueous subphase were transferred to gold tration of the solution. First. 49. and assume that the electrode potentials could later Sumi and Uosaki [209] showed that affect the formation process of SAMs.3 and +0. the data on the basis of the correspond- 47. including hex.1.3. 61]. isooctane [52. In particular. Nonetheless. If a more ordered monolayer is required Porter and coworkers demonstrated this for the experiment. organosulfur compound for an adequate Recently. These studies have been performed from Ma and Lennox demonstrated that this two viewpoints: (1) the potential control potential control technique for SAM for- of SAM formation process and (2) that of mation is critically effective to deposit already-formed SAM structures. and dimethyl. the potential-assisted deposition of alka- Studies on how an applied potential af. and the polarity substrates under the control of various and structure of solvents used. the ing deposition under open-circuit potential . reported that octadecylthiol (C18)- fore. control of SAM formation onto gold by which depends on the compound structure electrode potentials is effectively available and the purpose of the SAM formation.01–1 mM solution of the also Kakiuchi). such as wettability tentials. its concen. chemisorption of thiol molecules and thickness [44]. 52]. the immersion for possibility by taking into account reduc- a longer time will be recommended as tive desorption and oxidative readsorption described later. Later most the same macroscopic behavior in they also reported that. 52. SAM formation on gold [207]. 205]. as a SAM deposition technique. cyclooctane [47]. the thiol molecules were acetonitrile [47. et al. 49. nethiols on gold could lead to a faster fects the SAM formation and its structures deposition and ultimately more complete are of extreme importance for techniques SAM formation process than the common of molecularly functional organization. 1.2 SAMs on Au and Ag Electrodes 39 are easily obtained by exposing a clean gold interested reader is referred to [206] (see surface to a 0. point of zero charge (pzc) of gold [192] in carbon tetrachloride [47]. Ron and Ru- trode. attracted to the gold surface through the formamide [47]. 1. SAM deposition process. electrode potential at slightly positive to the adecane [46. 61].

213].3 SAM Deposition from Aqueous these are successfully transformed to the Micellar Solution Recently. closed circles). First. This electrochemical mech- SAM formation [215]. that is.6 V for 10 minutes. idation of alkanethiosulfates is shown in precursors of thiols must be designed in Fig. electrochemical self-assembly on gold. 4 [218]. open squares) and passive incubation (24 hours. 1. They and ferrocenyl peptide disulfides [214]. microelectrode by Ferguson et al. conditions. 3). 211] (Fig. A Another electrochemical technique ap.2. successfully demonstrated selective SAM These findings are also very important formation in specific locations on the gold for further understanding of the property microelectrode using this electrochemical of gold–sulfur bonding indispensable for method [217].3. Lines are drawn to assist data visualization [208]. expressed as the percent HSC15 COOH in mixed SAMs with C16 SH. an inter- corresponding thiols in situ on the gold esting idea for deposition techniques surface by an electrochemical reaction. salts) as a precursor [216]. this method can be called with no applied voltages [210. In this strategy. advance. This tech- alkanethiols. When the precursors are used for SAM formation under an applied voltage. such as thioacetyl-terminated nique was immediately applied to the oligo(phenyleneethynylene)s [212. anism was also discussed in detail.40 1 Preparation of Monolayer Modified Electrodes 7 6 5 4 [µ A cm−2] Current 3 2 1 0 0 20 40 60 80 100 % HSC15 CO2H Fig. This acceleration effect in the kinetics of Lukkari and coworkers demonstrated this SAM formation has recently been applied strategy using alkyl thiosulfates (Bunte to the SAM formation on gold with non. the common procedure Therefore. Current was measured at −0.1. of SAM from solution phase has been .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. proposed mechanism for the formation plicable for SAM formation has been of SAMs on gold by electrochemical ox- studied in several groups. 3 Dependence of SAM composition on the solution composition.

1.4 Preparation from Liquid and Su- ture [48]. such as low-energy solvents such as supercritical carbon diox- ide–ethanol can be used to control the electron diffraction (LEED). In addition been developed very recently by Wein- to these features. adsorbate in the UHV chamber can be ined in detail by Jennings et al. which is of crucial importance in the struc- yielding dense. [225.1 Structure of Alkanethiol-based adsorbates. defect-free. this technique has been exam. and properties of SAMs. Chemical Properties of SAMs face scientists. it has been demonstrated valve at the submonolayer level.1. precisely controlled through the dosage More recently. Vapor deposition of 1. density by simply altering the composition directly connected to the UHV chamber.2 SAMs on Au and Ag Electrodes 41 −e− CH3(CH2)n SSO3− CH3(CH2)n SSO3· CH3(CH2)n S· + SO3 Au surface H2O Au surface SAM 0. especially as a sophisticated deposition technique. has typically been performed un- formation based on deposition from aque.1. SAMs on Gold Since Nuzzo and Al- alkyl disulfides with less than 10 in carbon lara demonstrated the idea of SAMs on . The vapor concentration of an Afterward. dition [10]. and ordered tural characterizations of model SAMs be- SAMs [224]. The study of this can be kept all the time in the clean micelle-assisted SAM formation technique environment inherent to the UHV con- has been reported first by Kaifer et al. such as alkanethiols and di. 4 A proposed mechanism for the formation of SAMs by oxidation of alkanethiosulfates at a gold [218]. demonstrated. 48].4.4Structural Characterization and SAM formation. enable us to achieve in situ analyses of the structure of as-prepared SAM without 1. [220–223]. such as the defect X-ray photoelectron spectroscopy (XPS). der UHV conditions.5[CH3(CH2)n S]2 H2SO4 Fig.2. one more indispensable stein et al.3. of the mixed solvents [226].5 Preparation from the Gas Phase exposing it to the atmosphere [10.2. Adsorption from the gas phase is an- other technique of critical importance for 1. 226]. SAM formation of insoluble component. STM. It is a technique for SAM number. They have demon- advantage of the UHV technique is that strated that environment-friendly mixed various analytical tools.2.2. Tempera- that this technique is versatile for the ture is also another controllable parameter. The SAM in UHV ous micellar solutions. This situation is essentially differ- percritical Carbon Dioxide A novel type ent from the solution deposition in which of SAM preparation technique with liq- the adsorbate molecules are always sur- uid and supercritical carbon dioxide has rounded by solvent molecules. [219]. cause thermal fluctuations of the adsorbate structure can be reduced by low tempera- 1.1. 1. and is available for sur.3.

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

will be summarized. (b) Side view. . The structure of a c(4 × 2) superlattice is not presented here.4. 6 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. The light gray circles with dashed lines indicate the approximate projected surface area occupied by each alkane chain.2 Å S S S S Au(111) (b) Side view Fig. structure of long-chain alkanethiol-based acteristics of SAMs prepared on gold (111) SAMs. and the formal c(4 × 2) superlattice unit cell is marked. presenting a hexagonal close-packed √ gold √ (111) surface (open circles).2 Close-packed Structure of SAMs spacer on the SAM structure. such as octanethiol (C8)-SAM. decanethiol (C10)-SAM. 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. these on Gold (111) Surface Full-coverage structural aspects of importance for char. 1. (a) Top view.2 SAMs on Au and Ag Electrodes 43 is on the effect of intermediate backbone 1. 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 [9.1.2.884 Å 2√3 Gold atom Sulfur atom Approximate projected surface area occupied by each alkyl chain 4√3 4.995 Å 32° 4. and longer 2.995 Å (a) Top view 4. 10]. Here.

[47]. and electrochemistry [46]. [235]. as Delamarche et al. The top view explains This surface density shows that there are the structural characteristics of the full. 231]. 65]. have characterized vector [37. If the chains exhibit an upright are fully extended in a nearly all-trans structure. 6b). 43. The thickness of these SAMs alkane chains in a SAM are forced to increasing linearly with chain lengths a structure tilted by arccos(0. obtained by infrared spectroscopy. the methylene scissors when measured 228]. and also for a C8-based . the molecular occupied area conformation. as illustrated in Fig.44 1 Preparation of Monolayer Modified Electrodes docosanethiol (C22)-SAM on gold (111).63 × 1014 chains cm−2 . The result arrived from several experimental results obtained at by Chidsey and Scoles unambiguously using helium diffraction measurements revealed that the SAMs were closely packed for a C18-based SAM by Chidsey and in a hexagonal arrangement with an Scoles and their coworkers [232] and a √ √ overlayer of a ( 3 × 3)R30◦ structure GIXD study by Fenter et al. 6a. This crystalline order of SAM formed at 80 K [37.4. the positioning. This to observe the superlattice of C12-based structure corresponds to a neighboring SAMs by Anselmetti et al. therefore. surface. perspectives (Fig. 230. [233]. must be filled keeping (Fig. structure of the C22-based SAM.184 nm2 . which means an area per alkane- can be illustrated with two different chain molecule of 0. [236]. 43]. Later.16 × 1014 chains chain structures of alkanethiols. [7. Thus.216) from 9 to 21 in carbon number has ∼32◦ with respect to the surface normal been measured using ellipsometry by (Fig.4995 nm. it was performed by atoms chemisorbed on the gold (111) Bucher et al. which is identified and Whitesides [229]. 1. Porter et al. except for that van der Walls chain–chain attractive an essentially difficult issue of sulfur–gold interaction becomes maximum. labeling studies (∼4. that is. 6a). [234] and by alkane-chain spacing of 0.2. These structural views are the area per alkane–chain constant so generally accepted at present.216 nm2 /molecule. These features were the structure of a C22-SAM based provided from IR data with C16-SAM on the average structural information studied by Nuzzo et al. 4. and demonstrated the detection of there was an unambiguous splitting of crystalline order of the SAM surface [227. Very with respect to the underlying gold (111) low current detective STM was also used surface. 6b). optical ellipsometry. The result provides a segment of an alkane chain rotated by fairly good linearity between the measured ∼55◦ from the plane established by SAM thickness and the alkanethiol chain the chain axis and the surface normal lengths.3 Superlattice Structure of SAMs Chidsey and Scoles performed a more on Gold (111) The IR spectra also sophisticated analytical experiment of the provided the evidence for a superlattice C22-SAM cooled to below 100 K by using structure from the hexagonal close-packed low-energy helium diffraction (LEHD). The alkane ordered on a (111) oriented gold substrate chains. which cm−2 ) [37]. 6). this on gold (111) was previously suggested superstructure was assigned to a c(4 × 2) in electron diffraction studies by Strong superlattice structure. For a shorter chain determined by the spacing of the sulfur of a C6-based SAM.184/0. 43. which is roughly coverage SAMs (Fig. together with the trans-zigzag Bain et al.1. The side view consistent with the results of tritium- illustrates the tilted and twisted long. and are commensurately is expected to be 0.

65. In parallel with this binding site on gold (111). Moreover. as a candidate for the sulfur. ple alkanethiol-based SAMs with methyl- The reason is that it is difficult to measure terminating groups.2.2 SAMs on Au and Ag Electrodes 45 SAM by Poirier et al. Recently. surfaces are highly ordered [37. tation of the functional-terminated SAMs visible SFG by Yeganeh et al. 1. [237]. 65. ing with atomic resolution. performed on the structures of a variety the energy difference between the hollow of functional-terminating groups on the SAMs. 230. We can use STM All thiol-based SAMs assembled this flexible capability for SAM prepara. and the top site. mental results systematically. cyclic voltammetry.2. 243–245]. These experiments are carried out and bridge sites is not so large [66] that using analytical tools. indicating that these only a very thin gold–sulfur interface. This method periments on model surfaces using a makes it possible to characterize such local . it is (see also Sect. [238]. ture is the most important consequence obtained by developing a methodology 1. it makes it difficult to definitively prove XPS. The reason for variety of SAMs with the functional- √ √ exhibiting the ( 3 × 3)R30◦ structure terminating groups. spontaneously on gold have never exhib- tion to understand the fundamentals of ited perfect crystalline domains with single organic surface chemistry and to engi.4. Bain et al. the hollow. [239]. If a functional-terminating cannot be situated at such a single site group has a similar size as a methyl- but must be in a mixed arrangement is terminating group. based SAMs. ellipsometry. a number of studies have been the bridge. but can involve various Schreiber [65] summarized these experi- functional-terminating groups. by using up-to-date powerful analytical STM.2. 247]. SAMs. 71]. 1. Accordingly. structural specifications. which were followed can be explained intuitively. 228. the terminal groups [37. NEXAFS. strongly depend on the balance between the two structural parameters. or- believed that the features responsible for der and orientation of the functional- the formation of the superlattice structure terminating groups situated on top of are located in a very thin layer of the the SAMs are indispensable for their gold–sulfur interface [65]. low-energy atom diffraction the evidence for the binding mode even (LEAD). tools [65]. 240–242] is thus far not obvious. there are three characterization of the methyl-terminated types of binding sites.5 Characterization of Defects by of SAM-modified electrodes. This fea. STM is capable of ob- neer new technological applications. serving the appearance of local disorder or lowing Dubois et al. Evidence that the sulfur atoms and so on. that is. Kelvin probe technique [246. However. [44] molecular pinholes as a real-space imag- comprehensively demonstrated earlier ex. 231. such as IR. while the by many chemists who have made chal- reason why the superlattice is produced lenges to such issues [37.4. Until now. molecular lattice. 65.1. 1. the order and orien- proposed spectroscopically using infrared. Fol. GIXD. that is.4 SAM Surface Structure Model (1) polarity and hydrogen-bonding charac- organic surfaces that SAMs can form are ters of the terminating groups and (2) the not limited to hydrophobic surfaces with length of the alkyl chains connected to methyl-terminating groups on alkanethiol. However.1. there There is an unsolved problem related to have been numerous experiments for sim- the gold–sulfur bond as described above.11).1.

Fujihira and coworkers aries.9. In fact. site to the (111) oriented gold substrate. On the other hand. Formation of highly ordered close- gles) of alkanethiol-based SAMs on gold packed structures was realized in this SAM (111) [248]. When types of domain boundaries on gold. 7c). One is a structure design used alkanethiol results in the phase to provide structural perfection of SAMs separation [258]. 2D lattice is determined mainly by the size nism by which the gold vacancy is created of BCO spherical backbone rather than the at the domains of SAMs remains to be commensurability of the sulfur-binding solved. cause some defects.2. The flexibility dispersion [71].6 Structural Variation in the Back. The other typical example is a SAM formed of alkanethiols with an amide 1. The mixed solution of this amide-containing investigation has been carried out from long-chain alkanethiol with a commonly two viewpoints. 8) [256. amide moieties. 253. based SAM exhibits no tilted structure. but a possible mechanism is pro. The pit depth is alkane-chain domains with different az- 0. one of which is based ization of defects of a C12-based SAM on the boundary due to different azimuth on gold (111) is introduced by exhibiting angles of the tilted alkane chains on the high-resolution images of domain bound. 7a [255].e. ordered by STM [251. The formation mecha. which can be easily measured by imuth angles cannot be seen (Fig. A SAM formed from a entation of the SAMs [8. indicating that the pit area is also cov. the adlattice structure of but a closely packed upright structure on the monolayer within a pit was confirmed gold (111) surface (Fig. 257]. In addition. gold vacancy islands. Here.46 1 Preparation of Monolayer Modified Electrodes molecular and mesoscale defects on the with few defects. different azimuth an- level. 252]. 237]. particularly providing additional design to have some advantage of the func- details of domain shapes and domain size tional applications of SAMs. gold va- with a thickness less than 1 nm (see also cancy are usually observed using STM as single gold atom deep pit defects with a Sect. result indicates that bicyclooctane(BCO)- ered with the alkanethiol monolayer [249.1. vided by Poirier [71]. gold surface [248]. as well as domain SAM could be formed and each molecule boundary occurred because of difference was clearly discriminated at the molecular in tilt direction (i.25 nm. The other is a structure SAMs.1). This STM.1. Poirier has presented an in orientation of alkane chains tends to excellent account in which the character. . 7b). STM images indicated that the main boundary [71.2. surfaces. interaction but also due to hydrogen- points of the effect of the structural bonding interaction between neighboring variations on molecular packing and ori. 1. SAMs usually result in several ponent as shown in Fig. 254]. Such a SAM has of alkane-chain backbone in SAMs have stability based on the lateral interaction not probably been examined first by Ulman only due to van der Waals chain–chain and coworkers from fundamental view. and molecular succeeded in avoiding this type of defect vacancies observed by low current UHV.4. the these cage structure-based disulfide com- typical two of which are pure orientational pounds are chemisorbed onto gold (111) domain boundary and translational do. bond in the interior of a single alkane bone Unit of SAMs Structural variations chain (Fig. in this SAM variety of sizes and shapes in the domains a domain boundary between two tilted of SAMs on gold [71]. by using cage molecules as a SAM com- STM [71]. 250].

0 nm (c) 10 nm Fig. sample bias voltage = +1 V) [255]. H HS N (CH2)14CH3 O (a) N H N H N H N H N H O O O O O S S S S S Au substrate (b) Fig.3 nm 0. and the schematic side view presenting idealized SAM structure of the amide bond-containing alkanethiol-based SAM (b) [256]. 7 (a) The structure of BCO disulfide compound synthesized. 8 The structural formula of an alkanethiol compound containing an amide bond in the interior (a).5 nm 0. and (b) the schematic side view presenting the structure of the BCO-SAM on gold (111). (c) Constant-current STM image of a 20 × 20 nm2 area of a BCO-SAM on gold (111) (tunneling current = 50 pA.2 SAMs on Au and Ag Electrodes 47 S S S S S S Au(111) (a) (b) 0. . 1.

probably result- terms of solvent. formation of alkanethiol-based SAMs on gold. alkanethiol and dialkyl disulfide. of Chemical Adsorption at the Gold/Thiol because these have been most intensively Interface When we prepare SAMs onto investigated so far. provides some clues actually an important component of molecular helpful in choosing the better preparation electronic devices.5 Chemistry and Energetics of the Organosulfur compounds interactive to Formation of Alkanethiol-based SAMs on the surface of gold to form SAMs are Gold listed in Fig.2.5. nethiolate–gold bond [8. these two gold substrates by the solution deposition organosulfur compounds give indistin- method. In addition. Therefore.1. adsorption tempera. 9 Surface-active organosulfur compounds that form monolayers on gold [8]. 1. 259. These examples are de. and immersion time. Whitesides and coworkers compared HS S S S Alkane thiol Dialkyl disulfide Dialkyl sulfide O N S S− S S− Alkyl xanthate Dialkylthiocarbamate Fig. oligoth.48 1 Preparation of Monolayer Modified Electrodes Recently.10) to explain the trend of sorption chemistry and energetics for the these SAMs briefly. solution concentration ing in chemisorption through the alka- of the component. 9 [8]. here we focus on two types of organosulfur compounds. 76. a large number of structural different structures and properties of com- variations have been designed for their ponent organosulfur compounds them- potential applications. 1. 10. This is because 260]. case of such simple models as alkanethiol- iophenes. SAMs formed tion on the surface. we describe here scribed in a separate section below (see the fundamental issues relevant to the ad- also Sect. and so on can be used as based SAMs. it is not easy for us to decide the guishable SAMs on gold when examined most suitable preparation conditions in by ellipsometry and XPS. oligophenylenes. Understanding the from thiols with the backbone structures chemistry of SAM formation. selves strongly influence the energetics vanced studies on nonaliphatic SAMs and the mechanism of the SAM forma- have been done intensively. 60.1 Overall Reaction and Energetics that is.2. However.2. 1. conditions. ture. ad. .1. even in the of acetylenes. In particular.1.

Schreiber finally followed by a reductive elimination et al.2. which means this 1.2. the additive contributions of van der RS−Au (−40 kcal mol−1 ).5 kcal mol−1 important [48]. by a factor of 50 [60. 264–266]. and the corresponding alkanethiols [48. Gold/Organosulfurs Interfaces Gold– tion is probably a simple oxidative addition organosulfur interaction involves two of the S−S bond to the gold surface [8].2 Chemisorption Energetics for In the case of dialkyl disulfide. The fact that SAMs can son of these interactions by taking account be prepared from gas-phase deposition in of a large variety of structures of alkanes an environment completely free of oxy. free energy of this over- all reaction can be calculated to be −5 kcal mol−1 . and the latter interaction is derived dition of the S−H to the gold.5. gen strongly supports this overall reaction 267. Blanchard and coworkers es. 268].1.1.4 Structural Effects on SAM For- timated the molar enthalpy of adsorption mation and Stability The structures (−20 kcal mol−1 ) and the entropy of ad. In the discussions in the litera. 268].2. For decanethiol (C10) in for C18) [261]. of the SAM forming components. may have a strong effect on the . of sorption (−48 cal mol−1 K−1 ) [264. 266]. 267. alkanethiols was much faster than that by dialkyl disulfides. chemisorption. interaction will become more and more lated by Schlenoff et al. discussed quantitatively the compari- of the hydrogen [8]. the chain–chain This value is quite similar to that calcu. and 1/2H–H Waals interactions of the entire chain [48. while the rate of tributed orientations in solution to highly replacement of molecules from SAMs by oriented SAM lattices on the surface [10]. vaporization [48].5. canethiol (C10) on gold (∼25 kcal mol−1 The bond dissociation free en- (∼104 kJ mol−1 )) can be comparable to ergies for the chemisorption reac- the corresponding chemisorption energy tion process of RSH on gold are (∼30 kcal mol−1 (∼126 kJ mol−1 )) due to as follows: RS−H (87 kcal mol−1 ). 261]. They also demon. The physisorption energy for de- mechanism [8. 1. course. (−5.5. (−52 kcal mol−1 ) [8. 10. the adsorption re. In adsorption regimes.1. within the Densely Packed Monolayers ture. 263]. suring the temperature dependence of the value. sorbate. (66 kJ mol−1 ) based on the heat of isulfide to be −24 kcal mol−1 . the reac. By mea. 1.2 SAMs on Au and Ag Electrodes 49 SAMs formed from solution of disulfides This relatively large amplitude and nega- with those of thiols.3 Stabilization of SAM Structure chemisorption reaction is an exergonic due to Alkane Chain–Chain Interaction process. They also estimated the the bulk one would expect ∼16 kcal mol−1 free energy of adsorption for dioctadecyld. 1. 76. Consequently. head group and the gold surface. physisorption and the case of alkanethiol. alkanethiol-based SAMs. tive value of entropy apparently reflects the strated that the rate of SAM formation great degree of ordering that occurs as the from alkanethiols and dialkyl disulfides alkanethiols change from randomly dis- were indistinguishable. 262. there has been confusion between For densely packed monolayers of enthalpy (H ) and free energy (G). probably from the chemical bond between the sulfur through the hydrogen atom on the surface. The former interaction is action onto a clean gold surface may be one between the gold surface and the ad- considered formally as an oxidative ad.

The energetics of SAM formation. These chains straighten from the SAMs as a model case. and state and into ordered unit cells [8. the growth of an ordered tion Process Understanding the growth monolayer film follows the first regime. was be thermally activated at room tempera. are always formed. have a direct impact highly kinked conformations to the trans- on the growth of SAMs. The SAM matrix [270]. There. process of SAMs as well as the energetics of which was first identified quantitatively SAM formation is of fundamental impor. less closely packed SAMs result in that alkyl chains get out of the disordered gauch defects of the alkyl chains.1. processes [10]. ceeds. extended zigzag conformations predomi- Bain et al. indicating that the ph- try [8. the characterized in the SAM formation pro. Hence. it was analyzed in detail that this bility of SAMs. cess.50 1 Preparation of Monolayer Modified Electrodes formation and stability of SAMs. the energy cost for a gauch de. described as a surface crystallization pro- ture (RT = ∼0. Such a rinsing concentrations used in the measurements. 48]. Difference tance for the advance in physical chemistry in the timescale of these two regimes of molecular self-assembly and also for is at least ∼2 orders of magnitude [81. During the second process. ex situ using NEXAFS [80]. first studied the kinetics of nantly [80]. This is exemplified by Shon slow step can be further divided into two and Lee using uniquely designed chelat. The second regime. ethanol solution has to be removed by a very fast step that proceeds within a few rinsing with ethanol solvent after the solu- minutes and strongly depends on solution tion deposition procedure. ond regime.2. Another unique Comprehensive understanding at mole- system related to this issue is reported cular levels on the detailed growth pro- by Fujihira and coworkers using a single cesses of SAMs has been revealed using alkane chain inserted in a rigid BCO-based several in situ analytical tools [10]. it was presumed fore. instance.1. 47. first regime corresponds to the adsorption process onto gold. in which alkyl chains 1. 10. In this regime. chains are highly ordered to assemble to- as discussed above for alkanethiol-based gether. procedure with a solvent is indispensable can be described approximately by the for a procedure for preparing complete . The first regime. inevitably influence the formation and sta. alkyl gold.5 kcal mol−1 ). that is. 47].022 eV (∼0. ing alkanedithiols [269].2. a slow step in which fect in an isolated hydrocarbon chain is final macroscopic properties of SAM were ∼0. When further the wettability and thickness using ex situ continuous self-assembly in solution pro- macroscopic analytical methods. films thicker than just monolayer contact angle goniometry and ellipsome. which can reached only after several hours [76]. 10.6 kcal mol−1 ) [48]. 76]. A subsequent process occurs alkanethiol-based SAMs onto gold in the at a rate of 35 times slower than the chain- solution phase of ethanol by measuring straightening process [10].6 Growth Mechanisms of SAMs possess a high number of gauche defects on the surface [10. The results revealed that at ysisorption process proceeds continuously least two distinct kinetic regimes could be onto the monolayer films [272]. In the sec- 1.6.1 General Profiles for SAM Forma. 80. physisorbed adlayer produced by a proce- cess at the macroscopic resolution of such dure of a long time immersion into an methods [8. Later. preparation of various structured SAMs on 82]. 271]. For Langmuir growth curve for adsorption.

These images are Until now. such as method for SAMs is the solution depo. tive for the SAM preparation. SFG [78. For SAM growth is expected [48]. erties.6. numerous studies on the clearly obtained as a sequential molecular growth processes of SAM formation have evolution of the SAM growth. 1. toward the final structure of the SAM. The self. and UHV-STM described Phase The most convenient preparation above. sition method. 71. The control of the cleanliness of the sub- substrate surface and solution themselves strate and the use of a wide range of should be clean enough to secure no effect surface-analytical techniques. The process at the molecular levels.1. it is not EQCM [81].2. have a direct impact during the vealed unambiguously that the previously growth process of SAMs. the ysisorption between the sulfur compound fast step and subsequent slow step could and the solvent onto the gold surface be observed at the molecular levels. They re.2..2. because strong effect the growth processes of SAMs as well as of the contaminants on the process of the on their structural characterization. deposition of SAMs are very useful and derstanding comprehensibly the growth are summarized in table 2 of Ref. their structural characters and polar prop- using UHV-STM [48.3 Growth Studies from Solution ellipsometry. SPR [82].1. SHG [76. comparisons by Schreiber [48]. However. The following phase transition results in a denser phase by re- 1. the solu- description on these issues is found in a tion method has a shortcoming regarding review [10]. NEXAFS [80]. This situation is very different from the case of character- izing SAM structures. the in- prehensive understanding of the growth of terested readers are referred to the review SAMs from solution phase. Solvent molecules. 79].1. and FTIRRAS [83]. in and a more detailed and comprehensive comparison with the gas phase. depending on (111) surface was observed by Poirier et al. that is. Competitive ph- mentioned two-step process.2 Growth Studies from the Gas structure of the finally formed SAM re- Phase UHV technique allows precise quires the absence of contaminants. the substrate cleanliness. UHV-STM between the solution and the gas-phase seems to be extremely effective for un. 1. . The fast and slow necessary for us to use an expensive UHV regimes of SAM growth onto gold in the equipment. For a com- details of these useful techniques. The may influence mainly the first step of the fast step begins with the condensation growth process.2 SAMs on Au and Ag Electrodes 51 SAMs on gold surface. major difference between the two phases assembly mechanism of alkanethiol-based is the solvent being present in solution SAM of C10 on a gold single crystal phase.4 Further Techniques for Investi- alignment of the molecular axes parallel gating the Growth of SAMs on Gold to the surface normal. in which only the 1. has now gained consensus.6. 77]. but the solvent effect may of low-density crystalline islands with the not be negligible in the succeeding steps alkanethiol molecular axes aligned paral. 273].6. 48. and thus understanding of the solution deposition method first proposed SAM growth with this method is informa- by Bain et al. In this method. lel to the surface. In addition to wettability. various other techniques. These pow- of contaminants during the timescale of erful techniques reveal information on the growth process. In particular. been conducted using several instrumen- tal techniques.

nique that could be imagined from its in which specific self-assembling compo- analogy to our macroscopic world. many elaborated devices on the surface. That is. method for fabricating patterned SAMs. Such a set of tech- niques will be referred to as the top-down 1. spontaneous phase separation of mixed One is a processing technique that is SAMs as an example of the bottom-up widely recognized as a traditional pat. We have to scale down bon (FC) in L–B films described below the macroscopic architectural technique to (Sect. and so on. coding and decoding systems [278]. and nanohandling as examples semiconductor surfaces using various of the top-down method. a purpose could be accomplished. yet contrast of the phase-separated domain a premature one as compared to the top- between hydrocarbon (HC) and fluorocar- down approach.2. als that have a potential to make patterned ration of chemically modified electrodes nanostructures on various surfaces via with such patterns. chemical and biochemical processes [86]. techniques available to molecules can be ples having HC and FC domains by inspired since it has been found that nature utilizing photolithographic and liftoff tech. extensively undertaken from the viewpoint of fabrication of organized molecular in- 1.7 Patterned SAMs terfaces. If such tosynthetic reaction center systems [279].1 Two Approaches for Fabricating method for fabricating patterned SAMs. this technique could rication techniques of molecular patterns be naturally combined with SAM materi- would provide a direct impact on the prepa.52 1 Preparation of Monolayer Modified Electrodes have been applied to this issue. nology almost completely by using self- niques for tailoring such patterned SAMs organization. Generally. Toward such a devices in the systems.1. Fujihira and Morita [275] the molecular scale. in nanobiotechno- logical interfaces [9. 1.7. This type of technique in nanotechnology To confirm the origin of the friction is referred to as the bottom-up approach. 76. the fab.7. 274. nents have a deliberate spatial distribution in our daily life. has already accomplished similar tech- niques. Therefore. since it has and several techniques of lithography. 277]. techniques molecular self-organization. development of tech. Therefore.2). The realization of the prepared deliberately patterned SAM sam. been successfully applied to patterning printing. The results lithographic and chemical etching tech- are reviewed in Refs 48. tern formation method. Patterned SAMs: the Top-down Method and The other is a kind of architectural tech- the Bottom-up Method Patterned SAMs. are generated to fabri- have been made of a large number of small cate nanoscale architectures and to provide components and all buildings can be con- well-characterized supports for physico- structed step by step on the foundations. so-called nanotechnology is inten. such as genetic goal. These techniques . in particular. 86].1. These include scale are classified into two approaches. A unique niques. Nature exquisitely architects and controlling their functions at the many systems of predesigned nanostruc- molecular level is of critical importance tures and effectively uses lots of molecular in a future technology.2.1. for fabricating patterned structures onto a Such studies on the two approaches will local surface of a substrate at the molecular be briefly described here. pho- sively being pursued [9. 276. A wide variety of investigations technique using AFM cantilever as a sub.2. 75. using such a technique have also been strate is recently introduced in Ref.

By controlling tip-sample sep- direct imaging of nanometer scale pat. 291].2 SAMs on Au and Ag Electrodes 53 .2. Such a SPM tech- tion force microscopy (FFM) is also useful nique for lithography. as ers demonstrated for the first time that described later.7. tures [280]. and scanning probe microscopes (SNOM). Although stud. 62. be applied to a wide variety of functional . The readers interested in near-field opti- tribution of molecules on the 1–100-nm cal microscopic manipulation and a local scale [281].e. ellipsom. 280.2 Spontaneous Phase Separation aration of alkanethiol-based SAMs have Multicomponent SAMs.. op- terned SAMs [281]. Whitesides and coworkers FFM can be used to image the chemical reported recent unconventional methods contrast between the phase-separated do- for fabricating and patterning nanostruc. Such systems include the mixed SAM of two components. are usually formed by a solution of variation in the molecular compo- deposition method.1. and variation of the buried are quite similar. The 290]. techniques such as XPS. has been the surface to form domains of different explored. SPMs among them. In the latter case. tical patterning was readily achieved [292]. if the functional group [258]. are useful as methods for preparation G untherodt and Fujihira and their cowork- of chemically modified electrodes. to as scanning probe lithography (SPL). molecular features of the components are quite different phase segregates may result 1. such as AFM and STM. 289. can ies were conducted using L–B films. Fric. variation of the terminal func- mixed at the molecular level if the tional group) [281]. quired for characterizing the spatial dis. 288]. which is also called near-field (SPMs). adsorb on the substrate surface [86].2. variation of the alkyl- with two different adsorbates. as the location of the probe tip features depending on the component can be placed on the surface at a specific structure and properties. Their performance and intrin. ing the scanning. The simplest case is a sition [86]. alkyl fluoroalkyldisul- molecular features of the components fides [284. Many studies on spontaneous phase sep- 1. aration of SNOM by AFM [293–295]. both species chain length) [55. was lar. a review article [296].7. set of coordinates and the resolution of The phase separation of SAMs has been the patterns can approach the molecular characterized so far by various analytical scale [86]. In FFM. When a coadsorption of short and long-chain substrate is exposed to a mixed solution alkanethiols (i.1. molecules of similar alkane-chain resultant SAM is presumed to have length but with differing terminal groups domains of the two adsorbates uniformly (i. IR. scanning near-field optical microscopy etry. 1. STM is a powerful tool that optical observation should be referred to meets the requirement [281–283]. the two ing SAMs Patterning of surfaces with components are separately adsorbed on SPMs. have sufficient lateral resolution and found to be useful for optical patterning of therefore appear the most promising for SAMs [292]. which is referred for the purpose [284–286]. The analysis is re. in particu. scanning optical microscopy (NSOM). mains with a resolution of ∼5 A˚ [287.e.3 Scanning Probe Lithography Us- in mixed SAMs. In addition to STM and AFM. 56. both the normal and the lateral sic limits are summarized in tables in force were measured simultaneously dur- Ref. so-called mixed been conducted using different types SAMs. 282. On the contrary.

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

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

The mechanism lithography allows the creation of useful .7. bined with spatially defined patterns. reported the investi. Their results are reviewed strated several optional techniques: the use in [309]. We will describe this tech- on gold. They emphasize that strate as ‘‘ink’’ [315]. DPN is used to direct ‘‘write’’ patterns 1. writing [321]. The fundamentals of the ability to control surface properties DPN are intensively discussed. 297.2. 330]. DPN uses an AFM tip niques called soft lithography that offers as a ‘‘nib (penpoint)’’. 320]. Further intensive investigations of the tapping mode AFM rather than related to the application of this technique the commonly used contact mode [323]. 11). Dip-pen technology. to the fabrication of nanometer-sized pro. such as parallel and serial situ replacement with a second compo.2.5 Microcontact Printing by Use technology and DPN are analogous in of Organosulfur Inks Whitesides and style. understood [297. been used extensively throughout history to transport molecules on macroscale di- mensions [315]. The technique as a SPL tool of nanotechnol- most typical application of addition lithog- ogy [315. Porter et al.4 Dip-pen Nanolithography DPN consisting of a relatively small collection was developed by Mirkin and coworkers as of molecules in submicrometer dimen- a kind of SPL (‘‘direct write’’) [86. 315–318]. 316]. as Addition lithography using SPMs on depicted in the schematic representation of SAMs for fabrication of nanoscale pat. Soft plication [297.1. respect to the terminal groups. and the application of electrochemical tein and DNA patterned SAMs have been potential to the AFM tip in the DPN reported by Liu and coworkers [310–313]. 308]. together using SAMs is most useful when com- with charming demonstrations of its ap. In particular. Several im- SAMs can be removed by mechanical provements of the DPN technique are means using an AFM tip followed by in also discussed. still not fully another thiol [297. in which pursued their investigations for fabricating ink on a sharp object is transported to a a wide variety of patterned SAMs. process [324].7. however. it is naturally expected that terned SAMs is extremely important as DPN can become an extremely powerful a technique of SPL methodologies. In this method. that is. 319. 297].1. when the methodology of gation of approaches for the fabrication of DPN is combined with that of organothiol- protein patterns by SPL [314]. They referred to this technique as ter [322]. methods [89. tools for micropatterning that complement strate as a ‘‘paper’’. This expectation is based on raphy with organothiols as ink on gold a conspicuous advantage of the method- is well-known as dip-pen nanolithography ology of organothiol-based self-assembly (DPN) [86. sions [315]. DPN (Fig. Other researchers have demon- nanografting. based self-assembly on a gold surface. Mirkin and coworkers have 315. 316]. them can be used for biochemical and is approximately 4000-years old and has diagnostic purposes [324–329]. a solid-state sub. Similarly. and a multiple-pen nanoplot- nent. The traditional dip-pen 1. but are different in scale and trans.56 1 Preparation of Monolayer Modified Electrodes using an AFM tip in a solution containing governing DPN is. Some of paper substrate through capillary forces. and molecules with and extend the conventional fabrication a chemical affinity for the solid-state sub. coworkers have developed a set of tech- port mechanism. the flexible chemistry in nique in the next section.

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

terminated regions on the µCP patterned bly. Patterned SAMs on gold sample surface just before contact (in can be prepared by the combination of µCP noncontact) in air or in liquid. Patterning of charge on various oxide surfaces as a proteins and cells using µCP is reported function of the pH of the solution.and nanoscale Sect. On the patterned surface. that on transferring a pattern from an elas. they directly observe the process of pat. Fujihira and the subsequent solution deposition and coworkers demonstrated imaging of methods [342]. 1. force between the −CH3 and −COOH terned colloidal deposition and assem. topographic image. To achieve the quan- sides and coworkers have demonstrated titative analyses of the adhesive forces the microfabrication of chemically charged for chemical differentiation on the pat- patterned SAMs using µCP [347]. Frisbie et al.2. 345].1. Aizen- AFM to adhesive force mapping on a berg et al. 360] and chemical modi- terned electrode controlled by an applied fication of the tip surfaces [361] as well as electric field [348]. 343]. pulsed. which the oxides were dipped [353. and described the po. 354]. Re- force-mode atomic force microscopy cently. 363]. is. 341]. geometries [359. Before this study. which are controlled by electrostatic SAM was mapped simultaneously with its and lateral capillary interaction. 344. chemically patterned SAM surface. Bohn and coworkers used PFM- (PFM-AFM) designed by Marti and AFM to map the adhesion force between coworkers [349] is useful as scanning force an AFM tip and samples of ω-substituted microscopy with chemical recognition alkanethiol monolayer terminated with capability [350. In this mode terned SAM with anionic and cationic of PFM-AFM. a high-resolution printing technique based coined a word for such an SPM. which maps the force Several new approaches using µCP have between an AFM tip and a patterned been reported. alkanethiols substituted with Fujihira and coworkers extended PFM- anionic and cationic end groups. CFM: Fujihira). White. Michel and coworkers reported microscopy. 351] (see chemical force −CH3 and −COOH prepared by µCP . ink.58 1 Preparation of Monolayer Modified Electrodes µCP [340]. fabricated a chemically pat- patterned SAM [356–358]. patterned SAMs using a locally selective they investigated the change of the surface catalytic reaction [341.7. the precise environmental control. Using µCP with two types of tip and the plate were the same [355]. which leads to a new charges with opposite signs in aqueous type of lithographic approach to prepare buffer solutions [350]. ability [287] as already described in tential for emerging micro. They also measured the forces between a Electrostatic interaction on patterned gold-coated tip and a gold plate in aqueous SAMs fabricated using µCP are inves- solutions. Using the force mapping patterning technologies [91. such as As an analytical tool for such a electrolyte concentrations [292. CFM [352]. µCP can be applied to the a patterned surface with electrostatic top surface of a SAM. accurate panded this idea to directed self-assembly information about the tip and substrate of two oppositely charged particles on pat. in by Whitesides and coworkers [117. 330. with PFM-AFM. where electrode potentials of the tigated. terned surface by PFM-AFM. and humidity [364] are indispensable. that is. CFM was originally based tomeric stamp to a solid substrate by on FFM due to its chemical recognition conformal contact. difference in the adhesive regions [346]. They ex. 362.2.

they are well known as dimensionally controlled at the nanome. Patterned SAMs are candidates alternative to the 86. but Leggett without cross-contamination. Notably. the readers can refer to a re- µCP requires a prepatterned stamp that cent review by Zarnikov and Grunze [367]. useful as resists for lithography: (1) they whereas SPL is a serial technique that consist of individual molecules that oc- writes only one feature at a time [9].2.7. 1. e-beam lithography. whereas lithography. of SAMs by e-beam lithography and X-ray mined in situ and easily changed. SPL has ricating patterned SAMs. electron-beam (e-beam). 275]. which they refer to as Single Fea. The mechanism of this reaction has been tiple components with complex structures the subject of some debate. Therefore. UV photolithography. which the placement of the tip is three Correspondingly. Alkanethiolate formed by the ture INKing and Stamping (SFINKS) [366]. The and X-ray lithography respectively [9. SFINKS can pattern mul. 369.25 nm2 and contrast is the same as that between (2) they are very thin (<3 nm). in UV. Namely.2 SAMs on Au and Ag Electrodes 59 and to study electrochemically generated 1. A key difference be- polymer resist used in the techniques. and plays a central role in 10 nm remains a challenge for chemistry the nanofabrication of patterned SAMs [9. multiple into two methods. 330–333]. 330–333]. In the case of capable of replicating patterns written by µCP. and coworkers showed that oxidation can . One is a straightforward copies of the pattern can be produced method for photopatterning alkanethiol- using straightforward experimental tech. ter scale to fabricate patterned SAMs.1. and materials science [9. plays a central role for The development of photosensitive resists the nanoscale fabrication. µCP Whitesides and coworkers [9] describe that can generate many features simultane- two characteristics make SAMs potentially ously on the surface in a single step. Here we the photomask and the SNOM tip in will discuss UV photolithography for fab- the near-field irradiation [292]. and X ray.6 Photolithography for Fabricating gradients [365]. UV-photolithography can be classified once the stamp is available. here. a prepatterned stamp displaces the photons or electrons with resolution below scanning tip. Orden and coworkers of SAMs on gold and silver is well known demonstrated an alternative patterning at the phenomenological level [368. This cupy areas smaller than ∼0. 275]. Patterned SAMs Lithography has long The SPL described above is applicable been developed as a common technique for to a variety of patterning techniques us. scanning tip. fabricating microelectronic devices. the two with micron-scale resolution [368–372]. using ing a small STM or AFM tip end. has to be made in advance. For modification a patterning feature that can be deter. techniques are complementary to each The process underlying photopatterning other. tween SPL and µCP is as follows. adsorption of alkanethiols are oxidized on SFINKS combines elements of DPN and exposure to UV light in the presence of air µCP to generate patterns. based SAMs on gold and silver surfaces niques [89. 372]. in to alkylsulfonates: SFINKS multiple tips with different inks Au-SR(CH2 )n X + 3/2O2 −−−→ deposit inks to individual stamp features hν and then the different inks are transferred + − Au + X(CH2 )n SO3 (1) to the different locations on the substrate by µCP. Recently. 371. However. 89. technique.

8 Other Methods The bottom-up compounds are required than those of approaches intrinsically have numerous thiols [392].1. stamp with the relief feature. or postpatterning de. orthogonal self-assembly of elec- using photochemical reaction of photoac.1. and nanofabrication using a nanopipet ad- by Wrighton and coworkers [374. The other is the fabrication of SAMs by 384]. silicon lowed by the deposition of the deprotected wafer) substrates. 385–387]. possibilities by means of the hybridization Tour and coworkers have also found a of techniques compatible with each other thiocyanate to be an excellent precursor for . it typi. Such of a UV source emitting principally at approaches will be combined with other 254 nm [373]. in particular. vide an excellent method to alleviate the The method allows us to transfer metal problem of isolating and using the oxida- films from the raised regions of a stamp tively unstable thiols [392]. chemically unstable thiols. tions of deprotection and deposition as This technique.1. recently by Turro group [376]. the use of an exogenous base. has nanometer resolution.1 Protecting Groups for Unstable ing flat or curved surfaces over large areas Organic Thiols When we prepare a in a single processing step. Tour et al.8.7. They noted that onto various oxide surfaces.2. protecting the thiol etching procedures. 375]. such as micromachining [383. en- tive pendant groups. that is. is expected the preparation method of SAMs from to be useful in the fabrication of the elec. which has been have found that acetyl-protected thiols pro- developed by Rogers and coworkers [377]. and dressing [391]. They describe that us- sulfur compound onto gold surfaces under ing nTP.1. as demonstrated in zymatic nanolithography [388–390]. onto both con- would generate insoluble poly(disulfides). it is generally SAM of chemically unstable organic thi- subtractive in operation. 1. Acetyl-protected thiols are most commonly position steps.2.7 Nanotransfer Printing of Pat. methods. a wide range of patterns can acid or alkaline condition of the solution be printed in parallel with nanometer would be better than the stepwise reac- length scale resolution over large areas. although higher concentrations of the thioacetyl 1. 1. group is important during preparation. is impractical for the α. Moreover. ω-dithiols. we the use of disulfides (Ar−SS−Ar) as pre- are able to transfer the metal pattern from a cursors.7. Nanotransfer printing (nTP) used for organothiols. and 1993 by Fujihira and coworkers [292]. formal (thin poly(dimethylsiloxane) film The in situ deprotection immediately fol- supported on plastic) and rigid (e. troactive monolayers [57. especially for aro- is a purely additive printing technique that matic and π-conjugated thiols. of SAMs terned Gold Thin Films While µCP offers fast and low-cost approaches for pattern.g. Using nTP.2. molecules in the air.8 Advanced Modification Technique 1.2. they trical components of functional organic found that the acetyl-protected thiols can transistors and complementary inverter adsorb directly on the gold surface without circuits [377–382].60 1 Preparation of Monolayer Modified Electrodes occur in the absence of ozone with use for fabrication of patterned SAMs. ols that are easily oxidized to the disulfide cally requires the use of sacrificial resists. which defines since successive oxidative oligomerization the geometry of the pattern.

cage hydrocarbon units in spite of their marks of our profession. The can be removed by immersion into a difference can be interpreted by higher NaOH solution. which are com.6 using BCO-based 1.2 Modification Technique of SAMs SAMs [255]. of flexible SAMs and rigid SAMs. We can adopt gold yield monolayers. 1. However. ers have reported that in situ deprotection are two typical examples of rigid hydrocar- and assembly of S-tritylalkanethiols on bon molecules [397–401]. Therefore. 403].4. Recently. prepared using dithiols where one of the The most important characteristics of thiol groups was protected by a thioester these cage hydrocarbons are their higher group [395]. just alkanethiols [394]. Cage derived molecules. for molecular a variety of solvents and are an excellent design of the backbone of the compo- complement to free thiol and protected nent molecules of SAMs. as surely as short molecular lengths. such a spacer is called a geometrical hibiting a SH-terminated surface could be buffer [403].1. Weiss application of SAMs..1BCO and Adamantane SAMs be formed from disulfides with these Chemical structures are among the trade. beakers. with only unit and a thiol head group. Schreiber a small number of free −SH groups at the described that such an extra methylene surface of the SAM.1.1. in particular.8. There- high-quality organothiolate adlayers ex- fore. .9 Rigid SAMs of the linear single alkane chains [402. stable SAMs could 1.2 SAMs on Au and Ag Electrodes 61 thiolate assemblies [393].1. In addition. 1. the protecting groups chains with similar molecular lengths. ω-dithiol.2. Fujihira and coworkers also of Dithiols The generation of organic demonstrated that a stable adamantane- surfaces terminated by specific functional based SAM was formed successfully on a groups is significantly important for the gold (111) surface [402]. and distillation these spherical cage components formed . Hutchison and cowork. when chemical flasks. The most straight- and coworkers have also examined the forward approach for obtaining such a property of a SAM using an adaman- SAM surface terminated by free thiol tanethiol derivative [403]. we assembly procedures.2.2. boiling points than those of single alkane othiolate adlayers. After formation of the organ. their structures into the backbone units parable to those prepared directly from of component molecules of SAMs. it is useful to see that these easily synthesized molecules can the chemical structures in terms of flexibil- be assembled on gold surfaces directly in ity or rigidity. it has been based components of the SAMs is the pres- shown that this straightforward approach ence or the absence of a methylene spacer leads to the formation of disordered. Analogously. They described columns [396]. The structural groups would be the use of alkanedithiols. ill- connecting between a rigid adamantane defined alkanethiolate adlayers. In other words. van der Waals molecule–molecule interac- tions of the cage hydrocarbons than those 1. spacer plays a critical role for removing the W oll and coworkers demonstrated that steric hindrance in the SAMs [48]. difference between the two adamantane- HS–(CH2 )n –SH. This strategy was already de- scribed in Sect. molecules.2. like alkane chains in alkanethiol-based SAMs. This technique is are able to divide SAMs into two classes ideal for aromatic systems and α. such as BCO and adamantane.9.

1. 421]. Tokumoto and Fuji- chemistry. Early STM investigations by other pounds with thiol head groups. Studies on the kinetics and stability of aromatic SAMs have 1. head group and the aromatic unit. The result first prepared on gold as a new family was rationalized by the spherical shape of SAMs by Rubinstein and cowork- of the cage backbones. and this structure is its electrical properties due Terfort [431. ponent molecule forming a SAM were reported [419]. After the another type of rigid molecule. 41].3 Aromatic SAMs A different riety of instruments.2.2. These studies were fol- viewpoints of SAM preparation. phenyl-. Zharnikov [429. After that. In consequence of the thiols on gold or silver were charac- absence of the tilt. which were based SAMs were not observed. methylene spacer connecting the thiol tively. 413. which is early successful investigations. which exhibits rich molecular . such aromatic SAMs certainly exhibited mation of SAM matrices. that is aromatic thiol. investigated by Ulman and cowork- and thus. As to early studies using cage com. 441]. in this introductory account. terized by Tao and coworkers using lar defects instead of the defects due to IR [416] and STM [417]. the fab- present widely in biological membranes. 412.9. Here we will describe only chains of alkanethiol-based SAMs on some aromatic SAMs of interest from the gold [8. 404–410]. 432] and their coworkers.2 Cholesterol SAM Cholesterol is been undertaken [420. the struc- quire the molecular axes to be tilted in tures of SAMs of aromatic-containing the SAMs [402]. the grain oligophenylenethiols. respec. by W oll [422–425]. that is. only single molecu. They revealed that use these organosulfur compounds for for.1. to π electrons. Many other SAMs is composed of a series of relevant studies have been performed . using such systems [270. in which other a close-packed structure in a hexago- thiol molecules can be inserted into the nal arrangement with an overlayer of a √ √ single molecular defects as upright single ( 3 × 3)R30◦ with respect to the under- molecules. biphenyl-. 430]. The short heights allow us to ics simulation [418]. The families of type of rigid molecule is the aromatic terphenyl-based SAMs have been studied molecule. The single molecular electronic lying gold (111) surface if the component and mechanical properties were measured molecule. The most distinct attribute of hira [426–428]. SAMs on gold and/or silver have been extensively investigated using a wide va- 1. and terpheny thiols. They first studied aromatic it is impossible to take up all subjects SAMs to investigate the influence of aro- of the aromatic SAMs studied by many matic units incorporated in long alkane researchers. boundaries observed in the linear alkane. rication and characterization of struc- The studies using cholesterol-based SAMs tures and properties of various aromatic were reported by Yang et al. The structure was the grain boundaries were seen in the also discussed using molecular dynam- SAMs [404]. Many studies have been Biphenyl-based SAMs were intensively conducted using various aromatic SAMs. the readers groups using thiosalicylic acid as a com- are referred to Refs 411. ers in 1993 [415]. ers [433–439]. which do not re.9.62 1 Preparation of Monolayer Modified Electrodes SAMs on a gold (111) surface. lowed by recent researches by Grunze The most typical family of aromatic and coworkers [440. 414].. [5. has a by STM and noncontact-AFM.

2.3). and the studies by Szafranski the composition of the exposed surfaces et al.1. and fol. The fore.2 SAMs on Au and Ag Electrodes 63 by Zharnikov and coworkers [442.1 Click Reaction on SAMs SAMs temperature in aqueous solvent. early intensive studies by Crooks This category is defined as a structural ex. investigated by Tour [392]. 12). We can see SAMs [456]. 1. and Chidsey first applied this chemistry to the exposed surface of 1. nient method to modify well-defined elec- matic thiols have well-ordered structures. indicating that this offers a conve- SAMs formed from alkanethiols and aro. Love et al. and oth. that there are a number of studies on the reactivity of SAM surfaces. [451. Surface-enhanced Raman limited to a few metals such as gold study of phenyl.11.12. and three general strategies for engineering gold [450].1. and molecules needed for SAMs [453–455] and thiophene-based biology and biochemistry [9].10 π -Conjugated SAMs ample. we above. been extremely well realized in biophys. .. This new strategy is the application Otsubo [462]. are conjugated in covalent interactions (i. This reaction uses the and allow a wide range of functionalities to formation of triazoles through the classic . The re- provide ideal molecularly defined bases to action is extremely specific with high study reactions in two dimensions [464]. man. SAMs by (co-) adsorption. 1. The π. and Bao [463] and their of Sharpless ‘‘click’’ chemistry [475]. Here we will describe because of their potential applications in the recent new modification strategy. hydrogen-bonding. and later by oth- pansion of the aromatic SAMs described ers [472–474]. silver. although the substrates for SAMs are ers [446–448]. and (3) modification in 1982 by Taniguchi and coworkers [29]. [9]: (1) Synthesis of functionalized thiols Nonphenyl types of aromatic SAMs are for forming single-component or mixed also the subjects of importance. Devaraj. W oll and coworkers [444. 443]. These SAMs ligand bonding) can generate new inter- have been intensively investigated recently faces of SAMs [9].e. Several groups of surfaces that present the large. or alternately conjugated with interaction. trode surfaces [97]. They demonstrated that this reaction proceeds completely at room 1. com- have investigated pyridinethiol-based plex ligands.2. such as can realize that both covalent and non- phenyl and thiophenyl. Through these studies. Sita [458–461]. SAMs. and coworkers [466–471]. for ex- 1. Therefore. be incorporated into the monolayers [465]. and metal- ethynyl or acetylene units. 445]. van der Waals a series.11 Chemistry on SAMs SAMs (Fig. in which some aromatics.2.2. 452]. this field of bio-SAMs has formed SAM. click- molecular electronic devices [457]. (2) insertion sighted idea of fabricating bioaccessible of synthesized thiols into defect sites of interfaces of SAMs was first demonstrated preformed SAMs. Methods for modifying SAMs after their ical chemistry and electrochemistry [101] formation are critical for the development (see also Sect. yield.1. described that there are lowed by the study on copper. we can perform a disulfides adsorbed on silver [449] were rich chemistry on the exposed surface of undertaken as early as 1982. and silver. ing functionality onto exposed surfaces of conjugated SAMs have been intensively SAMs [97].and phenylmethyl.1. Coll- coworkers. of the structure composition of a pre- Recently.

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

1. the overall elec. SAMs themselves are also able to reactions consist of the combination of couple to electrochemical reaction pro- elementary processes. logical molecules at the nanoscale through transfer reactions. 12 (continued). 98. actions generated at the surfaces. that is. spatially and temporally coupled to the Many experiments relevant to electro- electron-transfer reaction.2 SAMs on Au and Ag Electrodes 65 R N N R-N3 : N O O O HN O O O N HO O O O H H O O H H R-N3 N3 H O N3 OH S S O O O NH2 N3 Au Au (c) Fig.2 Electrochemistry on Thiol-based surface of SAMs. Thus. Therefore. the chemical processes the exposed surfaces of SAMs. structure [480]. 105–107. If these chemical possibility for accessing chemical and bio- processes are fast relative to the electron. 153.2. We can take chemistry on SAMs ranging from the fun- advantage of this fundamental principle damentals to the applications have been re- of electrochemical reactions to provide ported so far. active species and electrodes coupled to The field of electrochemistry on SAMs the preceding and/or succeeding chem. cesses aggressively depending on their transfer reaction processes between redox. ized. . diating between electrodes and abundant ical processes are slow. modified at electrodes have an emergent ical processes [479]. electron. the electrode reaction can this system involves various issues of elec- express the specificity depending on the trochemical reactions coupled to chemical characteristics of the chemical processes and biological reaction processes [108].1.11. In such are thermodynamically reflected in the a system. As a nanoscale founda- SAMs Modified at Electrodes Electrode tion. 99. chemical and biological interactions or re- trode reactions are kinetically character. 1. The experiments on the fun- a wide variety of specificity into the damental issues include electron-transfer nanoscale electrochemistry on the exposed model systems [88. If these chem. SAMs play a vital role in me- overall electrode reaction.

which may tive approaches to the detection and be defined as SAMs that make it possi- identification of nucleic acids. sphere. amplification is extremely useful in an ul. ionic recognition [497]. prototype of the biocompatible SAMs. and so and direct electronic readout offer strong on. receptors [552]. a ready capacity for miniaturization. 530–532]. and Whitesides and cowork- Liu and Barton have demonstrated DNA ers [534. 551]. oligosaacharides. periments have been reported for the functional SAMs. 553]. such as proteins. Two fam- control of electroactive molecules on ilies characterizing biointerfaces by using SAMs [519]. 103. a central ble to interact actively with biomolecules activity of modern chemical biology [520]. the adsorption of nonspecific biomolecules ing that this method using the redox cycle and cells onto the surface. 535]. Plant [533]. 103. low costs of instrumenta. 523–526]. Until now.66 1 Preparation of Monolayer Modified Electrodes 481–492]. bio- intercalating to DNA through covalent membrane [550. 541]. this technology. materials do no mischief to life and bio- electrode ensembles coupled to electro. numerous ex- electrochemistry by developing method. thiol-based SAMs (OEG-SAMs) on gold is Electrochemical control is another im. and cross-link to guanine residues [521]. biofunc- ology to assemble DNA duplexes onto tional proteins [524. oligonucleotides. Early leading studies of the biofunc- motivations for the development of this tional SAMs were reported by several field [520]. cells. SAMs can be referred to as bio-SAMs. the expres. such as Ringsdorf and ing tendency toward the development of Knoll and their coworkers [136. demonstrat. White. 527. High sensitivity. electrochemical STM chemistry on SAMs through a series of [493–496]. and Yang and Kwak [528] realize that structural disorder and flexibil- and their coworkers have intensively ity of organized surfaces at the molecular . antibody [540. Mrksich [102. 542–549]. research groups. for instance. demonstrated the importance of electro- croscopy [155. type of SAMs is intriguing because we can sides [527]. there has been a grow. Recently. scanning electrochemical mi. a well known typical example and is the portant technique in this field [102. and systems. tors biomembranes. 1.11. a redox cycle as SAMs that make it possible to inhibit of Ru(NH3 )6 3+ /Fe(CN)6 3− . and coworkers have reported a nanoscale The other is the so-called biocompatible approach to DNA biosensing that uses materials [104. This 109]. 536–538]. and structural bioanalytical applications [529]. recep- tion. pling reactions and releases of the attached clude electrochemical polymerization of molecules and cells. and interesting experimental challenges to the biomolecular recognition [498–506]. 539]. Kelley cells [526. Oligo(ethyleneglycol) terminated alkane- trasensitive DNA detection system [522]. tissues. that is. Biocompatible SAMs are defined catalytic system. 493].3 Bio-SAMs Biomaterials are of sion of porphyrin functions in supramolec.1.2. Electrochemical techniques offer attrac. enzymes. electrically conducting polymers on the surfaces of SAMs [507–509]. to use daunomycin as a redox reporter oligonucleotides [520–522. gold surfaces with SAM techniques and enzymes [116. issue on electrochemically induced cou- The experiments for the applications in. great importance for many medical and ular systems [510–518]. 525. One is biofunctional SAMs. 123] in a sense that these oligonucleotide-functionalized gold nano. 528.

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

D. it is no exaggeration to say that various intriguing applications. R. electro- electronics (molectronics-SAM). B. J. F. J. E. R. we realized that of molecules themselves. We have supported SAMs can play a central role as described here only three topics. Nuzzo. G. 24. This finding is also of The well-ordered structural feature of importance in the fundamentals and ap- SAMs is available to the numerous experi. Laibinis. characteristics of SAMs on gold. organic. we can realize that porting substrates as well as the bulkiness such new researches stem from unique and shape of the molecular components. S.1. a ‘‘mediator’’ connecting our experimental electrochemical. B. can certainly control at the molecular level. G. from the aspect of chemistry on cause the SAMs and their preparation tech- SAMs. P. Mathias. T. L. Soc. 254. Am. Grzybowski. through the simple preparation principle 2. 6. J. techniques described here for fabricating 5. plications of SAMs. physical. 1983. Fusco. Nuzzo. precise identification of structures like that On the other hand. Allara. Whitesides. 3. Academic Press. in which chemical and biological nanotechnology. Allara. 4481–4483. A. Allara. Ad. P. 2418–2421. pp. Chem. Chem. patterned SAMs are effective approaches in Thin Films (Ed. Whitesides. in particular. Whitesides. in which J. 1995. These The availability of such a molecularly or- include the convenient techniques for dered arrangement remains the subject of preparation. electrochemical. Several 1990. for the lateral control at the nanoscale. Laibinis. and biological new ap. relatively stable SAM surfaces presenting disordered hy- forms presenting functionalized organic drophilic property are extremely effective surfaces. 1987. the techniques of SAM preparation are prerequisite to the arrangement of the ex. M. We have omitted another important niques have already been providing fruitful topic of the preparation and applications opportunities to allow us to challenge in SAMs useful to studies on molecular future technology. Soc.: A. Ulman). G. ments conducted so far for demonstrating Finally. not simple but relatively future preparation techniques. Biosens. is only Science 1991. underlying surface structure of the sup- In this section. 1998. L. Palmer. Seto. 105.12 Concluding Remarks structurally unique molecular components The idea of supported SAMs on gold themselves would serve an essential role in and the concept of chemically modified the controllable lateral order of molecules. tools and nanoscopic phenomena. to have access to the issue on the technique 6. as OEG-SAMs. 109. Vol. References periments. L. electrodes have naturally fused to produce Another order of SAMs. which are based on present in the well-defined adlattice struc- chemical. M. 1312–1319. E. 10. It is be- proaches. 87–96. Am. Science for height direction with respect to the sub- 2002. 1–41. San Diego.68 1 Preparation of Monolayer Modified Electrodes 1.. D. also intriguing as a solution. vanced organic chemical approaches are 7. C. and tures of SAMs. Langmuir over the two-dimensional surface.-W. 771–783. Bioelectron. . G. D. G. The structural order of SAMs that we 1. M.2. strate surface and not for lateral directions 4. Lee et al. of self-organization on substrates. 295. which is of a a new field of interdisciplinary researches higher level. 2358–2368. is the molecular order being as described here. This order depends on the biological fundamentals and techniques. and the capability of variations in for fabricating practicable bio-SAMs. such the backbone structures. P.

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

who used lipid bi- face at a molecular level. the lower for the realization of a highly efficient the surface density. regarding the pho. Thus. including our group.4–1. although this has transfer are achieved with a minimum re- the disadvantage that the synthetic yield of verse electron transfer [47.2. PQSH with porphyrin photo-induced electron transfer. aminetetraacetic acid (EDTA) as the elec- tron acceptor and donor.5%) [49. ical properties of the alkylthiol SAMs in We have achieved for the first time detail since 1990 [2. SAM was constructed on a gold sur- tochemical properties and review the pho. artificial photosynthetic system. and thiol as the surface- tion. 50] com- the elaborate molecular machinery. and application of luminescence. 57]. 1. are well nal group of the SAM. 2). Unfortunately. 6–46]. and Fujihira et al. control as the photon-absorber. the SAM with a wide variety of functionali- quantum efficiencies of these systems ties is a good candidate for constructing were quite low (0. 50] and the LB films [4. This con- For future nanotechnology. 1(a) [56. The appli. layer membranes [49. to arrange pose. respectively. that very efficient photo-induced charge This method has the advantage that multi. pling molecule (PQSH) as shown in search area. we should cept was first employed by Moore et al. and many re- these systems were not enough to achieve search groups. it is such a surface reaction is usually not high of great interest to mimic the elaborate enough to form a perfect monolayer. separation and photo-induced electron layer formation is easy. the alkylthiol molecules in order. induced electron transfer direction can be tems. than the re- photoelectric conversion device mimick. controlled by the electrode potential [56]. like pheophytins and quinones.2 Photo-induced Electron Transfer at anodic and cathodic photocurrents were SAM-modified Electrodes observed at potentials more positive and Construction of a very efficient artificial more negative. In this section. face. arrange the molecules on a solid sur. active group was synthesized and its especially to sensors. .. For this pur. we focus on Fig. as described above. Thus. 3. indicating that the photo- of the dreams of scientists. molecules of various functionalities. dox potential of the quinone moiety (curve ing a natural photosynthetic system is one (a) in Fig. 48]. the construction of an alkylthiol SAM cation in photoelectric devices. and molecular machinery of natural systems then the thicker the multilayer. is one using a porphyrin–quinone–thiol cou- of the most important fields in this re. 51–55]. quinone as the of electron transfer by photoisomeriza.52 1 Preparation of Monolayer Modified Electrodes on a substrate and then the functional such as a photon absorber like chloro- molecule. respectively. which has the terminal group phylls and electron donors and acceptors for the bond formation with the termi.2. transfer. especially for an artificial photosynthetic system for the SAM-modified electrodes. electron relay. respectively. In natural sys. have a highly efficient photo-induced electron extensively investigated the electrochem. pared with that of the natural systems the SAMs with many functionalities have because the molecular arrangements of been extensively employed. is synthetically organized with molecular dimensions so attached to this SAM-modified surface. In an electrolyte solution containing tochemical characteristics of the alkylthiol methylviologen (MV2+ ) and ethylenedi- SAM-modified electrodes.

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

After prolonged illumination of tron transport or relay. than 3 h without any signs of deterio- and thiol groups as the photoactive. Ag/AgCl). and therefore. if the potential was more negative than because PQSH has no alkyl chains and/or +650 mV (vs.3–3%). separated from each of the solution in front of the electrode other by alkyl chains (PorFcSH) was then changed to blue. lution containing MV2+ as an electron scribed above. the color groups. The photocurrent action spectrum that the reverse electron transfer and en.2 eV by visible light illumi- duced to form a well-ordered SAM so nation.5 (c) [56. the SAM of PorFcSH was illuminated by tion of the photo-induced electron transfer monochromated light (430 nm) in the so- system using the SA technique as de.1 M Na2 SO4 + 50 mM EDTA + 5 mM MV2+ at a pH of 3. elec. and 5. molecular layer was low.5 (a). Although we could achieve the construc. spectrum of the PorFcSH SAM. of more than 1.54 1 Preparation of Monolayer Modified Electrodes 40 (c) (b) 30 Photocurrent density/nA 20 (a) 10 [cm−2] 0 −10 −20 −30 −40 −400 −200 0 200 400 600 Potential/mV vs. showing that MV2+ was synthesized and its SAM was constructed reduced to the methylviologen cation rad- on gold [58]. the orders of the moiety in the PorFcSH SAM (Fig. Ferrocene was chosen as the ical (MV+• ).5 (b). 1b). a stable photocurrent flowed this system is relatively low (ca. we have transfer of this group is known to be very achieved the up-hill transport of electrons fast [38] and the alkyl chains were intro. which has porphyrin. 3). and surface binding this SAM-modified electrode. 2 Potential dependence of photocurrents of the PQSH SAM-modified gold electrode measured in a phosphate buffer solution containing 0. ration. confirm- When the gold electrode modified with ing that the porphyrin group in the SAM . Ag/AgCl Fig. 57]. 4. A novel molecule This stable photocurrent flowed for more (Fig. ferrocene. which coincides the adsorbed amount of the molecules with the redox potential of the ferrocene is low. of the PorFcSH SAM-modified gold elec- ergy transfer from the excited porphyrin trode matched well with the absorption to the gold electrode can be reduced. the quantum efficiency of acceptor. 0. respectively. Since the redox potential electron relay group because the electron of MV2+ /MV+• is −630 mV.

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

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

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

face is covered with the mixed SAMs eral hours. ZnS [105]. the gold electrodes modified with the vestigated the photophysical properties SAMs of molecular templates. whose ter- of gold nanoclusters modified with minal group is β-cyclodextrin [109]. observed pared by the above procedures shown in the photocurrent at the ITO electrodes Fig. Woo . which is not connected Nanocluster Layers with the gold. a photocurrent at the gold electrode mod- ing several different alkyl chain lengths ified with electrostatically deposited layers and observed the photocurrent [84–88]. many served at the gold electrodes modified with studies on photo-induced electron trans. AOT).2. 98] and observed a pho- the alkylthiol can be prepared by heating tocurrent at the SnO2 electrode mod- the solution containing the appropriate ified with electrophoretically deposited alkylthiol and simultaneously by dipping layers of gold nanoclusters. 8. the SAM forms with the alkylthiol SAMs. 8) [102–108].2. a alkylthiols can be used to examine how the unique preparation procedure is em- electron transfer rate constant depends on ployed. Li et al. in the dithiol SAMs on gold is covalently bonded to the surface Since Brust et al. whose surface is cov- They investigated the alkyl chain length ered with the SAM of a porphyrin-viologen dependence on the photocurrent and coupling molecule [100]. 7) [96]. the SAM of a porphyrin-thiol coupling face. pling molecules [99]. After this the dithiol the electronic coupling. easy to introduce to functional groups by Relatively large photocurrents were ob- a place-exchange method [93–95]. It 1. also observed ified with the SAMs of n-alkylthiols hav. whose sur- the semiconductor substrate in it for sev. such as CdS [103–106]. the thickness of the insulating layer. the photocurrent generation at the semi.58 1 Preparation of Monolayer Modified Electrodes of the alkylthiol SAM on a metal sur. whose surfaces were covered ters [102] and. They which are covered with the surfactant suggested that of particular interest is the sodium bis(2-ethylhexyl) sulfosuccinate ability of the alkylthiol SAM-modified elec. A relatively ordered monolayer of molecule [97. semiconductor nanoclusters. First. Imahori et al. There is an interesting preparation modified with the multilayer of gold method by which the tellurium nanoclus- nanoclusters and porphyrin-tetraalkylthiol ters were electrochemically deposited on molecules (Fig. and CdSe [108]. as a result. demonstrated that the studies of the For the gold electrode modified with photocurrent versus chain length of the the semiconductor nanocluster layers. of gold nanoclusters. Gu and Waldeck constructed of porphyrin-thiol and fullerene-thiol cou- the n-InP semiconductor electrode mod. and then the layers of the semiconduc- conductor electrodes were well studied and tor nanoclusters were prepared by dipping summarized in the literature [89–92]. many kinds of semiconductor nanoclus- fer using alkylthiol SAM-modified metal ters. reported that the gold atoms of the semiconductor nanoclus- nanoclusters. or semiconductor nanoclusters were re. PbS [107]. were prepared in trodes to probe the distance dependence of reverse micelles [101]. (Aerosol OT. the dithiol SAM-modified gold in a nan- ocluster dispersion (Fig. in. are stable and on the semiconductor nanocluster surface.3 Photo-induced Electron Transfer at was confirmed by XPS that the termi- Electrodes Modified with SAM-covered nated thiol group. which were pre- ported [96–111]. The principles of SAMs were prepared on the gold surface. Yamada et al.

2 SAMs on Au and Ag Electrodes 59 P P P P P P P (Step 1) P P ITO NH aq. 9) HD HS SH(HD) (Step 2) (Step 3) ITO ITO ITO (Step 2) C2H5OH 9 (Au/HD)9 /ITO AcS(H2C)12O O(CH2)12SAc N P : Porphyrin (P) NH HN N : Au particle (Au) AcS(H2C)12O O(CH2)12SAc P Fig. Each component is drawn in size according to the CdS CdS CdS CdS estimation from experimental results [102]. 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 formation of alternating layer-by-layer CdS CdS dithiol structure: (a) dithiol SAM on a gold substrate (Au-dt).6 9) and (Au/HD)9 /ITO [96].3. Fig. 1. 7 Schematic illustration for the fabrication of multilayer assemblies. (P/Au)n P/ITO (n = 0. 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 . (b) CdS nanoclusters Au attached on the SAM (Au-dt-CdS). 6. P (Step 2) P P P P P P P n (P/Au)nP/ITO (n = 0. (Step 2) (Step 1). (d) formation of a second CdS-nanocluster layer CdS CdS (Au-dt-CdS-dt-CdS). 3. (c) adsorption of dithiol layers on CdS (c) Au-dt-CdS-dt (d) Au-dt-CdS-dt-CdS nanoclusters (Au-dt-CdS-dt)./THF ITO P ITO P ITO P P 3 Au colloid aq.

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

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

5 mM K4 Fe(CN)6 to the cell. 12 CVs for (a) a pure cis-AzSH (a) (b) SAM in the absence of light and in the cis-1 film in Doping of 2 in presence of 0. Cathodic 5 µA 5 µA Amplified response −0.5 mM After cis-trans was 0. even if the orig. The wave due transfer rate at the gold electrode mod. When the potential was scanned to 0 mV. The geometric area of the working electrode (c) (d) Addition of 0. respectively. azobenzene moiety appeared. to the redox of azobenzene. we can control the charge scan (solid line in Fig. gold electrode can be reversibly controlled . 10(c) [118].4 0.0 0. 13c). (d) the 5 µA 5 µA two-component SAM. These range between 0 and +750 mV appeared changes in the electrochemical character- and did not change shape after the po. the redox also showed that only the redox peaks due potential and the charge transfer rate. The CV of On the basis of the structural analysis gold modified with the SAM of 20% cis.2 M NaClO4 . in the presence of 0. The electrolyte used in all K4Fe(CN)6 conversion of the above experiments was 0. that is. trochemical properties. Ag/AgCl (V) hydrazobenzene is electrochemically ox. in the second scan the SAM of 100% trans-form AzFcSH (dotted line in Fig. The redox poten- (Fig. we concluded that the elec- containing AzFcSH after UV irradiation. tential scan or UV irradiation. Scan rate = 100 mV s−1 [112].2 0. Ag/AgCl). istics of the latter electrode were reversible.2 0.6 Potential vs. In a to ferrocene became more negative and CV of the gold electrode modified with smaller. frared reflection absorption spectroscopy which was prepared from the solution (FT-IRRAS). results by in situ Fourier-transform in- and 80% trans-forms AzFcSH (Fig. (b) the 0.2 0. idized only to trans-azobenzene around a pair of waves due to the redox of the +200 mV (vs. however. and the redox potential and the zene–ferrocene–thiol linked molecule peak separation of the redox wave due (AzFcSH) shown in Fig. 13a). (c) the two-component SAM (1 : 99 = FcAzSH: cis-AzSH) after addition of 0. dis- ified with the SAM of the azoben.2 0.5 M K4Fe(CN)6 cis-1 film cis-AzSH SAM after doping it with 1% Anodic FcAzSH (no K4 Fe(CN)6 ).4 0. Using this to that of ferrocene in the first potential phenomenon. the ferrocene group in the SAM-modified tial range between +200 and +750 mV. only a pair of waves due to tial and the peak separation returned to the the redox of ferrocene in the potential original values after UV irradiation.5 mM K4 Fe(CN)6 . in addition inal form is the cis-form.21 cm2 .6 −0. of to ferrocene were observed in the poten.5 mM K4 Fe(CN)6 .62 1 Preparation of Monolayer Modified Electrodes Fig.0 0. 13c). after irradiation Current with >400 nm light for 1 h. appeared. 13b).

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

14 Schematic illustration 0/+ N Fc at the interface (a) between the S Fc 0/+ NN NO2 100% trans-AzFcSH S Fc 0/+ NN NO2 SAM-modified gold electrode Au N and the electrolyte solution containing perchlorate anions S NO2 ClO4− and (b) between the 20% cis- 0/+ N Fc and 80% trans-AzFcSH S Fc 0/+ NN NO2 SAM-modified gold electrode (a) N NO2 and the electrolyte solution containing perchlorate anions before the potential scan to 0 mV [118]. examined by Roth et al.64 1 Preparation of Monolayer Modified Electrodes S Fig. and investigated dimer formation of the In this case. Fluorescence from the mixed SAMs of the ferrocene-thiol derivative and Zn tetraarylporphyrin-thiol derivative were 1. Potential scan UV irradiation to 0 mV S 0/+ Fc N S Fc 0/+ NN NO2 S Fc 0/+ NN NO2 Au N NO2 ClO4− S 0/+ Fc N S Fc 0/+ NN NO2 (b) N NO2 using this SAM-modified electrode [131]. the polystyrene nanosphere doped as a . measured the fluorescence intensity from tensity and FT-IR spectrum of the SAMs. trochemical active myoglobin protein layer In addition to the photoisomerization on gold electrodes modified with the of the azobenzene and spiropyran/mero. Guo spiropyran/merocyanine-terminated and et al. trodes. they used the mixed SAM of anthracene moiety in this SAM [137]. tigated their fluorescence spectra [138]. constructed the photoactive and elec- 4-pyridine thiol. and diarylethene [136] were apomyoglobin in solution with the cor- used as the photoisomerization group responding metalloporphyrin and inves- in the alkylthiol SAM-modified elec. (Fig. molecules (Fig. [139] Bohn et al.2. 17a). Fox and Wooten constructed the SAM constructed the protein-connected SAMs of an anthracene-thiol linked molecule by using the procedures shown in Fig. (pyridylazo)benzene [134]. 17b) by reconstitution of stilbene [135].2. measured the luminescent in. 18. SAMs of metalloporphyrin-thiol linked cyanine system.5 Application of Luminescence from measured under open circuit conditions SAM-modified Electrodes and the amounts of the photo-storaged Luminescence from the SAM-modified charge in the SAM were quantitatively electrodes has been extensively studied.

+ EDC S NHC CH3 Au O− Au OH (MR) Au Au O 2N O 2N hv1 λ>475 nm hv2 400 nm>λ>360 nm S NH2 O N CH3 S NHC CH3 O Au (SP) NO2 Fig. O + N CH3 HO C CH3 OH NH2 S NH2 O S NH2 O 2N S + CH3 NH2 NHC N S O + S CH3 S NH2 N CH3 −H+ S NH2 HEPES. 15 Schematic modification procedure of a gold electrode by a photoisomerizable spyropyran SAM [130–133]. 1. pH 7.2 SAMs on Au and Ag Electrodes 65 .5.

The electrochemical and electrogener- tigated cellular adhesion and motility by ated chemiluminescence (ECL) from the measuring the surface composition gradi. fluorescent label in the SAMs. and inves. 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). (b) When the electrode is in the cationic merocyanine state. repulsive interactions disallow the functioning of the bioelectrocatalytic processes [130]. (Ru(bpy)3 2+ ) -thiol linked molecules . 141].2 -bipyridine) ruthenium(II) as fibronection [140. gold and ITO electrodes modified with the ents of extracellular matrix proteins such SAM of tris(2.66 1 Preparation of Monolayer Modified Electrodes H Cyt c (red) COx 2H2O S N N (ox) o o S N Cyt c NO2 (ox) COx O2 + 4H+ S N (red) e− (a) λ > 475 nm 320 nm < λ < 380 nm H S N +N o Cyt c Repulsion (ox) S N HO NO2 S N (b) λ > 475 nm 320 nm < λ < 380 nm H Cyt c LDH Lactate S N (red) (ox) N o o S N Cyt c LDH Pyruvate NO2 (ox) N (red) S (c) Fig.

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

19) and alate. 17c [142] and Fig. (Fig. electrochemically generated Ru(bpy)3 3+ oxidizes C2 O4 2− . 19). in the anodic current was observed as the served at the Ru(bpy)3 2+ SAM-modified potential becomes more positive (Fig. which were exploited to couple the nanospheres to amine-terminated thiol SAMs through amide bond formation [140]. Ru(bpy)3 2+∗ may considered to take place within the posi. The potential dependence acts as a mediator for the oxidation of ox- of the emission intensity (Fig. 18 Schematic modification process of the fluorescent nanospheres containing a large number (∼106 per sphere) of pendant carboxylic acid moieties. also used the follow- 3+ − 2+∗ Ru(bpy)3 + CO2 • −−−→ Ru(bpy)3 ing oxidation reaction of tripropylamine (TPrA) and the above reactions (1) and (4). Ru(bpy)3 3+ + TPrA −−−→ Ru(bpy)3 2+ forming CO2 and CO2 −• . and therefore. TPrA•+ −−−→ TPrA• + H+ (8) . 146]. and becomes + TPrA•+ (7) Ru(bpy)3 2+ which again donates an elec- tron to the electrode (reaction (1)).68 1 Preparation of Monolayer Modified Electrodes + NH2 NH2 HS S Au O O O OH + EDC N NHS O O O O + NH2 S N S N H O Fig. 17d [143. Bard et al. a monotonic increase luminescent spectrum (Fig. directly donate an electron to the elec- tive potential region where emission was trode (reaction (5)) or relax to Ru(bpy)3 2+ observed [142]: with a light emission efficiency controlled by the electron transfer rate of the reac- Ru(bpy)3 2+ −−−→ Ru(bpy)3 3+ + e− (1) tion (5) which should be dependent on Ru(bpy)3 3+ + C2 O4 2− −−−→ Ru(bpy)3 2+ the distance between the electrode and the Ru(bpy)3 2+/3+ head group in the + CO2 + CO2 •− (2) SAM. electrode in a solution containing CO2 −• reduces Ru(bpy)3 3+ to Ru(bpy)3 2+∗ C2 O4 2− and the following reactions were which has excess energy. + CO2 (3) and observed ECL from the generated Ru(bpy)3 2+∗ −−−→ Ru(bpy)3 2+ + hν (4) Ru(bpy)3 2+∗ at the SAM-modified gold and platinum electrodes [145. 144]) the Ru(bpy)3 2+/3+ head group in the SAM were reported. Thus. 20) were ob. Ru(bpy)3 2+∗ −−−→ Ru(bpy)3 3+ + e− (5) TPrA −−−→ TPrA•+ + e− (6) In these processes.

1 1 0 0 (b) 6 Light intensity [au] 4 2 0 0 200 400 600 800 1000 1200 1400 1600 Potential/mV vs.4 M Na2 SO4 + 0.4 4 (a) Current density 0.2 SAMs on Au and Ag Electrodes 69 0.15 V (dots) and the emission [au] 0.4 Emission intensity containing 0.2 spectrum of Ru(bpy)3 2+ -thiol in CH2 Cl2 solution (solid curve) [142]. Fig.1 M Na2 C2 O4 [142]. 20 ECL spectrum of the Ru(bpy)3 2+ -thiol SAM-modified ITO electrode in a solution 0.2 2 0. 19 Potential dependence of (a) the currents of the unmodified (broken curve) and SAM-modified (solid curve) ITO electrodes. Ag/AgCl Fig.3 3 [mA cm−2] [mA cm−2] Current 0.4 M Na2 SO4 + 0.1 M Na2 C2 O4 at 1. 0. 1.0 500 600 700 800 900 Wavelength [nm] . and (b) the ECL intensity of the unmodified (broken curve) and SAM-modified (solid curve) ITO electrodes in a solution containing 0.

They con- structed layers of 4. ity [145] and immobilization of DNA and and Mg–Ag alloy. the ECL behaviors respectively. which means the SAM shaped π-conjugated thiols and disulfide of the molecule (f) shown in Fig. evaporation. 4 8 12 16 (2) SAM(f). deposited both on the bare gold and bare electrochemical microring array [147]. protein [146] were investigated. ITO substrates were also used. order of SAM(f). . the above reports. and electron transport layers. (b) Voltage (4) bare gold. luminescence-voltage (L-V) curves of these Yamashita et al. these layers trodes were used to fabricate an opto. on these SAMs by vacuum at the Ru(bpy)3 2+ SAM-modified elec.4 -bis(3-methylphenyl- Using this ECL behavior of the Ru(bpy)3 2+ phenylamino)biphenyl (TPD). droxyquinolinato)aluminum(III) (Alq3 ). (3) SAM(g). used gold electrodes devices shifted to higher voltages in the modified with the SAMs of the tripod. Figure 21 There is a report that describes the shows the EL characteristics of these de- application of a SAM-modified electrode vices. the surface hydrophobic. 21 (a) I-V and (b) L-V 100 characteristics of (1) SAM(e). Both the current-voltage (I-V) and in an electroluminescence (EL) device. < 103 102 [mA cm−2] Current 101 2 1 5 4 3 100 10−1 (a) 104 103 Luminance [cd m−2] 102 2 5 1 4 3 101 Fig. As a reference. as a hole transport. Except for emission. tris(8-hy- /TPrA system. and (5) bare ITO [V] devices [148]. 16.70 1 Preparation of Monolayer Modified Electrodes Ru(bpy)3 3+ + TPrA• −−−→ Ru(bpy)3 2+∗ (Figs 17(e)–(g)) and investigated enhanced hole injection from the EL of these + products (9) SAM-modified electrodes [148].

the catalytic oxidation current bare gold device. The results of the detect glucose in the presence of glucose CVs at the gold electrodes modified with oxidase [150]. 22). of the thiol SAM(e) less. not on an electrode. The different effects of of luminol was observed (solid line in the SAMs on the EL properties of the Fig. 22b). In contrast. Ag/AgCl (NaCl) . the SAM(g) device oxidation peak due to the redox of fer- showed EL characteristics poorer than the rocene. These modifi. fluorescence from a porphyrin. investigated the electro- SAM(g).0 Current 4. con- cations influence the hole injection barrier structed Au and Au/Ni nanowires whose height at the Au/TPD interface and then surface was modified with the SAMs of affect the EL characteristics of the devices.0 Fig. and of the incorporated in a SAM. They applied this system to interface by the SAMs.0 2 mV s−1 . in addition to the ter stability. which is pact.2) (b) Light intensity with 100 µM luminol and 10 mM H2 O2 3. 22 (a) Linear sweep 2. electrode (Fig. Potential/mV vs.0 (a) [mA • cm−2] 6. and bet. although it is disulfide SAM(g) very poor. (b) ECL intensities of ferrocene-thiol SAM-modified gold 1. leading The ECL intensity depended on the pH of to the vacuum level shift at the Au/TPD the solution.1 M buffer solution. for example. Sweep rate: 2. these SAMs showed that the packing of There is an interesting report about the tripod-shaped thiol SAM(f) was com. hydrogen peroxide were contained in the permitting much higher current. When luminol and ing much greater maximum brightness. yield. It is quite important to apply the Fluorescence microscopy was used to opti- SAM-modified electrode to a biosen. gold-nickel nanowires for selectivity and 8. 22a) and light emission was simulta- devices were concluded to be due to the neously observed (open circle in Fig.2 SAMs on Au and Ag Electrodes 71 SAM(e) ≈ bare ITO < bare gold < 150]. oxidative chemiluminescence from a lumi- the SAM(f) device exhibited a significantly nol/hydrogen peroxide system catalyzed improved EL performance. electrolyte solution.0 voltammograms of ferrocene-thiol SAM-modified gold electrode measured 0 in electrolyte solution (0. mize the functionalization of two-segment sor using the fluorescence from it [149. Compared to the bare gold device. a porphyrin-thiol coupling molecule [151]. modification density of the SAMs. ECL intensity of unmodified gold electrode (closed 0 200 400 600 750 diamond) [149]. Sato et al. 1.0 NaClO4 /0.0 (solid line) and without luminol and (a u) H2 O2 (dotted line).0 electrode (open circle) simultaneously measured with the linear sweep 0 voltammograms. by the ferrocene-thiol SAM-modified gold greatly reduced operating potential. Reich et al.1 M 4. pH 8.

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Italy of the SAM molecules.1 Preparation Methodology and electroanalytical investigations on the de.Rubinstein. I.1 Introduction and Scope main aspects of the preparation. which repre- in Hg-supported phospholipid SAMs with sent the main constituents of biological the aim of investigating their behavior in membranes. Edited by A.1. Stratmann Vol. this review covers the 1. aiming at exploiting the unique prop- 1. as long as interactions an environment mimicking that of bio. between an aqueous phase and the polar cal membranes. and properties of the above SAMs defect-free surface that lends itself to the on Hg. when Miller Phospholipid monolayers consist of a hy- and coworkers [1.2 Phospholipid SAMs on Hg dates back to the early 1970s.3. usually at a submonolayer level. The interface for their applications as models of biologi. attention has been SAMs on Hg Electrodes and Si focused on analogous investigations on Hg. after the investigations on the in. 2] described the self.3. ization. and mainly. Firenze.1 erties of this liquid metal.F. Weinheim. From then on.3 SAMs on Hg Electrodes and Si 105 1.Fujihira.3 on gold electrodes. character- Mercury has a homogeneous.J. 1. on Hg this is mainly governed by intermolecular inter- actions. phospholipid ing ionizable groups (phosphate. alent to that between the same aqueous tides. formation of well-behaved self-assembled monolayers (SAMs). no apprecia- applications of phospholipid SAMs on Hg. Without having the pretension of be- ing comprehensive. KGaA. an aqueous dispersion of dipalmitoylphos- teresting properties of alkanethiol SAMs phatidylcholine (DPPC) to be adsorbed on Encyclopedia of Electrochemistry. Edited by M. lipophilic ions. featureless. 10 Modified Electrodes. This finding started a series of 1. Procedures The first attempt to deposit position of water-soluble thiol films on a lipid monolayer on mercury was car- Hg. To this end. which pre. SAMs on mercury electrodes have been carboxyl groups) whose polarizability im- extensively investigated not only for their parts to this region a higher dielectric intrinsic properties but also. as experimental models of biological mem- figured the formation of a monolayer of branes.2. and proteins have been incorporated phase and lipid bilayers.1. and J. ISBN: 978-3-527-30402-8 . pep.3.1.Rusling Copyright  2007 Wiley-VCH Verlag GmbH & Co. with foreign molecules are only confined logical membranes. Much before the first to the polar head region.3. this amino acid provided with a sulfhydryl group. Thus. Only ried out by Miller and Bach [1] by causing recently. ble differences are expected. While on a SAMs on Hg Electrodes solid substrate such as Au it is the lattice Rolando Guidelli structure that governs the organization Florence University. constant (from 10 to 30). amino. drocarbon tail region with a dielectric assembly of phospholipid monolayers on constant comparable with that of alkanes a dropping mercury electrode with a long (≈ 2) and a polar head region contain- drop time. Bard and M. This is why in 1940 Kolthoff and Barnum [3] described phospholipid monolayers supported by a dc polarographic adsorption prewave mercury have been extensively employed for cysteine electrooxidation. One of the first appli- cations of Hg as a support for a monolayer 1. molecules of head region of lipid monolayers is equiv- biological importance.

where it can (1/19) molecules/A˚ 2 over the potential form hydrogen bonds with the adjacent range from −0. 0.6 V/SCE.2 mm above the lipid film previously ing to two [5] or three [6] lipid monolayers. 8]. it is covered almost completely by ally pentane or hexane) on the surface a self-assembled lipid monolayer.2 to −0. especially if it at the equilibrium spreading pressure of incorporates a lipophilic substance capa- the lipid film on the aqueous subphase but ble of decreasing its fluidity. thereby creating more layers with a differential capacity of about favorable conditions for the attainment of 1. as 1–2 seconds. Miller and coworkers found trode (HMDE) in place of a dropping that well-organized phospholipid mono. A film of 3 H-labeled oleic head to attain a minimum in their adsorp- acid on mercury obtained by this proce. namely. A variant its equilibrium spreading pressure plus a of this procedure was later adopted by . this was adjusted above (pzc). Pagano and Miller [2] transferred onto an electrode. growth. neck remains in contact with the lipid ing the alkane to evaporate.106 1 Preparation of Monolayer Modified Electrodes the surface of a dropping mercury elec. ex. they choose to turn it dure had a surface concentration of about toward the aqueous phase.2 V. at the potential of zero charge cury electrode. in agreement water molecules. while its of an aqueous electrolyte and by allow. the lipid free black lipid membranes [4]. spread on the aqueous electrolyte [5]. and to continue growing the adsorbing lipid molecules have to de- for other 10–15 seconds before falling off cide where to turn their hydrophilic polar the capillary. This by no means implies that mercury rium spreading pressure from a deaerated has no affinity for the oxygen of water. the water molecules adsorbed on the film in such a position as to start mercury are slightly oriented with the oxy- growing in the nitrogen atmosphere. exploits the fact that Langmuir–Blodgett (LB) films of different mercury is the most hydrophobic metal. by using a hanging mercury drop elec- Subsequently. Because layer. in fact. The drop is also with lipid surface concentrations at formed after positioning the HMDE about the nitrogen/water interface correspond. This proce- hibiting a high differential capacity C dure. orga- range from −0. At any rate. In fact. nized monolayer from a Langmuir trough quently. Langmuir trough onto a dropping mer. its surface. the a well-organized monolayer is formed on film was less than monomolecular. lipid excess in equilibrium with the mono- trode with a long drop time. adsorption equilibrium.1 to −1. The technique was further improved tended molecules in a vertical orientation. However. could be monolayer may not adjust readily to an obtained by a similar procedure not only expanding mercury drop. with a close-packed monolayer of fully ex. although less touch the nitrogen/water interface after than on other metals [7. to gen turned toward mercury. as this film comes of the very low solubility of DPPC and into contact with the mercury electrode. by ‘‘self-assembly’’. twice that of solvent. which should be distinguished from of about 8 µF cm−2 over the potential the ‘‘LB transfer’’ of a preconstituted. its gel state at room temperature.7 µF cm−2 . As The lipid film is obtained by spreading a the drop touches the film following its solution of the lipid in an alkane (usu. Subse. amphiphilic molecules at their equilib. tion free energy. This lipid reservoir previously spread on the sur- film can be regarded as a monolayer at face of the aqueous electrolyte. mercury electrode.

7 V/SCE until a constant these conditions the film expansion main- value of 1. dipalmitoyl PS. whereas with dioleoylphos- monolayer on this electrode provides dif. including its thickness. this value.3 SAMs on Hg Electrodes and Si 107 Nelson and coworkers [9.3. by a capacity increase that precedes mer- cury electrode consists in contracting the cury oxidation. tains the amount of lipid material on the .1 Differential Capacity of Phos- lipid film spread on an aqueous electrolyte pholipid SAMs on Hg The differential in an amount >0.2. ensures and 2 are replaced by a single peak [14]. 8 to 2. the drop layer attains a constant minimum value was then slowly immersed in the elec. at negative potentials this lipid-coated drop while keeping its neck region is delimited by two sharp peaks in contact with the lipid reservoir spread that lie at about −0. Thus. minimum capacity varies proportionally while scanning the potential repeatedly to the drop area A [9. the DOPC liposomes for about 15 minutes. Since under from −0. and nature of the electrolyte. 1.9 V/SCE. ionic A special home-made HMDE that uses strength. by changes in pH.1. the mercury drop because of lack of fluid- traction divided by the decrease in drop ity.9 and −1. over a potential range from −0. If the area of a lipid-coated layer on an HMDE consists in keeping HMDE is expanded while keeping it im- it immersed in an aqueous dispersion of mersed in the aqueous electrolyte. as the drop is state cannot be transferred satisfactorily to contracted. 10]: a commer. The transfer of a lipid −0.35 V in the case of DOPC. At positive potentials the re- cedure for measuring the charge density gion of minimum capacity is delimited σM on the surface of a lipid-coated mer. With of lipid material between the lipid mono. is not affected lipid monolayer supported by mercury. with di- taining a constant area for periods of up oleoylphosphatidylethanolamine (DOPE) to 90 minutes. phatidylserine (DOPS) it decreases from ferential capacity values with an accuracy 1. A simple pro. 1) and by a third peak at cedure. more crystalline state is about 42 ◦ C.7 V/SCE (Fig.7 µF cm−2 and ranges from −0. The charge following the con. peaks 1 lipid film spread on the solution. peratures [9].2.3.9 to 1. Thus. amounts to ∼1.1. 15].3 µg cm−2 . whose transition area yields directly the charge density σM temperature from the gel to the liquid- on the mercury surface. an oleodynamic system for moving the The value of the minimum capacity and electrode vertically inside a water-jacketed its potential range vary slightly with the box and extrudes stationary drops main.85 µF cm−2 is attained [13]. with a reproducibility bet.02 µF cm−2 .4 to −0. nature of the phospholipid. This procedure −0.8 µF cm−2 . capacity of a self-assembled DOPC mono- ing to about three monolayers.3 [14]. This pro. correspond. was described by Moncelli ∼1.0 V (peaks at the water/argon interface [12]. transferred to mercury only at higher tem- oleoylphosphatidylcholine (DOPC) mono. which exploits the free exchange about −1. that the monolayer maintains its proper. can be lengthy procedure to self-assemble a di.15 to and Becucci [11].6 µF cm−2 as the pH passes from better than 0. the minimum capacity amounts to ter than 1%. 1).2. which gives rise to a self-assembled phospho.2 Structure and Physical Properties cial HMDE was used to form a mercury of Phospholipid SAMs on Hg drop in a nitrogen atmosphere above a 1. 1 and 2 in Fig. Lipids that are not in the liquid-crystalline ties. temperature.15 to trolyte across the lipid film. A further. dimyristoyl phosphatidylcholine (PC) and layer that coats the mercury drop and the bovine phosphatidylserine (PS). 1.

two- expansion causes a progressive tilt of the dimensional phase transitions. where d is the film thickness and ε0 the capacity minimum by shifting peaks 1 is the permittivity of the free space. are more strongly adsorbed on Hg. A decrease lipid molecules. such as . for a constant volume V = Ad of the more positive potentials positively.3 −0. this behavior can Peaks 1 and 2 of DOPC are capacitive in be explained by assuming that the drop nature and are due to field-induced. the latter capacity rise to d. 1 Curve of the differential capacity C versus potential E for DOPC-coated mercury in 0. A decrease in ionic formula. the direct proportionality between C is shifted negatively by those anions that and A requires the constancy of ε. The capacity C of the film can be to 60 ◦ C shifts peaks 1 and 2 negatively and approximately expressed by the Helmholtz peak 3 positively [17].3 −1.5 −1. strength broadens the potential range of tor.108 1 Preparation of Monolayer Modified Electrodes 1 20 50 TMACl 10 a 2 40 0 [µF cm−2] KCl 3 C [µF cm−2] 20 30 C 10 LiCl 20 20 10 10 −1. KCl.2 −1. without altering the dielectric constant ε of whereas an increase in temperature from 5 the film. drop surface constant. and hence in peak 1 and a negative shift in peak 2. At con- lipid material. without incorporation of in pH from 8 to 1 causes a positive shift water into the lipid monolayer. for a parallel-plate capaci. The inset shows C versus E curves for bare (dashed line) and DOPC-coated (solid line) mercury in 0.9 −1. ε0 ε/d.1 M solutions of TMACl. and LiCl [16]. A is inversely proportional stant ionic strength. noting and 2 negatively and the capacity rise at the that.6 −0.8 −2.1 E (SCE) [V] 0 0 −0.1 M KCl.5 E [V] Fig.

SAMs obtained by the spreading proce- of total desorption in this electrolyte dure. for bare Hg in 0. peak 1 shifts at the same value as the pzc on bare positively in response to the electrolyte mercury.850 V/SCE. −0. 1 shows C versus E plots in 0. Complete desorption takes place scan from the region of the flat capacity at potentials negative enough to cause a minimum to a potential just negative of merging of the curve of the differential peak 2 and the potential is then scanned capacity C versus the applied potential back.3 SAMs on Hg Electrodes and Si 109 bromide and iodide ions. −23. face dipole potential of ∼+200 mV [20]. The best overlap is vesicles. on DOPC-coated served in the reverse scan and the pristine mercury at −0. in tend to heal the defects in the SAM. By scan exhibits smaller peaks 2 and 1 and knowing the charge density.1 M TMACl. and that must potentials. no peaks are ob- −0. . the be- upon readsorption.1 µC cm−2 .1 M scanned back. −1. monolayer. χ. at −1.1 M KCl.1 µC cm−2 . This difference in behavior is due to layer shifts the pzc toward positive values. up to the desorption erwise identical conditions. A different behavior is havior in 0. they are formed at sufficiently negative companies such a coating. The charge at tial for the first time from the region of a DOPC-coated mercury electrode which the capacity minimum to a potential just follows a chronocoulometric step from the negative of peak 2 yields a capacity curve pzc. if the potential is scanned beyond peak 3 (say. as the surface dipole potential χ that ac. On the other hand.1 M practically identical with that recorded with TMACl. and their replacement by a PC the lipid. peaks 1 and 2 and the capacity min- E recorded on lipid-coated mercury with imum are fully recovered [13].4 ± 0.2 µC cm−2 − Q = is then scanned back. under oth. the capacity min- monium chloride (TMACl) both on bare imum is higher. −23. which This is due to the positive shift. LiCl. The inset of potential of −1.1 M NaCl and CsCl is similar observed with SAMs obtained from DOPC to that in 0. In fact. whose polar heads have a sur- The third peak in Fig. 1 exhibits hys.8 ± 0.1 µC cm−2 . 1. ered. however. the capacity minimum beyond peak 3 and the charge density. Na+ > K+ > Cs+ . peak 3 is shifted positively solutions of KCl.450 V/SCE. In this case. capacity minimum is substantially recov- Therefore. other hand. namely. the subsequent backward amounts to Q = −22. the coating involves cation in the order: Ca2+ = Mg2+ > Li+ > the removal of adsorbed water molecules. the constant presence of liposomes. revealing some defects and on DOPC-coated mercury [16]. probably because density on the metal to keep the ap- of a competition with the lipid for the metal plied potential on lipid-coated mercury surface. teresis in the reverse potential scan [9] If a DOPC SAM obtained by the spread- and is due to partial desorption of the ing procedure is subjected to a potential lipid. On the that obtained on bare mercury. If the potential is scanned from from electrocapillary measurements [18]. most importantly. in the order of whose surface dipole potential amounts the increasing binding of these cations to to ∼−100 mV [19] (negative toward the the phosphate group of the polar heads of mercury).450 V/SCE is obtained [16]. and tetramethylam- and. and may also fuse with the be compensated for by a negative charge SAM. scanning the poten- attained in 0.850 V/SCE on bare Hg tine one. to a potential.85 V/SCE) and is then Fig. coating Hg with a DOPC mono.2 ± a capacity minimum lower than the pris- 0.

This plot is particularly suit- which is known to interact strongly with able for representing a series RC network. the lipid molecules remain in Li+ or Ca2+ . 1 shows that in 0. Impedance spectra are than that of bare mercury. Thus. the various relaxation times neither the fluorescence nor the capacity often differ by less than 2 orders of mag- recover the pristine value. the fluorescent for their separation. In fact. the from a Au electrode. nitude. This indicates that. A similar behavior is chemical admittance and ω is the angular observed in the presence of Ca2+ [24]. 21]. cluding a small amount of an amphiphilic which prevents the merging of the C fluorescent dye molecule in the lipid versus E curve on PC-coated mercury with SAM [22]. this is probably to on the electrode surface with a posi. preventing an image analysis yielding trum can often be equally well fitted to their number density and size. thus requiring a certain amount fectively re-formed SAM. In particular. in the presence of orption. owing to the particularly strong orption/readsorption process was imaged interaction of the highly hydrated Li+ using epi-fluorescence microscopy and in. the phosphate groups of phospholipids. In contrast to of arbitrariness and of physical intuition a similar gold system [23]. On a Hg electrode. which are The inset in Fig. Upon scanning the potential progressively in the negative Impedance spectroscopy measurements direction up to film desorption. is 2 to 3 orders of magnitude of Ca2+ . as distinct that on bare mercury. even at far frequently reported on a Y  /ω versus Y  /ω negative potentials at which complete plot. and spread back readily negative potentials. density. denoting a de. Unfortunately. ion or of Ca2+ with the lipid film [25]. thus. where Y  and Y  are the in-phase desorption is observed with the other and quadrature components of the electro- alkaline chlorides. known that the same impedance spec- bile. tion of SAMs because the broad range a large increase in fluorescence is observed of frequencies covered by this technique at the far negative potentials. lower on Hg than on Au. different equivalent circuits. the the fluorescence quenching efficiency. indicating a (usually from 10−3 to 105 Hz) may al- separation of the DOPC monolayer from low processes with different relaxation the electrode surface. fluorescence can be presence of Ca2+ imparts a high stability detected even if the fluorophore is at a to the SAM [24]. potential back from −1. the flu. upon scanning the small distance from the electrode. By scanning back times taking place within the electrified the potential. to nonradiative energy transfer to the in contrast to experiments in the absence electrode. charged mercury surface even at the most lar aggregates.110 1 Preparation of Monolayer Modified Electrodes At potentials of complete lipid des. Electrochemical impedance spectroscopy orescence intensity maintains a constant is extensively employed for the investiga- low level along the flat capacity minimum. slowly down to the positive potential limit. the lipid aggregates are not close proximity to the mercury surface completely detached from the negatively for hours as positively charged micel. frequency. it is well particles or aggregates on Hg are freely mo. a series connection of R and C yields . In fact. This des. the fluorescence decreases interphase to be detected and sorted out.85 V/SCE.1 M consequently ascribed to different relax- LiCl the capacity remains constantly lower ation processes. due pristine capacity minimum is recovered. be ascribed to their high positive charge tive shift in potential [16.

This apparently anoma- Here. of the impedance Z = 1/Y . Depressed arcs are range of the capacity minimum (i. be.1 M SAM on mercury at its desorption poten- KCl over the potential range from the tial of −1. a Cdl Q ‘‘mesh’’. respec. At any rate. this consisted of the re- Y = [R + (1/iωC)]−1 . by the presence of a lipid layer at some tively. [24] flat capacity minimum to peak 2 [26]. also reported in spectra plotted in a Z  tween −0. simulating Y = R+1 the film. a β value <1 was ascribed to Setting a CPE in parallel with the film a certain ‘‘roughness’’ at the interphase. RC network to fit the impedance spectra To investigate the behavior of a DOPC of a DOPC SAM on mercury in 0.4 and −0. This organic material.and high-frequency limits. equivalent circuit. at this negative desorption which reduces to a pure conductance. Incidentally. The physical sig. Nelson and semicircular arc may be simulated by a . its use is justified if is assumed to be sufficiently close to the the relaxation time of the process under electrode surface to slow down the mi- study is not single valued. to account for all features of the SAM with that of a bare mercury electrode spectra. compared the impedance spectrum of this However. 1. by introducing two sistance. where Z  and Z  are unity. they modified the expression of the at the same potential using a less involved admittance for a simple RC series circuit. over the potential versus Y  /ω diagram. Rsol .e. In Eq. Cs and Cinf are capacities in the lous behavior was tentatively explained low. capacity Cdl has the effect of accounting while an α value <1 was ascribed to a for a depressed semicircular arc (namely. A depressed ple series RC network closely. signal. thus denoting that the behavior the in-phase and quadrature components of the SAM approaches that of a sim. the   −1 Cdl and Q elements are practically iden- Cs − Cinf A(iω)β + C inf tical for the bare and the DOPC-coated 1 + B(iω)α mercury electrode. with in series. when α = 0 and to a pure ca. pacity when α = 1. a feature often encountered nificance of these two CPEs is not entirely in the spectra of SAMs plotted in a Y  /ω clear. gration of ions in response to the ac tributed continuously around a mean [27]. of the solution adjacent to constant phase elements (CPEs) in place the film. the parallel ar- of iωC: rangement of a capacity Cdl and of a CPE   Q. potential. with principal component analysis and re- Nelson and coworkers used a series gression [28]. (1). but the solution resis- (1) tance Rsol is about 20% higher on the latter electrode. trode surface. continuous distribution of low-frequency an arc whose center lies below the hori- relaxation phenomena. a CPE is an empirical separation from the water-coated elec- admittance function of the type A(iω)α . zontal axis). vealed by epi-fluorescence measurements. Bizzotto et al.3 SAMs on Hg Electrodes and Si 111 a semicircle of radius C/2 in this plot. but is dis. At the desorption potential. spectra of DOPC-coated mercury in con- Y  /ω = 0) and a maximum characterized tact with different alkali metal chlorides by an ω value equal to 1/RC. also re- A = 1/R.7 V/SCE) both α versus Z  diagram (sometimes called a and β were found to be very close to Nyquist diagram). namely.85 V/SCE. coworkers also analyzed the impedance with center of coordinates (Y  /ω = C/2.

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

place [33]. tributions follow each other in the order even though O2 can penetrate these films. such an electroreduction can take aqueous solution adjacent to the film. Starting from the origin. on Hg The experimental behavior of tion of the Cd(II). and Pb(II) ions phospholipid monolayers on a metal sub- to metal amalgam and that of the Eu(III) strate can be analyzed on the basis of and V(III) ions to the divalent form. 1. 1. ence across the hydrocarbon tail region.1. schematically depicted in Fig. to the glycerol backbone. In tentials somewhat positive of peak 1 [32]. and its decay is which depends upon the sum of σM and interpreted on the basis of a model in of the charge density σin of any charged . which a model of the membrane–solution in- on bare mercury occur over the poten.2. 3 [34]. the polar heads.2. rent decreases in time. of tion along the foot of the wave inhibited thickness β and dielectric constant εβ ∼ 2. they can be ascribed. two-electron reduction of O2 to H2 O2 [10]. On the other hand.3. The hydrated Cd(II) ion permeates N µdip the monolayer more easily than the chloro − + φd (c. and the gen ions. The inhibition polar head region. the con. array of regularly distributed microelec- sented by the four dashed curves in the trodes [21].2 Inhibitive Properties of Phos. ε0 εγ polarizable anions such as bromide and io. 1. β γ φ = σM + (σM + σin ) at least over the potential range of its sta. Cu(II). the meability of the monolayer. σtot ) and sulfate complexes. In view of However. of thickness γ and dielectric constant εγ . this model the potential difference φ across the metal–solution interface con- This indicates that the phase transition sists of the sum of the potential differences responsible for peak 1 increases the per- across the hydrocarbon tail region. whose contributions are repre. whose incorporation in the order. are inhibited well inside the polar head region and is by the lipid monolayer and initiate at po.3 Modeling of Phospholipid SAMs pholipid SAMs on Hg The electroreduc. At potentials approaching peak 1 the cur. It can be written as: trode reaction indicates that no electron tunneling can occur across the lipid film. such as furosemide. which the permeable areas in the defec- The plot is fitted to a series of four RC tive lipid film are regarded as forming an meshes.1. by the lipid monolayer is independent of which depends on the charge density σM time. The current for Cu(II) reduc. of decreasing relaxation times. with : σtot ≡ σM + σin + σex dide facilitate Cd(II) reduction and Cd(Hg) (2) oxidation to the extent with which they penetrate the monolayer at more positive Here the first term is the potential differ- potentials. in the presence of substances their R and C values. ε0 εβ ε0 εγ bility.2. and the diffuse-layer of the E(III)/Eu(II) and V(III)/V(II) elec- region.2.3. Phospholipid films inhibit the figure. The second term is the poten- penetration of the ion across the film [32]. terphase that accounts for the presence tial range of the capacity minimum of of any charged ionizable groups buried the DOPC-coated mercury.3 SAMs on Hg Electrodes and Si 113 middle of the flat capacity minimum [31]. denoting exclusive control by the on the metal. the makes the lipid film permeable to hydro- hydrocarbon tails. tial difference across the polar head region.

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

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

Cm ε0 εγ over. and the thickness β and γ of the hy. A/A(θ). a function of θ in Eq. A(θ).1 0.5 0 0. More. solutions of 0. the dipole-moment nor.2 −0. (2) and consider- ing how the various parameters in this The charge density σM (θ) on the metal as equation change following the expansion. the charge densities σin and σex due to or.4 −0.1 (c + constant) [V] [V] cw 0. after rearrangement: the ionized groups of the polar heads.8 0. 4 Plots of (χ + constant) versus (σin + σex ) dashed line is a curve of χw against the charge for DOPS () and DOPA () self-assembled density σM calculated by Damaskin and monolayers at −0.1 M KCl [24]. σtot cos θ) ε0 εγ mal component µdip of their polar heads. (6) can be estimated the potential difference after the expansion by noting that the charge Q(θ) following .6 0. σM (θ) cos θ drocarbon tail and polar head regions.2 0.2 0.3 0. σtot cos θ) Cm after drop expansion will all be equal to   N µdip γ their initial values times cos θ.3 −20 −15 −10 −5 0 5 10 15 20 (sin + sex) or sM [µC cm−2] Fig. + φd (c.50 V/SCE in buffered Frumkin [36] for a metal–water interface. its will take the form: cosine is just equal to the ratio. For comparison.7 0. − cos2 θ + φd (c. the number N of lipid molecules N µdip per unit surface.3 −0.116 1 Preparation of Monolayer Modified Electrodes 0. of the initial unexpanded area A of the film σM (θ) γ φ = cos θ + σin cos2 θ to the final expanded one. the to the plane of the lipid monolayer. = − σin cos2 θ − φ ε0 εγ ε0 εγ ing that the potential difference φ across the whole interface before the expansion (6) has the form of Eq. Recall.

Application of Eq. which amounts to theory. +30 mV [15]. (5).3 SAMs on Hg Electrodes and Si 117 the drop expansion is clearly equal to: therefore. This also explains the low value includes the dipole potential due to the of the dipole potential of DOPA. positive toward the interior of the film. φd . At the higher pH values at Q(θ) is obtained by measuring the which the polar heads of DOPS and DOPA charge that follows the expansion of a become progressively more negative. but rather to a group common (8) to these two lipids and buried deeper where χm is the surface dipole potential inside the polar head region. buried in this region. across and DOPC monolayers having very similar the diffuse layer. rate of change with a change in the charge . by measuring the as estimated from Fig. can be polar head consists of the sole phosphate regarded as constant in view of its small group and whose glycerol backbone is. and 0). the whole left-hand side of Eq. tion of the absolute potential difference. whose slope is equal to monolayer and becomes progressively the surface dipole potential minus the more positive with an increase in the potential difference across the polar head negative charge on the polar heads of the region created by any charged groups lipid. By estimating the potential in phospholipids consists of two main difference φd across the diffuse layer as contributions: a contribution from the a function of θ by the use of the GC glycerol backbone. we obtain values lipid-coated mercury drop while keeping close to those directly calculated from the its neck in contact with the lipid film neutral DOPS and DOPA monolayers. The slopes of the plots for DOPC and which does not contain ionizable groups DOPS at those pH values at which these inside the hydrocarbon tail region (σin = monolayers are neutral are similar. (6) become progressively more electrolyte. φ. however. whose electron spillover. Upon ignoring is much smaller. and a further contribution plotting this quantity against cos2 θ at a from the orientation of the adsorbed water constant applied potential φ. (6) about +150 mV and is positive toward can be measured as a function of θ. The DOPS the small potential difference. which. the dipole potential for DOPA solution interphase [37]. (2) to a DOPC SAM. allows an extrathermodynamic estima- yield a dipole potential of +140–+150 mV. as already described. (2) can be written as surface dipole potentials indicate that this follows: potential is not to be ascribed to the σM N µdip φ = + χm with : χm = − serine or choline group of their polar Cm ε0 εγ heads. φ backbone. Eq. spread on the surface of the aqueous This indicates that the dipole potential electrolyte [12]. 1. a straight molecules. exposed to the aqueous phase and effectively screened by the water Q(θ) = σM (θ)A(θ) − σM A (7) molecules. which is small on a neutral lipid line is obtained. across the whole mercury–aqueous Conversely. 4 by setting χ = charge following the contraction of a 0 for (σin + σex ) = 0. their lipid-coated mercury drop with the drop surface dipole potential values estimated completely immersed in the aqueous from Eq. This can of the polar heads and the capacity Cm be reasonably identified with the glycerol of the lipid SAM is given by Eq. whereas the charge density positive. By the interior. If we subtract from these values σM on the unexpanded film is obtained the contribution from water reorientation.

8 µF cm−2 substrate is overtaken by that of the water ∼ = −(250 ± 50)mV (9) molecules. This transition is regarded as responsible for peak 1. has been still have a higher affinity for the substrate reported to assume values ranging from compared to water. Both σM and Cm in contact with the metal and the heads in Eq.1.8 µF cm−2 . both incorporating some be written: water molecules: in the thin bilayer the tails σM of the lipid molecules are directed toward φ(−0.80 µC cm−2 = + (0. not particularly high. Thus. 16).2. to a minor Ref.1 and Competition of the heads (and. Moreover. Cm flat capacity minimum. (8) can lipid monolayer. as responsible for peak 2. flat capacity minimum in passing from di- ments with the substrate are considered to oleoyl phosphatidylcholine to dipalmitoyl become progressively more attractive with phosphatidylcholine and to dimyristoyl an increase in the absolute value of the phosphatidylcholine.450 V/SCE) = + χm Cm each other.050)V tive potentials the affinity of the tails for the 1. A negative shift in on DOPC-mercury equals 1.2. as estimated by ment of tail segments by head segments different procedures both on BLMs and at potentials at which the tail segments on a mercury electrode [15. at sufficiently neg- layers and the reorientation peaks Leer. If the affinity of the tail segments for the substrate is The adsorption isotherm of lipids mono. this leads to one-half of the difference φ between mercury and the drop surface almost exclusively covered by aqueous phase can be obtained by in.450 V/SCE (see Sect. Accord- ments of heads and tails of the lipid ing to the authors [38]. At still more nega- −0. the dipole potential extent. In view of the constant amount of lipid molecules on the surface of the It follows that the absolute potential mercury drop.3.118 1 Preparation of Monolayer Modified Electrodes density σM on the metal. This further transition is regarded versus the SCE by about 250 mV. (8) are experimentally accessible and exposed to the aqueous phase along the thermodynamically significant. ative potentials head segments and water makers and Nelson [38] determined the monomers displace the tail segments from adsorption isotherm of lipid monolayers the surface in a single transition. 20]. in view of their assumption that an increase in the hydro- polarizability. This gives rise to a +150 and +250 mV. water and the other half covered by a lipid creasing the applied potential E measured bilayer. the interactions of the and a decrease in the potential range of the water monomers and of the lipid head seg. The model predicts the tails carbon chain length and the presence of . 1. of the water monomers) with the χm due to the oriented polar heads of tails for the substrate causes a displace- a DOPC monolayer. positive toward the inhomogeneous layer of two phases con- hydrocarbon tails.8 ± 0. bilayer and of water covered areas. Eq. under the reasonable interfacial electric field. giving on a metal substrate by an approximate rise to a single peak due to a direct passage statistical treatment of a lattice model in from a lipid monolayer to patches of lipid which apolar water monomers and seg. this may explain the molecules interact with each other and merging of peaks 1 and 2 into a single peak with the substrate. Upon ascribing to χm sisting of a thin lipid bilayer and of a thin an average value of +200 mV.200 ± 0. −0. the applied potential causes an increasing while σM equals −0.1 µC cm−2 at attraction of the heads for the substrate.

8 µF cm−2 . un- be somewhat disorganized and permeable decane and dodecane have a high partition to water. and was ascribed to the growth tends to attain a limiting value.1 Electroinactive Compounds 4-monochlorobiphenyl is more effective Electroinactive neutral compounds As a than 2-monochlorobiphenyl. but then process. 1. even though the lipid mate. decay to zero [21]. is not bilayer along peak 2. At any rate. ing a mixed solution of the compound ity remains much higher than the value. This effect becomes compounds. Both clear aromatic hydrocarbons [39].3. by the that the lipid molecules tend to form a lipid octanol/water partition coefficient. the adsorption isotherm by a maximum and by an exponential of the given compound can be obtained. mixture to an HMDE. twisted ones. Hydropho- for mercury. Thus. negative shift and a depression of peaks 1 The slight decrease in the flat capacity and 2. Planar and coalescence of the preexisting defects polyaromatic molecules intercalate more formed along peak 1.3. it becomes expected increase in capacity stemming . expected for a compact of the electrolyte and by transferring the lipid bilayer. easily between the lipid tails than the nonplanar. appreciable with hydrocarbons with three.3 Incorporation of Lipophilic more effective in shifting the peak po- Molecules in Phospholipid SAMs on Hg tentials in the negative direction. by keeping the neck of coefficient but no observable effect on lipid the lipid-coated mercury drop in contact monolayers. say. while the effect of benzene should more than compensate for the and naphthalene is negligible. and by comparing the re- now available [12]. In fact. sponse of the film so obtained with that The current transients obtained by obtained by slow equilibration of a lipid- stepping the potential across the potential coated electrode with an aqueous solution range of peak 2 show a minimum followed of the compound. Thus. increase in the bulk concentration of these pacity minimum. such a bilayer must sufficient to explain this effect. as measured. even assuming bicity alone. and hence their affinity four or five aromatic rings [41].2. incorporation in the lipid monolayer. ture is distorted by the steric hindrance bic organic compounds.3. and phenothiazine [40] effective than biphenyl because of their into DOPC monolayers on Hg causes a greater molecular polarizability. which is often observed with an a slight decrease in the differential ca. this pound. such as polynu. of the ortho-chloro substituent [40]. 1.3 SAMs on Hg Electrodes and Si 119 C=C double bonds enhance the hydropho. the differential capac.1. and hence are 1. incorporation of neutral hydropho. is probably to be ascribed to more pronounced with an increase in the a thickening of the film following their aromaticity and hydrophobicity of the com. polychlo. thus. bicity of the tails. the above chlorinated biphenyls are more rinated biphenyls.2. whose struc- rule. and of the lipid in pentane on the surface 0. which is often accompanied by minimum. the time dependence The negative shift in the capacity peaks of the current satisfies the expression for increases with the bulk concentration of an instantaneous nucleation and growth the compound first linearly. The hydrophobic compounds with a lipid film spread on the surface of may be adsorbed in the film from very an aqueous electrolyte at potentials slightly dilute aqueous solutions or else by spread- negative of peak 2.1. In the latter case rial required for the formation of a lipid the mole fraction of the compound in the bilayer covering the whole drop surface is film is known.7–0.

250 to −0.750 V on a mercury electrode coated with a lipid 0 50 100 monolayer consisting of 67 mol% t DOPC + 33 mol% KC and immersed in [ms] aqueous 0. tures may act as powerful inducers of ≈2. was reported caused by the intercalation of the foreign to form pores inside a mercury-supported molecules. ence of a carbonyl group. With DOPC by an increased flow of negative capacitive monolayers. The result- by KC molecules give rise to the potentio- ing change χ in χ can be determined static charge versus time curves shown in from Eqs (2) and (5) by measuring the Fig. and KC has the same ef- surface dipole potential of phospholipid fect as cholesterol in increasing the rigidity monolayers [42].250 V to final potentials E varying by −10 mV increments from −0. where of a DOPC SAM containing 33 mol% KC Cm = 1. the differential capacity is practically equal to −σM /Cm . Hence χ = −(N µdip /ε0 εγ ) of −0. DOPC SAM by a mechanism of nucleation Adsorption of neutral molecules in the and growth similar to that of a number of polar head region may appreciably alter channel-forming peptides [43]. whose sigmoidal shape reveals two change σM in σM that accompanies consecutive two-dimensional phase transi- this adsorption at constant applied po- tions. It was thus ditions. peaks 1 and 2 and their broadening are 6-Ketocholestanol (KC).250 V/SCE.120 1 Preparation of Monolayer Modified Electrodes from the higher dielectric constant of why compounds with such different struc- aromatic compounds compared to that. 5. Under these con- DOPC monolayer (see Eq. of the lipid tails. 5 Charge versus time curves following a series of potential steps from a fixed initial potential Ei = −0.2 µF cm−2 . the DOPC and KC molecules are shown that the so-called hybrid polar com. 5. a steroid that due to a decrease in the cooperativity of differs from cholesterol mainly by the pres- the reorientation of the lipid molecules.1 M KCl [43].7 µF cm−2 is the capacity of the is as low as 1. an effect that can explain of the film and decreasing its differential −2 [µC cm−2] −1 Q Fig. . and the charge and by a concomitant increased sep- changes in φd (c. The concomitant terminal differentiation of various types decrease in the height of the reorientation of tumors. expected to be randomly distributed within pounds produce a positive shift in the the monolayer. 8). σtot ) that accompany aration between consecutive charge versus the small changes in σM are negligi. These transitions are characterized tential E = φ + constant. At potentials positive bly small. The poten- tial steps responsible for pore formation its surface dipole potential. σin equals zero. time curves in Fig.

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

The cysteine resulting DOPC and DOPS monolayers [45]. however.3. This indicates that hydrophobic in- envisage two potential energy wells for teractions are also operative. We can therefore Ca2+ . (RS)2 Hg or (RS)2 Hg2 . (see Sect. the lipid film. drocarbon tail region. The an. before penetrating the tail prothrombin. This procedure allowed the which the cystine residues form with determination of the adsorption isotherms the mercury surface atoms at the most of the TPhP+ and TPhB− ions in positive potentials. 1. the prothrombinase complex in the pres- This may indicate that these anions start ence of Ca2+ ions. yields directly the peak due to the reduction of the charge- opposite of the charge density of the ion in transfer complex. attains the limiting capacity region on the negative side value of 7 µF cm−2 . namely. This indicates that tions if Ca2+ is absent or if the pure PS .2. which ionic diuretic furosemide causes an initial stimulates blood coagulation. in addition these ions at x = 0 and x = β. minimum and the pseudocapacity peak increase with the prothrombin concen- Peptides and proteins The cationic an. discreteness. 47] electrode surface (x ≈ 0) rather than in found. All these ment II. Both the capacity of-charge effects were considered. results from slight decrease in the capacity minimum the cleavage of the plasma protein pro- at low bulk concentrations [33] and then an thrombin under the catalytic action of increase at higher concentrations [33. tration until about 3 µg cm−3 . when the tibiotic polymyxin narrows the minimum capacity minimum. 3) and in direct contact with the by mercury. Thus. once itive minimum at about −0. 44]. In from such a reduction tends to desorb interpreting these isotherms. prothrombin adheres to negatively charged just as neutral compounds. by complexing Ca2+ with EDTA. By adsorbing located in the polar head region (x ≈ β prothrombin on PS monolayers supported in Fig. that appreciable adsorp- the much less polarizable intermediate tion is also obtained in the absence of hydrocarbon tail region. membrane surfaces by Ca2+ bridges be- Small lipophilic ions such as tween the negative charges of PS and tetraphenylphosphonium (TPhP+ ) and the γ -carboxyglutamic acid residues of tetraphenylborate (TPhB− ) prefer to be fragment I of prothrombin. It is generally assumed that ions depress and broaden peaks 1 and 2.2). In the presence of prothrom- located at x = β to a potential positive bin. Thrombin.35 µF cm−2 [46]. The charge involved in a potential step not all the prothrombin incorporated in from a potential negative (positive) enough a PS monolayer is displaced from the for the anion (the cation) to be entirely surface [5]. 44].5 V versus decreased by the charge involved in the Ag/AgCl. the quadrature component of the (negative) enough to induce a complete electrode admittance shows a flat capac- translocation of the ion to x = 0. with a to electrostatic interactions.1. fragment I and frag- region at higher concentrations. This value is attained and decreases the capacity minimum by at higher prothrombin bulk concentra- ∼0. stance. for in- potential energy barrier in between [45]. At more negative potentials this same potential step in the absence of is followed by a rounded pseudocapacity the incorporated ion. This cleavage also interacting with the polar heads at low yields two other molecular fractions of concentrations. C. Lecompte and Miller [6.3.122 1 Preparation of Monolayer Modified Electrodes derivatives cause a moderate increase in this peptide does not penetrate the hy- the capacity minimum [40.

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

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

E 0 .4 0. which creates a and Ql is the limiting charge in the pres. as shown by the dashed curve b rior. This prediction agrees with experi. The an additional homogeneous chemical step mechanism predicts a plateau that is con. 6. with the aim of altering their dipole po- where Qd is the diffusion limiting charge tential.5 × 10−7 M gramicidin by stepping from a fixed initial potential Ei = −0. Since the transfer of the thallous ion in in Fig. 1. 6 Plots of the ratio of the chronocoulometric charge Q (t = 100 ms) to its diffusion limiting value Qd against (E − E0 ). mimicking the deactivation and release of trolled partially by diffusion toward the a Tl+ -gramicidin intermediate from the film and partially by the binding step at electrode surface. it also predicts surmounting of the potential energy bar- a positive shift in the half-wave potential rier located within the channel. of Two lipophilic neutral molecules are the thallous ion/thallium amalgam couple commonly incorporated into membranes by an amount equal to (RT/F) ln(Qd /Ql ). in competition with the the mouth of the channel. More the mercury with amalgam formation is recently. because of the presence of a carbonyl . (b) on mercury coated with a DOPC monolayer upon stirring to allow gramicidin incorporation. dipole potential negative toward the inte- ence of the gramicidin-modified DOPC rior of the lipid film. which creates film.2 0 150 100 50 0 –50 –100 –150 –200 –250 E– E0 [mV] Fig.1 M KCl aqueous solution containing 4 × 10−4 M Tl+ + 1.6 c 0. Rueda and coworkers [56]. with respect to the formal potential.8 b Q /Qd 0. obtained from a 0. (c) on mercury coated with a DOPC monolayer containing 23 mol% 6-ketocholestanol upon stirring. ical impedance spectroscopy.250 V/SCE to progressively more negative potentials: (a) on bare mercury. the dependence investigating this system by electrochem- of the faradaic charge upon the overall ap. namely. by expected to be Nernstian. and KC. phloretin. which was calculated on the direct contact with the metal surface to basis of the above mechanism. postulated plied potential E is also Nernstian. The dashed curves were calculated on the basis of the mechanism outlined in the text [55]. a dipole potential positive toward the inte- ment.3 SAMs on Hg Electrodes and Si 125 1 a 0.

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

7 The left-hand side of the figure shows Ei = −0.700 V in 25 mV increments. UQ−• . determining protonation of this radical tically parallel. The faradaic contri- Equilibrium bution. followed by the rate- Fig. against the applied po.s.d. UQ reduction takes place via the reversible ing portion preceded by a sloping foot and uptake of one electron yielding the UQ followed by a sloping plateau. The foot and the plateau run prac.075 M borate buffer of pH 9. of UQ electroreduction increases progres. to Q(t) due to the reduction UQ + e ←−−−−−→ UQ−• of UQ is readily estimated by measuring   the charge from the straight line obtained F [UQ]/[UQ−• ] = exp (E − E 0 ) by extrapolation of the foot of the charge RT versus potential curve. The maximum r. UQH• : the lipid monolayer. ferent potentials and pH values allow the ting the charge Q(t) at a constant electroly. the film and agrees with a two-electron sively.6 V Q f. limiting value Qf . reduced in less than 1 ms. mechanism of UQ reduction to be clar- sis time.7 V –1.0 –0.3 SAMs on Hg Electrodes and Si 127 –0. with a ris. ified on the basis of a general approach. after which Q(t) The charge versus time curves at dif- becomes again independent of time.5 V [µC cm–2] Q –0.225 to −0. 7.max –0. The a 0.3 V 0 25 50 −0. for UQ con- rated in the lipid monolayer is completely centrations in the lipid film < 1 mol%. Qf (t). reduction of UQ to UQH2 .4 V –0. until ultimately the UQ incorpo. as shown in radical anion. as obtained by right-hand side shows the corresponding stepping the potential from a fixed initial value Q(t = 50 mV) versus E curves [60].45 −0.5 –0.4. 1. say 50 ms. tential yields a sigmoidal curve.200 V/SCE to final values E varying from Q(t) versus t curves for 1 mol% UQ reduction in −0.max attained by Qf (t) UQ−• + H+ −−−→ UQH• measures the charge involved in the com- plete reduction of the UQ incorporated in Rate = k[H+ ][UQ−• ] (10) . Plot.2 −0. and their common slope is anion yielding the corresponding neutral a measure of the differential capacity of radical.7 t E (SCE) [ms] [V] Fig.

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

as in where the concentrations [V+ ] and [V0 ] the case of UQ reduction. points to a re. E) hand side of Eq.3 SAMs on Hg Electrodes and Si 129 the electrochemical behavior of vitamin versus t curves at different potentials E by K1 . The only difference is represented by the fact that. an essential constituent for blood co. the kinetics of transfer steps are in quasiequilibrium K1 H2 oxidation is independent of pH. as obtained from the Q(t. value corresponding to the first Q versus logical quinone in a self-assembled DOPC E wave. 1. rds. upon incorporating this physio. E10 E20 K1 H2 . keeping the faradaic charge constant at a agulation. if we higher than the second [67]. Consequently. the still unreduced V2+ species). rather than OH− . carried out by the d[V2+ ]/[V2+ ]2 = 2k exp[f (2E10 same potential-step procedure adopted for UQ (see. exp(−3f E) with : f ≡ (15) RT versible electron-transfer step followed by a rate-determining protonation step. V+ + e ←−→ V0 . yield two sigmoidal [V2+ ](t) waves in the plot of the charge Q(t. [V+ ]/[V0 ] = exp[f (E − E20 )]. e. to a con- uptake of two electrons per V2+ molecule stant value of the concentration [V2+ ](t) of in the lipid monolayer. monolayer supported by mercury [64]. (12). UQ/UQH2 couple. This equation shows that. At V2+ con. tions: [V2+ ]/[V+ ] = exp[f (E − E10 )] and V2+ → V+ and V+ → V0 .g. E) + E20 )] exp[−3f E]t (16) against the applied potential E at con- stant electrolysis time t = 100 ms: the first where [V2+ ]* is the initial viologen con- chronocoulometric wave is three times centration. The data analysis. both incorporated in a Hg-supported DOPC = k exp[f (2E10 + E20 )][V2+ ]2 monolayer. carried out F on the basis of Eq. (16) is kept constant and. k dation. The This slope can be rationalized on the basis mechanism of K1 reduction and that of of the mechanism: oxidation of the corresponding quinol. the main proton acceptor involved V+ + V0 −−−→ V+ 2 (14) in the rate-determining deprotonation of the K1 H+• where the first two elementary charge- 2 cation radical is H2 O. . The and the third one is a chemical rate- chronocoulometric procedure was also determining step. Fig. The plot of ln t ver. By integrat- metric measurements on the lipophilic ing this equation after separation of vari- dioctadecylviologen (C18 )2 V2+ (henceforth ables we obtain: briefly denoted by V2+ ) incorporated in 2+  ]∗ [V a DOPC monolayer. 7). In this case the rate employed to study the electroreduction v of the process is given by: of the polyaromatic cation safranine [65] d[V+2] 1 d[V2+ ] and that of the azocrown ether L16 to v= =− = k[V+ ][V0 ] dt 2 dt the corresponding hydrazo form [66]. in K1 H2 oxi. are analogous to those for the V2+ + e ←−→ V+ . hence. E) versus t curves the centrations less than 1 mol% the overall pairs of values of t and E corresponding to height of the two waves corresponds to the a constant value of Q (and. is linear and exhibits a slope of 3. Chronocoulo. are expressed as a function of [V2+ ] Viologens are electroreduced in two through the corresponding Nernst equa- pH-independent electron-transfer steps. extract from the Q(t. the left- sus FE/(RT).

an n value of 1. V2 + e −−−→ 2V 0 versus t 1/2 plots is indeed proportional to (17) the viologen bulk concentration and yields the first of which agrees with the mech. plus a the ln t versus FE/(RT) plot. The pro. These initial findings started a DOPC monolayer. 1. Only af- along the plateau of the two waves consist ter the extensive studies of self-assembled of a capacitive contribution Qc . in the reduction of the diheptylviologen many of these investigations were focused dication (C7 )2 V2+ incorporated in a DOPC on electroanalytical detection of thiols by monolayer [68]. t) versus t curves was barely investigated [76–79]. where n is the number of cesses responsible for the two waves are Faradays exchanged per mole of the therefore: reactant and D is the diffusion coefficient of the latter. All the main features first wave and of 2 along the second one.1. further faradaic contribution Qd due to anism of Eq. E) versus during the electrolysis time t at the E waves.5 along the plateau of the anism of Eq. These authors acts as an electron-transfer mediator from demonstrated that thiol films form spon- Fe(CN)6 3− dissolved in the aqueous so. The mechanism is diffusion controlled. Consequently. t) upon t and agreement with the mechanism of Eqs (15) E are quantitatively accounted for on the and (17). 69] in studies of the cysteine/cystine to the two V2+ and V0 monomers. The incorporation step is. Since the overall contributions flow almost instantaneously. height of the two waves corresponds to Qd increases progressively in time and the uptake of 2 F mol−1 of V2+ . the of formation of these SAMs on mercury chronocoulometric Q(E. t) 2V2+ + 3e −−−→ V+ + 2 .130 1 Preparation of Monolayer Modified Electrodes therefore. of films of water-soluble thiols on Hg An analogous mechanism is operative from their aqueous solutions. 81]. . contribution Qf due to the amount of which have provided a route to well- viologen incorporated under equilibrium ordered. in of the dependence of Q(E. the first of which is three times final potential E. The mech. taneously on Hg in solutions containing lution to the mercury surface across the cysteine. (14) is consistent with the (C7 )2 V2+ diffusion from the bulk solution presence of two Q(t = 100 ms. respectively. the increasing separation be. Qd (t) = 2nF (Dt/π)1/2 3/2 and 1/2 of 1 F. the same is true for the right. that sparingly soluble. a faradaic alkanethiols and their derivatives on gold. oriented monolayer films [80. The main difference is stripping [70–72] or square-wave voltam- represented by the fact that (C7 )2 V2+ metry [73–75] under conditions in which is incorporated in the lipid monolayer the amount of the thiol deposit on Hg is from its aqueous solution. conditions at the initial potential Ei hand side. where it is proportional to its bulk concentration. This explains the slope of 3 for where it is still electroinactive. [(C7 )2 V2+ ]*.3 Thiol SAMs on Hg tween the two waves with an increase The formation of thiol monolayers on Hg in [V2+ ]* is explained by the increasing was first reported by Kolthoff and cowork- stability of the V2 + dimer with respect ers [3. (14). for instance. Thus. which is impermeable series of investigations on the formation to Fe(CN)6 3− in the absence of V2+ . The slope of the linear Q(E. V2+ system by dc polarography.3. While the first two higher than the second. the two its time dependence is expressed by the consecutive waves involve the uptake of Cottrell equation. However. basis of the above mechanism [67]. at submonolayer levels.

1.1 Preparation Methodology and Thus. layers can be gained. (18). in the presence of oxygen [88]. according to the general re. featureless. Moreover. hydrogen evolution in the absence of tion them prior to use. 1. defect-free sur. such thioguanosine were reported to form on an as cysteine. with λ = 1. partial charge transfer. Hg has a external circuit. much more easily. which removes electrons from the Hg deprotonation. Self-assembly of thiols on Hg also takes Moreover. pro- assembly is accompanied by partial or total ceeds to full electrode coverage because it electron transfer from the sulfhydryl group occurs simultaneously with oxygen reduc- to the metal and by concomitant sulfhydryl tion. electrode. these action: electrons can only be removed through the flow of an oxidation current along a closed Hg + RSH ⇐. Hg has a not involve a flow of electrons along the high affinity for thiols. the reaction of Eq.3 SAMs on Hg Electrodes and Si 131 the use of liquid mercury in place of evidence for the formation of these mono- gold [16. referring to homogeneous. with renewable and there is no need to condi. self-assemble spontaneously HMDE under open-circuit conditions only on mercury from their aqueous solutions. Like Au. As distinct from phospholipids. In this case.3. full SAMs of 6-thioguanine and 6- Procedures Water-soluble thiols. because the passage terest because of the unique properties from mercurous to mercuric thiolate does of this liquid metal. mercurous or mercuric thiolate monolay- face. the self. In the absence of oxygen.3. while Au exhibits surface steps and ers becomes meaningless in the case of kinks that play a significant role in es. with oxy- gen reduction to water in its presence. tablishing defects in the deposited films. mercury electrodes are readily place under open-circuit conditions. oxygen or. However. 82–87] has attracted much in.1.

α and ergy (∼200 kJ mol−1 ) with respect to the λ are expected to assume close values. and α is Thus. but detectable. As a rule. Au−S binding energy (∼400 kJ mol−1 ). the mercury upon adsorption. tal charge transfer (α = λ = 1). No such dissolution of gold by As a matter of fact.⇒ Hg − SH1−α R+λ−α electric circuit. However. transfer of SAMs of rather soluble thiols from the thiol solu- Here λ is the partial charge-transfer co. a SAM of mercaptopropionic acid the degree of dissociation of the sulfhydryl in a thiol-free solution is disrupted on a group. may be due to the lower Hg−S binding en- nation are strictly correlated events. solve [73]. tendency of chemisorption of the RSH thiol on Hg. or The Hg notation is merely used to denote also to a slight. formation SAMs of water-insoluble thiols. but not on a Au support. at an appropriate applied + λe + αH+ (18) potential. the fraction of electron a thiol-free solution in the same solvent charge transferred from a sulfur atom to causes a partial dissolution of the SAM. thiols has ever been reported. Since partial electron transfer from Hg support. no definite ing a mercury drop in a 20% (by volume) . at the Hg–water and mercuric [77. This the sulfhydryl groups and their deproto. namely. 69] or both mercurous long-chain alkanethiols. Hg-thiol adducts such as Hg(SR)2 to dis- and has no stoichiometric implications. such as of mercurous [3. tion in which they have been formed to efficient. under conditions of to. 79] thiolate monolayers interface are usually obtained by immers- has been postulated.

The structure cane from 10 seconds to 2 minutes [82.3. as opposed to to nine monolayers. In Langmuir monolayers the or- these SAMs. allowing aqueous or organic subphases.1 Surface-sensitive Techniques the reflectivity data to a density-dependent Owing to the difficulty of applying surface. does not affect the SAM prop. pentane or hexane). 87]. These SAMs are stable for mismatch between this support and alkane a long time in thiol-free aqueous solutions. at least for alkanethiols with insoluble in water are soluble in organic nc > 10–15.1. The thiol-coated mercury drop ob.2.3. The atomic surface such as mercury. the strong Au−S bonds prevail atoms firmly bound to the surface of the over interchain interactions. Same considerations apply to tial to order the thiol SAM. the small to the solution.g. such as rinsing. 85] and Hg−S interactions prevail over interchain acetonitrile [84]: in electrolytic solutions of interactions. dissolved in a suitable analogous SAMs on solid supports such solvent (e. or to Langmuir monolayers on surface of an aqueous solution. which probes the where they are soluble under the form of electronic density profile along the surface alkanethiolates [74. Another procedure surface plane [89]. on the as Au.3. On liquid mercury the strong polar solvents such as ethanol [16. After one or two immersions and interactions of the monolayer with and subsequent emersions. Alkanethiol alkanethiols with up to eight carbon atoms SAMs on Hg were also investigated by in 0.3. On a solid support such as monolayer is formed. indicating that the . in a cell. X-ray diffraction (GIXD). Figure 8 shows this normalized profile for bare Hg (dashed line) and 1.2 Structure and Physical Properties for n-octadecanethiol and n-dodecanethiol of Thiol SAMs on Mercury monolayers. layering of bare mercury persists in the tural investigations by these techniques thiol-covered surface.1.2–0. an alkanethiol its support. but since the liquid mercury these solvents they can self-assemble on surface has no intrinsic long-range order. are available in the literature. nc of carbon atoms from 8 to 30 on mer- tained by this ‘‘soaking procedure’’ is then cury was investigated by grazing-incidence rinsed with the solvent to remove un. mounting der is induced by interchain interactions. normal. model reflectivity calculated from the sensitive techniques to a liquid surface Born approximation. spacings is compensated by a molecular tilt Normal handling of an HMDE coated with of ∼30◦ . with the sulfur Au(111). long-chain alkanethiols subphase. The main result was (spreading procedure) consists in spread. X-ray reflectivity [89]. of SAMs of n-alkanethiols with a number 86]. which is sensi- adsorbed alkanethiol and immersed into tive to the molecular structure within the the aqueous solution. or stirring the solution with a which exceed the strength of the hydro- stir bar. imposing a mercury drop and the alkyl chains exposed well-defined long-range order. This was obtained by fitting 1. This dif- the solvent to evaporate and immersing ference in behavior is explained by a the mercury electrode into the solution competition between interchain van der through the thiol film at a well-defined Waals interactions within the monolayer velocity [86]. the observation that these SAMs have no ing an amount of thiol corresponding to six in-plane long-range order.132 1 Preparation of Monolayer Modified Electrodes solution of the thiol in ethanol or hexade.5 M NaOH aqueous solutions. Hg and be investigated by electrochemical there is no underlying corrugation poten- techniques. Naturally. only very few struc. gen bonds between the monolayer and the erties.

the in-plane peaks of the GIXD pat. esti.0 surface layers of mercury. estimated from scan (x) one. which than 2 minutes.3 SAMs on Hg Electrodes and Si 133 Fig. the surface roughness. The upper and lower figures are aligned with each 1. pointing to whose volume was regulated by a syringe.8 <r(z)>/r∞ layer [89]. 8 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. atoms.4 0. which of the outermost mercury layer. Lea et al. while fatty acids. were avoided by resetting the height an in-plane order is observed [90]. due to slow waving of the mercury sur- terns of thiol multilayers on Hg. For alkanes. A baseline at every x scan. Vertical lines in the model mark the position of the three outermost 1. . exhibit standing-up phases at high bare mercury are a shoulder in the den. The length SAMs on mercury was made by Bruckner- of this step matches that of the fully ex. STM vertical orientation appears only when images of bare mercury appear smooth. is about interact with Hg more weakly than thi- ˚ The only differences with respect to 1 A.23 A˚ 2 .6 0.02 e A˚ −3 ).34 ± 0. In this way. a slight decrease in the amplitude An attempt to obtain scanning tunneling of the first mercury layers. where face. lacking such head- both cases. These y-directed oscillations. cury show broad oscillations along the This agrees with a cross-sectional area slow-scan (y) axis. the STM images of bare mer- points to a densely packed monolayer. with the origin of z coinciding with the first mercury 0. tended alkanethiol molecules.2 other. but not along the fast- per molecule of 19. ols. a vertical orientation of these molecules was partially coated with n-octanethiol by within the SAM. groups. 1. 0. Using the constant height is close to that in crystalline alkanes. exposing it to the thiol vapor for less tron density (0. mode. The high SAM elec. In exist. [93]. and a step at microscopy (STM) images of alkanethiol the position of the alkyl chain. only lying-down phases on mer- mated from the width of the density profile cury are found [91]. coverage and lying-down phases at low sity profile at the position of the sulfur coverage [92].2 0 –30 –20 –10 0 10 z [Å] thiol monolayer induces no major changes strong headgroup–mercury interactions in the liquid/(metal surface) structure.

by im (t) = Q(t)/t = 0. 69. This volume of the sessile drop is decreased fur. with many thiols. the time t elapsed from drop birth. In particular. Under these conditions. increase in the thiol bulk concentration.3. no STM images of single purely hypothetical [3. A(t). it is ex- mean limiting current attains a maximum pected to ultimately deposit and form a value that does not increase with a further multilayer on the mercury surface [74. At an HMDE cysteine limiting height and whose limiting current yields a dc adsorption polarographic pre- is diffusion controlled. which is one of the most exten- as the prewave has attained its maximum sively investigated. mercuric cysteine thiolate monolayer are Unfortunately. the thiol. of which. the spherical drop being proportional to sure–area curve. This indicates that in the present case volume ratio. 69]. thiolate and Hg [74]. Sim- thiol molecules have been obtained so far ilar dc oxidation prewaves are observed on Hg. At concentrations >∼ the product is a Hg(I) thiolate [69. Hence. case of cysteine. At more positive potentials. consensus on the nature of the resulting This is due to cysteine adsorption with par. oxidation product. N-oxide the formation of the correspond- At very low cysteine concentration the ing disulfide was postulated [78]. the the STM image shows reproducible islands maximum mean limiting current is given of similar tunneling current on a back. This value corresponds owing to an increase in the surface area-to. by tion is equal to m A(t).2. There is no general wave over a pH range from 2 to 9 [3.134 1 Preparation of Monolayer Modified Electrodes while those of thiol-coated mercury show transferred to the mercury upon adsorp- large surface features. where m is decreasing the drop volume slightly.85λF m m2/3 t −1/3 . the the maximum surface concentration of sessile drop maintains its spherical shape. For 2-mercaptopyridine tial charge transfer.3. such as benzyl mer- captan. and 2-mercaptopyridine N-oxide [78]. according to Eq. being insoluble in water. and the is also sparingly soluble in water. Linear sweep voltammograms of cysteine Under these conditions the charge Q(t) at an HMDE yield an oxidation peak that .2 Electrochemical Properties 0. 1-butanethiol and 1-decanethiol in 1. As the where m is the mercury flow rate. total film is now in an ordered two-dimensional charge transfer can be safely assumed for solid state. ground of lower tunneling current. 77] 2 × 10−4 M the growing area. it is usually assumed that fusion controlled. in practice. 74. 75]. The resulting STM images all soluble thiols.85 m2/3 t 2/3 in view of the volume of the liquid-like region of the surface pres. (18). 77. to a compact cysteine SAM for λ = 1. equation allows λF m to be estimated ther.1. the drop assumes a flattened shape at ∼70 µC cm−2 . Soluble thiols The electrochemical behav- cysteine and other water-soluble thiols [74] yield a dc polarographic wave (the so-called ior of water-soluble thiols is exemplified by main wave) that starts developing as soon cysteine. This suggests that the thiol charge transfer is total. Any arguments in fa- show small parallel n-octanethiol ridges vor of the formation of a mercurous or of higher current density (1–10 nA high). noting that A(t) equals thus suggesting that the thiol film is in 0. 79]. In the limiting current of this prewave is dif. dispro- the drop is instantaneously covered by a portionates into the corresponding Hg(II) compact thiol monolayer as soon as it pro.2 M NaOH [74]. Since Hg(II) thiolate trudes from the capillary orifice.

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

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

adsorbing the thiol on an HMDE from Cyclic voltammograms of soluble thi. due to the forward elec. the charge under the resulting reductive des- reductive desorption peak may undergo orption peak increases with an increase in splitting [96.0 E [V] Fig. The At higher bulk thiol concentrations. during tion–desorption peaks. rinsing it with during the positive potential scan. Thus.2 0. due to the under a potential positive of the adsorp- corresponding backward reaction. 1. 10 (a) Cyclic voltammogram of mercury in a pH 4 aqueous solution of i 0. of two ω-mercaptoalkanoic acids. a thiol solution at a potential negative of ols are often characterized by an oxidative the adsorption–desorption peaks. (18) with λ = α = 1. which group. The nature of the func. the thiol concentration used for the adsorp- tional group affects the sharpness and tion. This procedure was also potentials with an increase in thiol length used to measure the adsorption isotherms and a decrease in the size of its head.4 –0. the same applied potential. potential in the negative direction. ing the electrode from the solution under trode reaction of Eq. were found to satisfy the Frumkin model tion–desorption peaks. If the ex not desorbed. while the A term is regarded case of ω-mercaptoalkanoic acids [98] by as the constant contribution associated ex situ measurements.025 V/SCE across the oxidative adsorption peak of 0 t 0. attaining a maximum limiting value potential of the reduction peak. [s] . thiols are generally with attractive lateral interactions. At potentials negative of the adsorp.6 –0. but remain physisorbed on situ procedure is modified by immersing the mercury surface. 10a). remov- adsorption peak. and scanning the the negative potential scan (see Fig. immersing it in a thiol-free solution a reductive desorption peak.1 Fig. 97]. (b) Current versus time (b) curve obtained by stepping the potential from −0. this corresponding to a full monolayer cover- peak sharpens and shifts to more negative age (83 µC cm−2 ).l M acetic acid containing 1 × 10−4 M 6-thioguanine. Clear evidence for the thiol-coated mercury drop in a thiol- such a physisorption was provided in the free solution at a potential negative of 40 [µA cm−2] i 0 –40 (a) –0.35 to −0. these consisted in with the Hg−S interaction. 10a [100b]. and by water.3 SAMs on Hg Electrodes and Si 137 metal surface.

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

about five. This is due to the highly im. and can spread back onto the electrode surface without any loss of material. aqueous solution. while in water it varies . the negative direction by about 60 mV per ity. a close. This occurs C18 to C6 [84]. The flat capacity minimum from ethanol [16] and ∼80 µC cm−2 for of n-alkanethiols extends over a broader n-hexadecanethiol from acetonitrile [84]. If.1. It is usually higher atoms. from 3 to 6 µF cm−2 on passing from ties is often restored [16. This neous nucleation. procedure (see Sect. This phe- linear voltage scan yields a desorption peak nomenon is ascribed to a slow hydrogen due to the backward electrode reaction of evolution resulting from the penetration Eq.3. increase in scan rate. just after the such as long-chain n-alkanethiols. 85]. the charge under the hexadecanethiol is not oxidized until about reduction peak of C18 decreases with an 1. In mercury electrode coated with a SAM of n. it amounts peak attains an almost constant maximum to ∼115 µC cm−2 for n-octadecanethiol value [84. In the case of 6-thioguanine. potential region in water than in organic Henceforth.3 SAMs on Hg Electrodes and Si 139 that involved in the voltammetric adsorp. The charge under ordered C18 SAM and their electroreduc- the peak depends to some extent on the tion by the catalytic action of the sulfur nature of the solvent. yields an oxidation readsorp- which they form stable SAMs with a low tion peak. capacity minimum in acetonitrile varies packed SAM with exactly the same proper.3. Thus. un. This range extends in both directions each unitary increment in pH [16]. owing to the nc of carbon atoms will be briefly denoted increased hydrophobic interactions result- by Cn . 1. the mercury electrode is kept for water. remain in the proximity of the electrode dered thiol molecules [100c]. The peak may also split into two of water molecules into the partially dis- at high pH values [16]. Thus. which stant minimum value of ∼70 µC cm−2 for protects Hg against oxidation.1 M sulfhydryl group to the metal is accom- NaF takes place at about 0.4 V [82]. For n-alkanethiols with are moderately soluble and are directly a number of carbon atoms higher than adsorbed from the solvent. indicates that charge transfer from the while oxidation of bare mercury in 0. whose peak potential shifts in and practically constant differential capac. and can be interpreted restoration can be explained by postulat- quantitatively by including an additional ing that the desorption gives rise to thiol contribution from double-layer charging micelles or similar organizations. Re- Insoluble thiols Water-insoluble thiols. 1. This with an increase in chain length. (18). where n-alkanethiols high scan rate. attaining a con- permeable and defect-free SAM. it is usually higher in or- 2–4 minutes at a potential corresponding ganic solvents than in water.4 V/SCE. in which the current transients are close to those the aqueous solution is saturated with the predicted for a two-dimensional instanta. n-alkanethiols with a number solvents such as ethanol. after reductive desorption of the ing from the lower solubility of thiols in thiol. a panied or preceded by deprotonation. this is prevented by a sufficiently in organic solvents. more frequently by using the ‘‘spreading’’ tion peak. Thus.3. verting the potential scan. negative-going scan that causes reductive acterized by a broad potential range over desorption. are char. the charge under the reduction der saturating conditions. Moreover. 86]. the flat to the flat capacity minimum. which and one from slow adsorption of disor. A negative scan rates ≥ 100 mV s−1 [16]. thiol that is spread on its surface.1).

On the other hand. experienced versus log f (Bode plot) has a slope of by the diffuse-layer ions to be estimated at −1 (Fig. A different A closer insight into the electrical proper. this has of- trolyte concentration. 0. At very high frequencies the −3 µC cm−2 . and is the equivalent circuit in inset 2 of Fig. SAMs. namely. Over a allows Cd to be measured as a function broad frequency range. This oc.1 M and regarding Ct as independent of nal. The mercury–thiol solution in. 2. due to the the order of 10 µF cm−2 . because of the presence of any traces of impurities capa. important parameter of alkanethiol mono- curs at higher frequencies the lower is layers is the charge involved in their R . Therefore. the aqueous In this case the diffuse-layer capacity Cd electrolyte is represented as a resistor R can be estimated by making it comparable is series with the thiol monolayer (see in.95 µF cm−2 on passing greater than Rt . high polarizability of the peptide bonds. constant ε equal to the value. These relatively terface can be satisfactorily simulated with hydrophilic molecules form SAMs that ex- an equivalent circuit in which the thiol hibit a high resistance comparable with monolayer is represented as a capacitor that of n-alkanethiols. 11). q. of Cd is entirely negligible. the control of the from C18 to C14 [86].1. pacitor. of decane Strictly speaking. oligopeptide molecules that by using electrochemical impedance spec.3.1. the plot of log |Z| allows the charge density. −j/(2πf Ct ) tends the reductive desorption peak. as shown in inset 3 of Figure 11.0 [85]. impedance tends to pass to Rt . In practice. and ultimately or without [87. C = ε0 ε/d. ten been identified with the charge under at very low frequencies. and the ter are in fairly good agreement with the Bode plot tends again to become hor- differential capacities calculated from the izontal. impedance of the capacitor becomes so low that the control of the impedance passes 1.2. 11). theory. 11 therefore frequency independent. Rt is of the order of 20 M cm2 .3Total and Free Charge Density to the series resistor R . pacitor Ct . 11). with [103] to become comparable to.3. The values in wa. and hence the higher is the elec. KCl concentration range from 5 × 10−3 to where f is the frequency of the ac sig. thiols in the most extended configuration. by setting the dielectric and starts controlling Z for f < 10−1 Hz. While the impedance of c as low as 5 × 10−3 M. choring to the metal [102]. |Z|. With well-behaved n-alkanethiol Helmholtz formula for a parallel-plate ca. terminate with a sulfhydryl group for an- troscopy. the equivalent circuit and the thickness d of the thiol film equal should also include the capacity Cd of the to the length of a space-filling model of the diffuse layer adjacent to the thiol SAM. the impedance of the resistors Rt and the electrolyte concentration. the use of R is equal to their resistance. By covering a the capacitor Ct is given by – j/(2πf Ct ). and the Bode on Mercury Coated with Thiol SAMs One plot tends to become horizontal. Hence. situation is encountered with thiolpep- ties of thiol-coated mercury can be gained tides. with Ct by the use of KCl concentrations set 1 of Fig. the capacity Ct of n- from 8 to 18 also satisfy the Helmholtz alkanethiols is so low that the contribution formula with ε = 2. self-assembly on electrodes. ble of penetrating the film. in series with the Rt Ct mesh (inset 2 of C values of n-alkanethiol SAMs with nc Fig. but a capacity of Ct with a parallel resistor Rt . of c.70 to 0. Fitting this dependence to the GC of the impedance is controlled by the ca. the modulus. 104] correction for the .140 1 Preparation of Monolayer Modified Electrodes from 0.

namely. corresponding to the same KCl concentration. Inset 3 shows the reciprocal. adsorption with charge transfer. the latter tial E constant when the electrode surface quantity can only be estimated on the basis is increased by unity and the composi. density on the metal side of the inter- sorption processes involving partial or total phase.87 K cm2 (d).000 V/SCE over 1/Cd . 1.14 Mcm2 . due to the surface excess of free charge transfer between the adsorbate and electrons. 61 (b).06 d Cd (σM = 0)–1 [cm2µF−1] 0 2 4 Log (f ) [Hz] Fig. The method of choice to measure σM This quantity is called ‘‘total charge’’ by both on solid and liquid electrodes consists Frumkin [105] and will be denoted here in starting with an uncoated electrode . The solid curves are 1/Cd (σM ) equivalent circuit of inset 2. in series with an GC theory for different charge densities σM on Rt Ct mesh representing the self-assembled thiol the metal.3 × 10−2 M (b).04 0. Rt = 0. Cd = 68 (a). The solid calculated on the basis of the Gouy–Chapman curves are least-squares fits to the simple (GC) theory. only the experimental points for the lower KCl concentration were reported.02 0.01 20 1 c 0 0 0. 11 Plots of log |Z| and of the phase angle layer. which is actually experienced by the electrode is the charge to be supplied the diffuse-layer ions. whose values are reported on each and a further Rd Cd mesh representing the diffuse curve [102].1 M (d) KCl.3 SAMs on Hg Electrodes and Si 141 Ct Cd (2) RΩ 5 80 Rt Rd Ct (1) RΩ 4 60 –Phase angle (°) Rt a b c d [Ω cm2] Log |Z| 3 40 0. the ‘‘free charge’’ q(E). Ct = 11 µF cm−2 . and drop immersed in 5 × 10−3 M (a).02 a C −1d –3 b 0.27 (c).6 × 10−2 M (c). which consists of versus 1/Cd (σM = 0) plots calculated from the the electrolyte resistance R . 80 (c) and 1. versus log f for a thiolpeptide-coated mercury Rd = 4. of extrathermodynamic assumptions. 1.03 (3) –1 2 –2 [cm2 µF−1] 0. in the presence of to the electrode to keep the applied poten. as obtained at −1. 4. and 84 µF cm−2 (d).53 (a). 0. tion of the bulk phases is kept constant. as hence. capacitive contribution. It should be distinguished from it should be pointed out that the only ther. 0. In this connection by σM (E). the charge modynamically significant charge in ad. 3.1 to 105 Hz. At capacitance versus the 1/Cd (σM = 0) value frequencies < 102 Hz all Bode plots coincide.17 (b). of the experimental diffuse-layer the frequency range from 0.

Q accompanying the potential step pzc which yields a σM value of ∼70 µC cm−2 . 1.3. In fact. → Ef is then just the common value. it initial potential E to Ef at an adsorbate. while tions high enough to ensure an almost the σM value on bare mercury at a po- instantaneous adsorption equilibrium dur. thiol desorption charge accompanying the expansion of is not complete. yields a potential E2 just negative of the des- a σM value of ∼ +56 µC cm−2 over the orption peak and that at a potential E1 whole broad potential range of stability just positive of it.142 1 Preparation of Monolayer Modified Electrodes immersed in a solution of the supporting resulting σM values range from 70 ± 10 electrolyte alone and in stepping the to 80 ± 10 µC cm−2 . Application of this procedure to a C18 The charge under the reductive desorp- SAM on a mercury electrode immersed tion peak of n-alkanethiols is not a precise in aqueous 0. tained by the more accurate potential-step where they are sufficiently soluble. The chronocoulometric procedure (vide supra). tion peak amounts to −70 µC cm−2 . This procedure was −16 µC cm−2 [16]. of n-alkanethiol SAMs. where this SAM is completely ference between the capacitive charge at desorbed at Ef = −1.1. in aqueous 0. tential just negative of the peak equals ing drop expansion. the former is the very low differential capacity of the C18 monolayer.85 V/SCE. because of itive charge is very small.1 M tetramethylammonium plied potential E. will be shown that the capacitive contribu- coated electrode in the same supporting tion can be approximately identified with electrolyte will be equal to σM (Ef ) − the free charge density q(E). While the latter capac- of the monolayer [16]. of the total charge density both impossible to separate σM into a capacitive in the presence and in the absence of and a faradaic contribution [106]. since it includes the dif- chloride. It can be applied only chloride.3. The charge accompanying possible only on the basis of extrathermo- a further potential step from any given dynamic assumptions. such as the oxidation adsorption is experimentally accessible: the charge prewave of cysteine (see Sect. sity σM at E2 on a bare mercury electrode.2). provided such a potential waves. the charge under the desorp- in the presence of surfactant concentra. In the following. at potentials just negative liquid electrodes consists in recording the of the desorption peak. excellent agreement with the value ob- cury from methanolic NaClO4 solutions. in These thiols were self-assembled on mer. this potential range lie within the limits of it can be identified with the charge den- experimental accuracy. which is very σM (E). An alternative procedure applicable to even though. In the case of a C18 an HMDE immersed in a solution of SAM on a mercury electrode immersed the adsorbing surfactant at constant ap. the changes in σM over not negligible. range of stability of the C18 SAM. This is the adsorbate. thus allowing the estimation of small over the potential range of stability the total charge density σM (E) at E. From a thermodynamic point of view. This yields a total adopted to measure σM for monolayers charge density of +54 µC cm−2 over the of n-alkanethiols with 8 ≤ nc ≤ 18 [85].2. This procedure is applied potential from the pzc to a final substantially identical with that based on potential Ef negative enough to exclude the measurement of the maximum limit- the adsorption of the adsorbate under ing height of dc polarographic adsorption investigation. it is σM (Ef ). As a first approximation.1 M tetramethylammonium measure of σM . .

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

11. In view of the considerations made in con- ble to a good approximation. (9)) and from the differential ca- transfer of a negative charge density λσi pacity. At −1. of a zero degree of dissociation α. (9). Ct = 0. as dis- deprotonation of the sulfhydryl group are tinct from the C18 alkanethiol. of the C18 SAM. In the limiting case cury–aqueous solution interphase.000 V/SCE by the potential-step pro- Combining Eqs (19) and (20) yields: cedure equals +17 µC cm−2 . C of thiolpeptide-coated Hg is high enough Differentiating Eq. we can set charge density is negative and equal to α ≈ −σM /σi = 0. (19) with respect to not to obliterate diffuse-layer effects.3. the dipole potential χt of the tial χt of the thiolpeptide through Eq.2). this is also an approximate estimate neglect the (β/ε0 ε∞ ) (α − λ)σi term with of the partial charge-transfer coefficient λ respect to the other. In the thermodynamically significant and practice. the charge density σi estimated on the of the differential capacity of the thiol assumption of a close-packed hexagonal monolayer: array of thiolpeptide molecules is ap- proximately equal to −20 µC cm−2 .7 to a good approxima- (1 − λ)σi . φ. In the opposite limiting case of ing into account that σM and |σi | are both a unitary degree of dissociation. The [(d − β)/ε0 ε∞ ][(α − λ)σi ] term and ασi are much greater than their al- is the potential difference across the gebraic sum. In this case the partial charge-transfer coefficient λ ≈ σM + ασi φ = + χt (21) (q – σM )/σi is. to the metal leaves an equal and opposite |σM + ασi | turns out to be about 2 orders positive charge density −λσi on the sulfur of magnitude smaller than |σi | [16]. approximately C equal to unity. the charge density (σM + ασi ) is experimentally accessible charge density small. this much greater than |σM + ασi |. thus σM under the assumption that the dipole allowing the free charge density q = σM + potential χt and the partial charge-transfer λσi experienced by the diffuse-layer ions to coefficient λ ≈ α are not appreciably be estimated at −3 µC cm−2 from the GC affected by a change in σM . plus of C18 anions is about −80 µC cm−2 . σi . on the −S− groups versus the SCE by ∼ 250 mV. However. n-alkyl chain can be regarded as negligi. 1. since the absolute values of σM σM . Thus. (d/ε0 ε∞ ) (σM + ασi ).7 µFcm−2 . After rearranging terms. extrathermodynamic estimate of the abso- created by the charge density on the lute potential difference across the mer- sulfhydryl groups. its dipole potential χt cannot values. we can tion. the (see Eq. for C18 . the capacity strictly correlated events.144 1 Preparation of Monolayer Modified Electrodes by the negative charge λσi transferred of a hypothetical close-packed monolayer from the sulfur atoms to the metal. Moreover. φ is more positive σM equals +56 µC cm−2 (vide supra) and than the applied potential E measured the charge density. More- following expression for the reciprocal over. The knowledge of q also If we apply this equation to the C18 allows an estimation of the dipole poten- alkanethiol. of length (d − β).000 .3. while dφ 1 d = = (20) the total charge density σM measured at dσM C ε0 ε∞ −1.1. nection with Eq. from the approximate chain of the thiol.2.(21). therefore. since partial charge transfer and be regarded as negligible. yields the theory [102] (see Sect. both because β is d and because α In the case of the water-soluble thiolpep- and λ are expected to assume close tide of Fig. Tak- atoms.

1. the differen- Fe(CN)6 3−/4− but also lipophilic couples tial capacity C per unit surface increases such as UQ/ubiquinol-10 or viologens.09 [85]. Upon estimating σi at length of the hydrocarbon chain. as in the case of phospholipid- TPhB− and TPhP+ are prevented from coated mercury (see Sect. Thus. and i0 is regarded as the current density in the absence of the thiol monolayer.4 Electron Transfer across Thiol Monolayers of n-alkanethiols with nc SAMs on Mercury While short-chain from 9 to 14 maintain their imperme- n-alkanethiol and ω-thiocarboxylic acid ability and dielectric properties upon slow monolayers.2. a typical example stant of the SAM. drop and for C12 on a progressively ex- alkanethiols with 8 ≤ nc ≤ 18 from panded drop. where c∗ is the hydrophilic thiol.3 SAMs on Hg Electrodes and Si 145 V/SCE. C and q equal to +13 µC cm−2 . From density measured at constant applied Eq. and dielectric properties shows a reduction current across a C16 through a gradual tilting of the thiol chains. say with nc = 2. which may reach up to 4% of that Figure 12 shows plots of ln i versus the on bare mercury [82]. where C equals 11 µF cm−2 [102]. However. Moreover. values of σM .2. electron tunneling kinetics and depends Using the same approach for an SAM upon the overpotential η according to of triethyleneoxythiol. with kap = kapo exp(−αηF /RT ).750 V. Pb2+ . state at room temperature. is higher than room temperature block the Ru(NH3 )6 3+ reduction current con- almost completely not only inorganic tinues to be limited by slow electron redox couples such as Ru(NH3 )6 3+/2+ and tunneling kinetics.5 M KCl was thoroughly upon drop expansion increases with a de- investigated by Majda and coworkers [85. the decay constant per methylene group ficient λ of 0. according −70 µC cm−2 from a space-filling model to the relation i = i0 exp(−βnc ). long.5 µC cm−2 . 109]. a Thus. This translocating across a C18 monolayer on denotes a constancy in the dielectric con- Hg [86].1. n-alkanethiols whose transition of ∼5% [85.1. a partial charge-transfer coef. 11 µF cm−2 bulk reactant concentration and α is the and −3. another relatively the well-known relation i = F kap c∗. volume. upon mercury drop expansion in excess 86]. 84. 110]. Sub. The current measured at −0.14 ± 0. (21) it follows that χt amounts to potential decreases exponentially with the ∼ −200 mV [37].3. Thus. thanks to their liquid-crystalline such as Ru(NH3 )6 3+/2+ only slightly.3. (21). crease in film thickness much less than . affect the stepwise expansion of the HMDE up rate of electron transfer of redox couples to 30%. it is exclusively controlled by slow χt value of about −470 mV is obtained. It is apparent that the current aqueous 0. proportionally to the drop area during drop Even the electroinactive lipophilic ions expansion.2. Conversely. 1. SAM. by keeping the temperature to the liquid-crystalline state drop expansion within the above limits. respectively. were charge-transfer coefficient.1). which maintains its of a metal ion/metal amalgam couple.3. This current density is much φ is therefore equal to −0.24 was determined. 108. film thickness at constant E both for dif- The reduction current density i ferent n-alkanethiols on an unexpanded of Ru(NH3 )6 3+ across SAMs of n. stituting these numbers in Eq. lower than its diffusion limiting value.785 V/SCE [107]. density. here β is of this thiol. n- chain thiols inhibit electron transfer the alkanethiols with nc > 14 fracture easily more the longer is their chain [82. 1. The β value amounts to 1.

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

A (a) redox probe is located outside the S S S S dcc monolayer/solution interface. are bell-shaped (see Fig.05 A˚ −1 . case of IrCl2− 6 ). 109]. tunneling from the continuum of elec- rocene derivative. in the i versus −η plots requires extremely To exclude the possibility that the small negative overpotentials (−eη > 2λ) and increase in the tunneling current following corresponds to Marcus’ inverted region drop expansion might be ascribed to par. (b) S S S S (b) Hg drop expansion results in the Hg formation of pinhole defects. if sion for kap is obtained by integrating the partial penetration of a redox probe into expression ρ(metal)Hd 2 (ε)ρ(ox) over the an expanded monolayer causes a certain electron energy levels ε. 1. Thus. On an unexpanded the metal. The Hg chains exhibit a tilt adopted in response to monolayer expansion. 13 Schematic representation of two possible different structures q adopted by an alkanethiol monolayer upon expansion of an HMDE. In addition to the through-bonds pathway. recorded at a scan rate the redox probe according to Marcus.31 ± 0. but then tends to a plateau. as shown is played by a metal. FeCH2 N−(CH3 )3 2+/+ . When the role of electron donor the n-alkanethiol monolayer. high enough (>5 V s−1 ) to exclude partial and Hd 2 (ε) is the electronic coupling. where ρ(metal) = increase in tunneling current as a result of {exp[(ε − εF )/kT ] + 1}−1 is the Fermi dis- a shorter tunneling distance. Fitting this equation to the experimental diffusion control. for homogeneous electron-transfer reac- tial penetration of the redox probe into tions. because probe and of the more hydrophobic fer.01 A˚ −1 and tially.91 ± 0. βts = 1. while the plots of dkap /dη. (a) The x dcc q monolayer is essentially pinhole free.3 SAMs on Hg Electrodes and Si 147 Fig. where obtained by ab initio calculations [85]. tronic states below the Fermi level εF were determined on both unexpanded and is still possible for −eη > λ. . no decrease in schematically in Fig. 13(b). 14 for the significantly weaker than the through. the reorgani. increases with a negative i versus θ plot for the C12 SAM (inset of shift in the overpotential η first exponen- Fig. 12) yields βtb = 0. An expres- expanded mercury drops [109]. The attainment of a plateau bonds coupling. which S S S S dominates in perpendicularly oriented Hg monolayers. In fact. the chain-to-chain coupling is stant. The latter value is the i versus −η plots show an inflection in excellent agreement with an estimate point. As kap = i(η)/F c∗ is the apparent rate con- expected. the electron-transfer rate can be observed zation energies λ of the IrCl6 2−/3− redox with an increase in driving force. it should also tribution density of electronic states in cause a decrease in λ. A redox probe can partially permeate the alkane region of the monolayer [85. ρ(ox) = (4πλkT )−1/2 exp[−(λ− C16 -coated HMDE the reduction current eη)2 /4λkT ] is the distribution density in i for both probes. an additional pathway (marked by the densely dashed line) involves a chain-to-chain coupling.

0246 cm2 . corresponds to the Gaussian fit through the electrode surface area = 0.0 × 10−3 M IrCl6 2− .2 0.4 0. in good the SAM takes place.0 −0.148 1 Preparation of Monolayer Modified Electrodes × 10−7 –4 × 10 B 6 5 8 4 [cm s V ] –1 –1 dkap/dh 3 2 6 1 0 0. This function ρ(ox). in the agreement with the predictions of the Mar. Fitting this expression to indicates that the λ value is invariant with the experimental dkap /dη versus η plots the monolayer expansion and that no pen- (inset of Fig. 14) yields λ values close to etration of IrCl6 2− into the alkyl chains of 1 eV for both redox probes [109].12 V s−1 .5 −1.0 −0. scan rate = 5.2 −0. a monolayer. When carrying out analogous chlorophyll molecule lacking the phytyl . dkap /dη takes the dkap /dη versus η plots for the IrCl2− 6 probe form (4π 2 / h)ρ(metal)Hd 2 ρ(ox). the ac. The inset data [109]. cus dielectric continuum model for an even a small expansion (2%) of the C16 aqueous environment. Therefore. SAM results in a very large increase in cur- cess of IrCl6 2− and FeCH2 N – (CH3 )3 2+ rent and a destruction of the monolayer. a plane outside the C16 unexpanded A film of chlorophyllide (Chlide). Assuming that the Fermi distribution measurements on differently expanded is a step function and that Hd 2 (ε) is C16 SAMs.5 M KCl in the reduction of IrCl6 2− under the same absence (A) and in the presence (B) of experimental conditions. The solid curve 1.0 −1. 14 Current versus potential curve of shows a plot of dkap /dη versus η for the C16 -coated mercury in aqueous 0. the maxima of the Gaussian independent of η.6 −0. Conversely. case of the hydrophobic ferrocene probe.8 E (SCE) [V] Fig. to the electrode surface is restricted to due to mercury oxidation.4 −0.5 [A] 4 Overpotential i [A] 2 A 0 0. which lie at the same overpotential up to a maxi- depends upon η only via the Gaussian mum tilt of the alkyl chains of ∼20◦ .

thiol-coated Hg electrodes.89 ± 0. in by decreasing the alkanethiol chain length place of a methylene group. two contacting mercury phases.3 [113]. The reduction photocurrents chain intercalation at the resulting bilayer following illumination of the Chlide film midplane [113. with no ical anion. mercury surfaces.7 ± 0. 1. The latter device that observed with chlorophyll molecules allows the formation of both symmetric adsorbed on mercury-supported thiol and asymmetric Hg−Cn //Cm −Hg bilayer SAMs [112]. rather. the photocur. the dielectric constant ε of the junc- sian maximum was used to determine tion was found to be 2. in the bi- on a nonexpanded drop. roughness. If the thickness of cording to the relation i = i0 exp(−βnc ). thus confirming layer junction results in an increase in that electron transfer takes place primarily the tunneling current. the junction area can be estimated SAM by increasing its chain length causes with sufficient accuracy. Differentiating extended alkanethiol molecules in a per- these photocurrents with respect to the pendicular orientation with respect to the applied potential and plotting the result. tube. electronic coupling.1 [114]. positioned vertically and coax- decrease regularly with an increase in the ially one above the other. the film against its thickness d. the double dash denotes zation energy λ for Chlide electroreduction van der Waals interactions at the inter- with an increase in the thiol chain length is face between terminal groups of the two tentatively explained by a concomitant de. When us- bell-shaped curves that can be fitted to ing two volumes of mercury in a glass a Gaussian. λ was found to HMDEs. with n and m ≥ 9. Inser- rent increases much less than observed tion of an amide group −CONH−. as distinct from solid elec- creasing the thickness of the alkanethiol trodes. the length of the hydrocarbon chain. As in the case of the photocurrent. equated troinactive in the dark. group equal to 0. was adsorbed on top of mercury. to decay exponentially current density measured at a voltage bias with a decay constant β as low as 0. In. 114]. This trend is opposite to value of 2.5 V decreases exponentially with This low β value is explained by a concomi. they form a Hg−Hg tion of Chlide causes the photoexcited junction consisting of two alkanethiol molecule to take one electron from the monolayers anchored to the surface of the metal. ac- tant energy transfer. the tunneling ganization energy. in the following. 114]. satisfies the Helmholtz ing derivatives against potential yields formula. The potential of the Gaus. Thus. Junction experiments . yielded an ε thiol chain length. an alkanethiol monolayer is decreased by with the decay constant β per methylene expanding the drop surface. The decrease in the reorgani.17 A˚ −1 . and hence in the along a ‘‘through σ -bonds’’ pathway. and their action to the sum of the lengths of two fully spectra were determined. corrected for the reor. where λ is greater for C14 than junctions. V = −1. not coalesce. while the reorganization energy λ for the Chlide the use of two contacting thiol-coated electroreduction process. When two volumes of mercury are sep- supported SAMs of n-alkanethiols of chain arated by an alkanethiol film. the plot of the were measured over the potential range in reciprocal of the differential capacity C of which this photoexcitable molecule is elec.3 [114]. Thanks to the liquid nature of mer- crease in the amount of water molecules cury. Illumina. with formation of the Chlide− rad.3 SAMs on Hg Electrodes and Si 149 chain. here and for C12 [112]. which has no macroscopic surface incorporated in the thiol SAM [111]. C = ε0 ε/d [113.0 ± 0. SAMs. they do length from C12 to C18 [111].

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

stimulated research aiming at exploit. biomembrane models Thanks to the high affinity of mercury for consisting of lipid bilayers (often referred sulfur. In fact. without the disturbing presence of stray ing self-assembly for the realization of currents due to defects.1. the transport of hydrophilic ions electron transport. obtained by immersing the mercury drop tBLMs) should meet a number of require. which must RuII /RuIII couple. an alkanethiol monolayer is first to as tethered bilayer lipid membranes. crystalline state. (2) they should be as of its own SAM. across the lipid bilayer. their protruding hydrophilic sections are step hopping mechanism. they also have is bell-shaped. More- bridge for an appreciable time during over. and more positive electrode (the anode). Mixed alkanethiol–phospholipid bilay- rating integral proteins in a functionally ers on an HMDE are readily prepared active state. for 1 or 2 minutes in a thiol solution in ments: (1) they should be robust enough ethanol.3 SAMs on Hg Electrodes and Si 151 conditions. This has potential not only by exploiting the hydrophobic interactions for fundamental research on protein func. Requirement (4) is The possibility of self-assembling bilayers needed to make the biomembrane model covalently on metals with the formation sufficiently blocking as to characterize ion of rugged functionalized electrodes has channel activity by electrochemical means. with electrons actually teins into biomembranes must ensure that populating the molecular bridge. with the maximum lying hydrophilic sections protruding by over in the proximity of the RuII /RuIII redox 60 A˚ outside the lipid bilayer. the plot of the resulting therefore be sufficiently flexible to accom- current against the potential of the anode modate this section. integral proteins have a hy- as to move both Fermi energies from drophobic section buried inside the lipid above to below the electronic states of the leaflet of the biomembrane. In one experiment. and be easily and re- (the cathode) transfers an electron to RuIII producibly prepared. To avoid potential. This (4) they should be sufficiently free from electron transfer takes place only when the pinholes and other defects that might pro- electronic states of the RuII /RuIII couple vide preferential pathways for electron and fall between the Fermi energies of the two ion transport across the lipid bilayer [120]. so state.4 Tethered Bilayer Lipid Membranes layer is interposed between the bilayer and on Hg the electrode surface. via ion channels or ionophores. biomembrane models capable of incorpo. nethiol and those of the phospholipid [64]. the resulting RuII releases flexible and fluid as lipid films in the liquid- its electron to RuIII of the adjacent SAM. Requirements (2) and (3) are necessary for the potential difference between the two the incorporation of integral proteins into electrodes was kept constant at 0. 1. is possible only if an aqueous 1. The phospholipid monolayer on . To achieve this goal. (3) they should have water which transfers it to the corresponding. the more negative electrode for long-term stability. on both sides of the lipid bilayer. The mechanism responsible their denaturation and to promote their for this current is considered to be function. the incorporation of integral pro- resonant tunneling. mercury electrodes.1 V. with electrons accommodated in a hydrophilic medium localized somewhere in the molecular on both sides of the lipid bilayer. Often. between the hydrocarbon tails of the alka- tions but also for biosensor applications. or a two.3. and the lipid bilayer in a functionally active both potentials were shifted upwards.

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

3. der the simplifying assumption that the A particularly convenient thiolipid short-range interactions of K+ with the named DPTL consists of a tetraethyle- thiolspacer medium are comparable with neoxy chain covalently linked to a lipoic those with the aqueous phase. and the dure yields a lipid bilayer anchored to the conductance of the tBLM increases up to a mercury surface through the hydrophilic limiting value. 1. valinomycin [30]. layer. A tBLM obtained by self-assembling triethyleneoxythiol thiolspacer [107]. with the hydrocarbon tails turned while the ω value at the maximum of the toward the aqueous solution. both in the absence on top of mercury-supported hydrophilic and in the presence of the ion carrier thiolspacers. and bound via ether linkages the curve of the conductance against the to two phytanyl chains at the other end applied potential E corresponds to a zero (see its structure in Fig. it has been value of the transmembrane potential [37]. used by Naumann et al. in. The impedance spectra fortable. tivity. the K+ ions causes a lipid monolayer to self-assemble are electrostatically repelled from the thi.8 V. spacer terminated with a sulfhydryl or which can be straightforwardly fitted to disulfide group at one end. Un. with the olspacer. [124] for the prepa- The voltage-gated channel of melittin. 15). especially tBLMs are obtained if the HMDE is coated when reported in a ωZ  versus ωZ  plot with a monolayer of a ‘‘thiolipid’’ [30. 37. (see Sect. 1 × 10−2 to 1 × 105 Hz and over a poten- tained with lipid bilayers self-assembled tial range of 0.3 SAMs on Hg Electrodes and Si 153 the bilayer. and covalently RC meshes in series. for anchor. Shifting the applied potential hydrocarbon tails of the two monolayers to more negative values.1). This plot shows four 121–123]. This consists of a hydrophylic partially fused semicircles (see Fig. Immersing semicircle measures the reciprocal of its the thiolipid-coated mercury drop into an time constant.2.5 × 10−7 M solu- on the surface of the aqueous electrolyte tion in aqueous 0. τ = RC. ultimately. the diameter at the other end. layer on top of a DPTL-coated mercury brane potential practically equal to that electrode was investigated by impedance reported on a BLM. portion of the thiolipid. was a diphytanoylphosphatidylcholine mono- found to open at a calculated transmem. of the capacity of the RC mesh.1 M KCl are particularly during measurements. the conductance decreases aqueous phase on the metal side of the owing to saturation of the thiolspacer. When q is positive. which mimics the ative potentials. their use is rather uncom. 15). The frequency in- aqueous electrolyte. spectroscopy over a frequency range from In spite of some satisfactory results ob. 1. . K+ ions start turned toward each other. bilayer. This proce- penetrating into the thiolspacer. at still more neg. 1/C. Each semicircle cor- linked to the polar head of a phospholipid responds to a RC mesh. it can be acid residue for anchoring to the metal demonstrated that the inflection point of at one end. More convenient rich in characteristic features.2. an equivalent circuit consisting of four ing to the mercury surface. thus increasing its conduc. Tethering the thiolipid of the semicircle measures the recipro- to the metal surface yields half a lipid bi. on top of the thiolipid monolayer. cal. on whose surface a creases in the direction of increasing ωZ  . since the drop neck must be obtained upon incorporating valinomycin kept in contact with the lipid reservoir in this tBLM from its 1. ration and characterization of tBLMs on corporated in a tBLM prepared with a gold. lipid film has been previously spread.

Bach. R. I. The four RC meshes are ascribed to dif. Rev. 15 Top: structure of the DPTL thiolipid in 1. J. 3061–3065. 1973. E. M. This tBLM was also used to incor. Am. J. 123. 3439–3446. the 4. tetraethyleneoxy moiety. 19. Colloid Interface characterizing these dielectric slabs. M. due to interfacial polarization at the substructural-element interfaces. tBLM. In narrow potential range straddling the zero fact. and conductance properties of the sub- structural elements are different. 250–260. M. the lipid bilayer. When Sci. D. R. Barnum. Biochemistry porate the channel-forming protein OmpF 1980. M. F. Bottom: plot of ωZ  versus ωZ  for a ωZ  versus ωZ  plot to the different tBLM in aqueous solution of 0. proceeding in the direction of increas. 1969. Kolthoff. Chem. this gives rise to a dispersion of the impedance with References frequency. 126–137. Miller. Lecompte. R. The arrows relate the semicircles of the molecule. 29. 62. 1940. 5. Miller. I. Miller. which provides a means of detecting and 2. 15 are Soc. 1976. Annu. Colloid Interface Sci. J. on the basis gent [123]. Lecompte. Bioeng.41 contact with a diphytanoylphosphatidylcholine V/SCE. 259–266. ascribed to the lipoic acid residue. which is interpreted by a creases the conductivity of the tBLM over a model of the electrified interface [30]. 5. Biophys. 119–175. Miller. F. R. The analysis of the impedance of the potential dependence of their R spectra indicates that OmpF porin in- and C values. ing ωZ  . Pagano. 1988. I. 6. J. C. .154 1 Preparation of Monolayer Modified Electrodes Solution o s o o Hg s o o o o o o o o o o P o + o o N 10 ωZ’ × 107 [Hz Ω] 6 2 2 4 6 8 ωZ’’ × 107 [Hz Ω] Fig. Montal. I. 3. 1. the RC meshes in Fig. R. recorded at −0. 45. I.5 × 10−7 M valinomycin. Colloid and the aqueous solution adjacent to the Interface Sci.1 M KCl and substructural elements of the tBLM [30]. porin from its aqueous dispersion in deter- ferent portions of the tBLM. the tBLM is a heterogeneous system value of the potential difference across the with a substructure in which the dielectric lipid bilayer moiety.

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

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

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

avoided completely in treating H:Si(111) in To obtain a homogeneous thickness of aqueous/nonaqueous solvents in conven. Oxidative reagents times pretreated in HF (a few percent) should be avoided in solutions. Then the wafers are subjected to ex- linked to Si by C=C and those by NH2 [28]. the oxide layer. NH4 OH + H2 O2 (Ammonium- amino-terminated hydrocarbons [29]. 34]. Peroxide Mixture. (90 ◦ C. HPM). etching in dilute HF or 40% obscure the target adsorbates and bother aqueous solution of NH4 F at room temper- surface analysis. which can hardly be eliminated is a good idea to use two kinds of solvents. Photoadsorption of 1. ide layer after treatment in such so- Oxidation of Si substrate cannot be lutions is approximately 10-nm thick. HCl + H2 O2 In general. SPM or ‘‘piranha’’ applied on Si(100) surface to deposit solution). such as trichloroethylene and acetone.3 SAMs on Hg Electrodes and Si 161 than terminal C=C.2 Handling of Si Specimens for treatment of clean Si(100)-(2 × 1) or heat- Adsorbate Preparation and Surface Analysis ing in high-pressure hydrogen gas [42]. the wafers are some- tional sealed glassware. The pro- quate information on contaminants with duced surface can be kept clean in air for at high fidelity. To learn more of surface Si−Si dimers with each Si about the development of this field. useful D:Si(111)-(1 × 1) can be prepared cussed in terms of deposition reaction and by fluoride solution in D2 O [38. 39]. Wolkow [32]. of H:Si(111)-(1 × 1) was well studied by niques. by extensive hydrogen treatment [43]. and so on. some topics on hydrogen-terminated Si(100). which often For Si(111). diluted HNO3 + H2 O (1:1. Then. Spectroscopically handle Si wafer surfaces are briefly dis. Hydrochloric acid-Peroxide Mix- products and contamination during the ture. the terminated by one hydrogen atom. Due . For surface analysis. APM). The signs of impurities should be carefully watched and quan. The sacrifice ox- ing the procedure of surface analysis. In this article. Wayner H:Si(100) (3 × 1) surface is composed of et al. [31]. The surface usually contains unterminated chased usually starts with degreasing by dangling bonds (neutral Si surface mono- sonication or rinsing in organic solvents. tensive oxidation in reagent mixtures such The technique of protected derivatives as H2 SO4 + H2 O2 (3:1.3. 90 ◦ C). 37]. Surface treatment of Si wafers as pur. [33. the procedures to various methods [36. 100 ◦ C. The review articles by Yates et al. H:Si(100)- hydrogen-terminated Si(111) and chlorine. alternate rows of monohydride dimers and Buriak [35] are excellent. Sulfuric commonly used in organic synthesis was acid-Peroxide Mixture. process of deposition as well as dur. Bent et al. 1. These surfaces can be prepared by atomic H 1. We also to remove irregular precovering oxide have to be careful of the hydrocarbon layer. least a few minutes. It radicals). [30]. H:Si(100)-(2 × 1) is composed few years are introduced. amino-3-cyclopentene in liquid phase onto which dissolve different kinds of organic H:Si(100) seemed to deposit molecules debris. Most surface-sensitive ature effectively removes the oxide layer to analytical tools can usually present ade- form ideal H:Si(111)-(1 × 1) [20]. we should assess the by.2. and dihydride silicon atoms [41]. contaminants in atmosphere. and microscopic perfection under cross-checking with different tech. (2 × 1) and H:Si(100)-(3 × 1) are well terminated Si(111) that emerged in the last known [40]. The surface is strongly tified by proper methods of calibration hydrophobic.

and gas exposure treatments. mospheric pressure to ∼10−4 Torr.3 Summary of the Latest Researches the surface [9]. The resid. H:Si(111) and organic-modified Si are not Linford et al.3. by the laboratory procedures can be done heating [6]. tubings are convenient for most heating In UHV. stabilize Si surfaces and to make modifica- just a short period of exposure to the tions over the adsorbates. and the surface is much less defined than After quick. and the O2 dissolved in the reaction fluid.162 1 Preparation of Monolayer Modified Electrodes to such dangling bonds. first hypothesized that the positively contaminated within a short spacing species to accommodate alkyl period. The adlayer of long should be rinsed and dried under a dry alkyl chains is robust and convenient to atmosphere after the reaction.1 Adsorption of Terminal Olefins an extended period of time in aqueous on H:Si(111) Since 1995 when Linford solutions unless some reducing reagents et al. It is difficult to perform liquid-phase reactions on H:Si(111) for 1.2. saturated alkanes) improves the quality of When the specimen is in the atmosphere.3. Most . or conveniently. The deposition atmosphere does not usually oxidize the reaction was activated by the coexistence surface to any detectable extent and of a radical initiator in liquid phase [6]. Immersion of H:Si(111) in water without deaeration promotes oxidation of 1. latter causes severe hydrocarbon contam- not survive in the atmosphere [44]. Reactions in organic solvents ods of long alkyl chains (>10 carbons) [6]. UHV is ideal in storing the By this procedure.2. electron sources sometimes de- liver hydrocarbon contamination on Si. by light irradiation [46–48]. The largest chance of contamina. the surface can. UHV chambers and below the limit of spectroscopic detection. It is necessary to use an oil-free of Si(100) in fluoride solutions results in pump. chains on Si(111) is OH species accord- tion is when the surface is in the stage ing to X-ray photoelectron spectroscopy of initial vacuum pumping. (XPS) observation [6]. However. the alkyl adlayer [49].3. Use of di- Introduction of the Si specimens into a luted olefins in an inert solvent (such as vacuum chamber should be done carefully. vacuum or purged containers through air. H:Si(111) Operation of a B–A gauge placed on a and organic-modified Si surfaces are line of sight from the specimen should be resistive to air and can be passed between avoided. the The process of adsorbate deposition vacuum container can be switched to a tur- should be carried out in a well-controlled bomolecular pump running at top speed. partially (100)-(2 × 1) and (111) facets [45] for evacuation from atmospheric pressure. by using Lewis-acid catalysis. Etching ination. The origin of OH ual gas in the vacuum generated by oil might be the peroxide radical initiator or rotary pump is water and oil. The specimens of organic deposition. environment. such as N2 or Ar. first reported the fabrication meth- are added. contamination by hy- surfaces and is indispensable for handling drocarbons and oxidation can be reduced clean Si surfaces of Si. such as liquid-nitrogen cooled sorp- an inhomogeneous surface composed of tion pump or helium cooled cryopump. clean evacuation from the at- H:Si(111)(1 × 1). are successfully performed in airtight the reaction between H:Si(111) and ter- minally double-bonded olefins (1-alkenes) glassware or glove boxes purged with inert has been accepted as a practical method gas.

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

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

RMgX + Cl:Si(111) −−−→ As one of the most attractive topics in the R:Si(111) + MgXCl (4) field of Si surface science. surface in alkyl–Li solution or alkyl–MgX Cl:Si(111) and Br:Si(111) slowly react solution. [56. Lopinski. (c) Br/Si(111)-6. 2005. I) has been widely used in on H:Si(111). The surface was composed organosilicon synthesis. Lopinski preparation and to exploit its characteristic et al. 55] chlori- than hydrogen-terminated Si(111) (Fig. G.3. pioneering in the use of alkylating reagents Recently Rivillon et al. 579. which are commercially 1-butene was destroyed [39]. Sci. 5 STM constant current images of 40 pA.3. solutions in diethylether or tetrahydro- indicating that the original methyl end in furan (THF). J. Br. −0. of a bridge type adsorbate on Si(111) has The precursor halogenated Si surfaces not been recognized widely so far but it will had not been put into detailed be interesting to find a concrete method of investigation until recently. (Figure 2 of B. this work was handled in vacuum or in inert gas. Despite imperfect impurity re- with components of air and should be jection and surface analysis. 5). [58. L89 [57]).2 Grignard Reaction on Halo- and high-resolution electron energy genated Si(111) The formation of C−Si loss spectroscopy (HREELS) formed by bond by Grignard reagents (Cm Hn MgX. [54. and Si(111) was almost solely of monohalide Si atoms. 57] reported well-ordered macroscopic properties. even better early stage. monolayers of Cl:Si(111)-(1 × 1) and Br:Si(111)-(1 × 1) examined by STM 1. reactions at room temperature.2.5 nm. −1 V (sample bias). The mechanism is simply outstanding method of surface infrared formulated as: spectroscopy and detected Cl−Si vibration signals.5 × 6. .5 V. (b) Cl/Si(111)-6. (photo-)reaction in gaseous Cl2 or Br2 X=Cl. Surf. 1. halogenated Si(111) prepared by gas phase 50 pA. P. (a) Cl/Si(111)-50 × 50 nm. the formation (a) (b) (c) Fig. Eves.5 nm. −0.5 × 6. The existence available. 59] applied an on Si surfaces.3 SAMs on Hg Electrodes and Si 165 photoadsorption of 1-butene on H:Si(111) Grignard reagents are delivered as did not yield CH3 vibrational signals. 400 pA. Bansal et al.4 V. The halogenated surfaces were atomically also subjected to Grignard reaction in the flat with low defect density. nated H:Si(111) in a benzene solution of Removal of surface Si atoms as gaseous PCl5 under coexistence of radical initia- Si halides is considered to be involved tor and then immersed the chlorinated in flattening the modified surfaces.

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

Such Cl atoms are consid- et al. Kawai. 7 HREELS of the methylated Si(111). 1423 cm−1 : CH3 umbrella motion. incident angle = exit angle = 60◦ from the surface normal. 1099 cm−1 : Si−O stretching in SiO2 . Phys. 789 cm−1 : CH3 rocking. 10660 [24]). A. J. HREELS incident electron energy 2.84 eV. The full width at half maximum of inelastic peak = 7. Chem.5 eV in the occu- alkyl groups larger than methyl. must be left over in the space between ized in an electrolytic phenomenon. 1. the space pied levels additionally to the I–V curve filling of adsorbates does not geometri- of H:Si(111). It is interesting to address the elec. CH3 :Si(111)- only for the purpose of application as (1 × 1) was also applied as the ul- the lithography resist layer but also trathin channel medium of field-effect as the basis of nanoelectronic devices. electronic conduction through the surface. transistor [14].. 507 cm−1 : C−Si bending. 121.6 meV. (Figure 2 of T. ered to be replaced by oxygen-containing (1 × 1) as an electrode in an aqueous species during rinsing or by exposure . The I–V characteristic curve of STM As for Grignard reagents containing reached a peak at −1. 1268 cm−1 : CH3 asymmetric bending. and a certain part of terminating Cl atoms This conducting property is also material. redox solution exclusively lowers the peak tronic property of CH3 :Si(111)-(1 × 1) not potential of redox reaction. This peak corresponds to the electronic state that contributes to cally allow every Si atom to be terminated. M. 2004.3 SAMs on Hg Electrodes and Si 167 106 683 Counts [cps] 507 789 2944 1268 1099 1423 x2000 x50 0 0 500 1000 1500 2000 2500 3000 3500 4000 Wavenumber [cm−1] Fig. 2944 cm−1 : C−H stretching. Wawro et al. Yamada. 683 cm−1 : C−Si stretching. [61] demonstrated that CH3 :Si(111). Niwa alkyl adsorbates.

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

28. R. Hirao. 435. 14. 17. G.. R. Yamada. A. The mechanism of H:Si(111) replace. J. B 2003. Peck. Lewis. K. J. B 2003. W. Soc. 406. Chem. D. Eisenberger and component detachment. Lercel. Chem. Pitters et al. B. The chance of unwanted References substrate oxidation during the fabrication process can be minimized. 2. C. Niwa. 14. P. Kawai. Phys. Technol. 3145. A. cyl bromide yielded a finite amount of Nature 2000. Homma et al. Chem. P. A. 1995. 117. reagent. 39. Smith.. 8039. Webb. H. 56. L. lution [69]. P. alkyl adsorbate and a significant amount 18. 2001. Am. H. proposed a mechanism involving et al.. M. areal density is constant. alkali solutions [64]. B 2004. M. Cai. Langmuir 1998. H.. 19. Fukunaga. Yamada. can be deposited with adequate Phys. Phys. Chem. Decyl bromide intentionally Chem. C. 2004. Yamada et al. G. L. W. Chabal G. 5. Bernard et al. 107. de Villeneuve. T. Sch¨o1necker et al. D. by using n-type probably the most useful method to obtain and p-type silicon. Nissink oxygen in water [9]. mixture of alkyl and H regardless of the Although this analysis was not com- chain length. C. P. Vac. M. 1990. Yamada et al. M. P. Lie. J. L. 5404. Sugimura. 532. 106. K. Acid Res. Demirel. . Y. DiLabio. G. 2002. compared to 1. Lett. Bioelectron. we can expect the application of and XPS [55] indicating the saturation alkyl halides as the alkylation reagent to coverages are proportional to the chain open a new route to organic deposition length. Wolkow. Lopinski elucidated on the basis of concrete ex. R. S. 2415. 16. 3. 2000. J. J. 15030. Hossain. T. 520. Strother. Phys. 247. added in a diethylether solution of de. L. D. 7821. Chem. 108. S. 4140.. Yamada. Soc.. 19. J. 10. T. Biosens. Stewart. Phys. Higashi. J. T. Sieval. Fedorov. hydrocarbon groups are transferred to Chem. A. Grignard reagents without isomerization 6. cyl magnesium bromide significantly ac. 4085. Soc. Phys. The effects of alkyl halide were 20. G. J. A. 365.. and Si. unsaturated hydrocarbon moieties [26. Piva. J. stability. 1. 1996. G. J. Appl.. It was difficult to compare Chem. 1996. Sieval.. et al. Sci. R. the reaction kinetics with the Grignard Nature 2005. Fisher.. M. Huisman. 34. Vac. 65]. G. Hofer. 1997. C. RMgX. T. J. of SiO2 . of hydrocarbons. Lett. N. W. Z. M. M. celerated deposition of decyl groups. such as branched or J. B14. Chem. Fenter. Buriak. Whelan. 1759. 2002. Am. M. S. M. D.3 SAMs on Hg Electrodes and Si 169 The Grignard reaction on H:Si(111) is of Grignard reagent. W. even in a Cu-plating solution containing 9. perimental evidences. B101. J. Soc. Treatment of H:Si(111) in pure tetrade. 125. J. 3535. a trace amount of alkyl halide residue 13. Technol. M. regardless of the chain length. H. The alkyl. The C signals of AES [26] pleted. Am. J. W.. Chem. J. 3240. ing the electronic and thermodynamic The adlayers formed are constantly a energy levels of RX. Nakagiri et al. Lopinski. More varieties et al. the 4. Inoue.. Recently Fellah 12. N. Electroanal. 2005. hydrophobic and resistive toward dissolved 8. contained in the Grignard reagent so. Hamers. Wayner. Craighead the case for Cl:Si(111). Niwa. A. 656. Homma et al. Phys. or et al. D. In nearly all the cases. 1013. 48. Am. Trucks scrutinized by voltammetric electrolysis et al. Okiguchi. the Si surfaces within the precursor Chem. ment by Grignard reagent has not been 11. 123. Takano. J. Linford. 15. A 2002. 2005. J... T. 2003. Pinson. G. 107. Chem. J. K. 7057. 127. B14. B. Lett. H. Y. van der Weide et al. J. N. et al. D. F− for a short period [9]. P. J. K. A. Nucl. indicating that the adsorbate-wise on Si. 129. 658. J. Kato. Sci. and by consider- robust Si surfaces for practical purposes. hydrogen mixed adlayers are strongly 7. S. L. W. 6846.

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

G. 435. Piva.158 1 Preparation of Monolayer Modified Electrodes C H Si C-Si bond (a) (b) Fig. L. A. Pitters molecules to appear bright (topographically et al. (c) In the absence dangling bonds labeled DB1 and DB2. increasingly so at chain on H:Si(100). the details of structure and faces is that every dangling bond gener- composition of the organic adlayer. DiLabio. elevated) and of nearly constant height across explained on the basis of molecular-orbital have not been always well recognized. G. calculation.6 V. (b) At an intermediate bias of −1.. molecular p-states are ‘‘turned on’’. but the molecules nearest molecules. causing (Figure 1 of P. At increased sample bias of −2. to the dangling bond remain prominent. (b) Bridging hydrocarbon fixed by two C−Si bonds. The practical criterion that characterizes Despite those prospects of practical ap. covalent adsorbates on semiconductor sur- plications. (a) With negatively charged greater distances from DB1. should be terminated by an adsorbate. Nature 2005.4 V. 658 [19]).8 V. 2 Visualization of the electrostatic potential the line. (a) (b) (c) Fig. which ated by the truncation of a single crystal directly influence the quality of surface. J. 1 Schematic view of hydrocarbon adsorbates covalently bonded on Si(111) surface. The . emanating from a point source for a styrene molecules appear darker. The of a negative dangling bond all molecules would prominent white bar is a line of surface-bound appear dark at −1. (a) Single-chain alkyl fixed by one C−Si bond.

was an of the organic moieties cannot make epoch-making event to open up the field one-by-one termination of Si(111) in a of organic chemistry on semiconductors macroscopic area [12]. Liu. that in mixed adlayer with small adsorbates that which the stoichiometric full coverage is at. Appl. uid. 66. can be expected only when the adsorbate is On real adlayers. namely. dated without such spacing species [25]. OH. on which every surface is anticipated between adsorbates. Hamers. such as terminat- tained. fill the spacing areas. Hovis. fills of air and would result in the deterioration most of the space over a single-crystalline of the whole surface. On the basis cyclopentene (C5 H8 ) in UHV environ. of fundamental surface science on single ment [22]. This is a difficulty in (2 × 1) supercell. it was demonstrated that are reactive with O2 and other components even CH3− . R. most Si is monohydride terminated [20]. S553 [23]). complete rejection of dangling bonds Even a C2 H5− group is slightly too should be achieved by appropriate reaction bulky to be accommodated within Si(111)- and handling conditions. bates inevitably lead to formation of a nated by one C−Si bond. J. handled out of ultrahigh vacuum (UHV). is terminated by one CH3 group [24]. S. Long-chain can be formed by cycloaddition of cyclic alkyls and aromatics cannot be accommo- olefins onto surface Si−Si dimers [21]. (a) Cyclopentene adsorbed on ‘‘on-axis’’ Si(001). the adsorbates are ar- small enough to be contained within one ranged randomly [26]. H. (c) Cyclopentene adsorbed on 4◦ -miscut Si(001). A 1998. This sort of full-coverage adlayer nated (m × n) periodicity (m. obtaining ordered adlayers due to the lack (a) (b) (c) Fig. On clean Si(100). Phys. 3 High-resolution STM images of cyclopentene. If the surface is Si(111) surface when every surface Si supposed to be handled in air or in liq. or silicon oxide. (Figure 3 of J. presented a highly ordered This sort of monolayer usually exhibits adlayer terminating all Si atoms just by a good robustness and is as useful as exposing clean Si(100)-(2 × 1) to gaseous fully terminated surfaces. Figure 3 shows STM images of crystals. the smallest alkyl moiety. it is preferable to arrange or- cyclopentene molecules bonded in paral. (b) Clean surface of 4◦ -miscut Si(001) showing double-height steps. showing retention of molecular orientation across step edges. Hamers et al. such as desig- terraces. Attempts to make an adlayer with There are some typical cases in which species bulkier than those typical adsor- every surface Si atom is actually termi. Because steric hindrance H:Si(111)-(1 × 1). ganic adsorbates and spacing adsorbates lel to the dimer rows of Si(100)-(2 × 1) in a well-ordered manner. 1.3 SAMs on Hg Electrodes and Si 159 dangling bonds on surfaces of Si and Ge On Si(111). . n: integer). The discovery of (1 × 1) unit cell. (2 × 1) adlattices ing H.

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

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

The adsorbates are bulky (XPS) observation [6]. in the preadsorbate as a result of C−Si Adsorption of O can be due to acciden. terminating hydrogen atom to form a Si fected by the existence of oxygen adsorbate. and The mechanism of hydrosilylation has the wetting and chemical properties of the been elucidated as the ejection of a whole adlayer usually seem not to be af. Strother et al. in which the best quality was the reaction between H:Si(111) and ter. of organic deposition. A small extent of luted olefins in an inert solvent (such as substrate oxidation was not inevitable. and a neighborhood surface-terminating H. The deposition terminated alkyl grafted on hydrogen- reaction was activated by the coexistence terminated Si(100) by a rather so- of a radical initiator in liquid phase [6]. groups to Si surface can be avoided by the chain alkenes lack in assessment of oxygen difference of reaction rates between the ter- directly bonded on the Si surface. The adlayer of long This category of methods has been alkyl chains is robust and convenient to most utilized to form adsorbates including stabilize Si surfaces and to make modifica. saturated alkanes) improves the quality of probably due to the treatment in aqueous the alkyl adlayer [49]. In O2 dissolved in the reaction fluid. chains on Si(111) is OH species accord. Most some cases the attachment of functional of the succeeding researches using long. or just H2 O molecules 1. at Si surface is often detected by XPS [25] or Auger electron spectroscopy (AES) [9]. immediately picks up tal oxidation from the environment.3. solution for hydrolysis. attained by Grignard reaction on chlori- minally double-bonded olefins (1-alkenes) nated Si substrate discussed in the next has been accepted as a practical method chapter. generated the nuclei of SiO2 island enlargement [7].2. depending on the method of reaction ac- ods of long alkyl chains (>10 carbons) [6]. 51]. bond formation. group [39.2. Webb et al. first hypothesized that the deposited amino-terminated decyl by a spacing species to accommodate alkyl similar protection/deprotection method. and Si surface [50]. The leftover .162 1 Preparation of Monolayer Modified Electrodes line of sight from the specimen should be adlayer. [15] Linford et al. sum- on H:Si(111) Since 1995 when Linford marized the extent of substrate oxidation et al. or process to avoid direct reaction of NH2 by using Lewis-acid catalysis. Use of di.1 Adsorption of Terminal Olefins entangled in the adlayer. first reported the fabrication meth.3. well-defined alkyl adsorbate is then formed. the residual amount of surface oxygen is leaving one Si dangling bond. tivation [13]. and furthermore grafted DNA on the ing to X-ray photoelectron spectroscopy amino group. bates nearest the surface Si atoms. dangling bond followed by an attack of the Small portions of SiO2 deposited during terminal double bond in olefin to form the adsorption process are considered to be C−Si bond [6]. 1.3 Summary of the Latest Researches which is supposed to be oxygen attached to the adsorbates. The origin of OH and the substrate–adsorbate interface did might be the peroxide radical initiator or not perhaps affect the function of DNA. A complete an index of the reproducible. by phisticated amine protection/deprotection heating [6]. The C radical. Oxygen not incorporated in SiO2 avoided. by light irradiation [46–48]. functional groups.3. Sieval reported amino- tions over the adsorbates. The minating double bond and the functional long-chain alkyls may screen the adsor.

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

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

various methods. (a) Cl/Si(111)-50 × 50 nm.5 × 6. 2005. 2004.21 V (sample negative). Eves. The CH3− group is prob. images. −1 V (sample bias). J. The . 2.3 SAMs on Hg Electrodes and Si 165 (a) (b) (c) Fig.38 nA. termination was presented by Yamada tron diffraction and spectroscopy aided et al. 400 pA. (c) Br/Si(111)-6. 121. P. (b) Cl/Si(111)-6. J. 10 nm × 10 nm. −1. ably the only hydrocarbon species that Webb et al. The fea- longer alkyls and assumed that CH3 can tures representing methyl groups changed terminate every surface Si atom on Si(111) according to the STM gap voltage. 5 STM constant current images of 40 pA. preset tunneling current = 2. [24. on the basis of geometrical consideration. halogenated Si(111) prepared by gas phase 50 pA. −1.186 nm. They con. Wawro et al. −0. [13] also extensively compared can terminate Si(111) in (1 × 1) periodicity the perfection of alkyl adlayers prepared by with practical stability. L89 [57]). Yamada. Figure 6 shows the flatness of the cluded that the length of C−Si bond methylated surface viewed in a wide zone. Lopinski. Phys. methylated Si(111).5 nm. Sci. 19. G..48 V.65 nA.4 V. −0. vertical to the surface is 0. Chem. (Figures 3 and 4 of T.5 × 6. Bansal as well as the lattice of methyl moieties et al. reactions at room temperature. M. Surf. ined a methyl-terminated Si(111) from A concrete evidence for methyl (1 × 1) Cl:Si(111) and CH3 Li by X-ray photoelec. (b) A 10660 [24]). 61] as high-resolution STM by synchrotron radiation [60]. Kawai. (a) (b) (c) Fig. (Figure 2 of B.5 V. studied in detail.58 nA. Scan size = 500 nm × 500 nm. 1. gap voltage = −1. Terry et al. 6 (a) A wide-range STM image of high-resolution STM image. 579. (c) 4 nm × 4 nm. [55] listed the results for CH3 and arranged in (1 × 1) periodicity.5 nm. A. exam.51 V.

features actually represent the electron or. Yamada. A. 7).. J. The amount of SiO2 of 4. 121. so far no meth.1%. 2004. (Fig.6 meV. Chem. (Figure 2 of T. sensitively detected by HREELS. Wawro et al. They claimed that the rotation impurity. indicating all the characteris. away from the center of the neighboring sorbed CH3 group. 7 HREELS of the methylated Si(111).166 1 Preparation of Monolayer Modified Electrodes 106 683 Counts [cps] 507 789 2944 1268 1099 1423 x2000 x50 0 0 500 1000 1500 2000 2500 3000 3500 4000 Wavenumber [cm−1 ] Fig. Kawai. HREELS isolated CH3 −SiH3 molecule. However. incident angle = exit angle = 60◦ from the surface normal. 2944 cm−1 : C−H stretching.84 eV. which cor- of CH3 :Si(111)-(1 × 1) was also presented responds to a frequency of 590.5 cm−1 . Yu et al. 1268 cm−1 : CH3 asymmetric bending. 10660 [24]).7 K [62]. the C−Si axis vertical to the surface It is interesting to address the elec- is attractive. performed STM imaging of tic vibration modes including the C−Si CH3 :Si(111)-(1 × 1) at the low temperature stretching motion. 1099 cm−1 : Si−O stretching in SiO2 . 789 cm−1 : CH3 rocking. The energy barrier bitals. and it is difficult to extrude the of rotation excitation may be analogous geometric arrangement of H atoms in to that of torsion of C−Si bond in an CH3 just by viewing the images. 1423 cm−1 : CH3 umbrella motion. tion of C−H bonds rotated by (7 ± 3)◦ In terms of the movement of ad. of every CH3 group was locked at a posi- was controlled below 0. rotation collectively. The full width at half maximum of inelastic peak = 7. Phys. M. tronic property of CH3 :Si(111)-(1 × 1) not ods have been found to observe this only for the purpose of application as . 507 cm−1 : C−Si bending. the rotation about −CH3 group. 683 cm−1 : C−Si stretching. HREELS incident electron energy 2.

was considered to be quenched in Si−D trathin channel medium of field-effect by the presence of deutrated acetic acid. products. tization of hydrogen-terminated porous pied levels additionally to the I–V curve silicon by Grignard reagents. The replacement photoadsorption or by Lewis-acid catalysis. They in- of H:Si(111). terminating D species was detected. The formation of C−Si bond in methyl Grignard reaction on H:Si(111) 1. transistor [14]. concluded that a new controllable and introduces more chances mechanism of Grignard reagent should of contamination. [63] first reported deriva- reached a peak at −1. to replace a part of the terminating On flat H:Si(111). Niwa et al. Webb et al. H:Si(111) is less likely than Cl:Si(111) The STM images of CH3 MgBr-treated to react with alkylmagnesium reagents H:Si(111) showed that methyl groups according to the classic formulation of just formed small lattice patches and Grignard reaction. However. This interpretation fitted with a rather As for Grignard reagents containing rough surface of porous Si. [5]. Replacement of terminating H deposition of C2 H5− or C6 H5− CH2− on with decyl groups was recognized. reported that high. chapter. It is certainly easier be proposed to replace terminating H [64]. and the Si−MgX species (1 × 1) was also applied as the ul. The ro- Cl:Si(111) rinsed in methanol [25]. Kim ized in an electrolytic phenomenon. Such Cl atoms are consid. CH3 :Si(111).3Grignard Reagents and H:Si(111) was first evidenced by Yamada et al. which was alkyl groups larger than methyl. using CH3 COOD. rinsing in a THF so- hydrogen atoms on H:Si(111) by alkyl lution of CF3 COOD did not introduce groups. to be the same as those formed by alkene pated to be hydrogen. This issue is discussed in the next D−Si [65]. explained this process by dissocia- et al. By electronic conduction through the surface. et al. of pit formation related to the backbond resolution XPS did not detect Cl after breakage. [64] The atomic force microscope ered to be replaced by oxygen-containing (AFM) images of alkyl-terminated Si(111) species during rinsing or by exposure show a flat Si surface without any sign to air. redox solution exclusively lowers the peak The formation of Si−R and Si−MgX potential of redox reaction.2.3. 1. incorporation of Si- This conducting property is also material. The bust properties of this surface were found possible terminating species was antici. Boukherroub et al. so far. the space advantageous in the detection of surface filling of adsorbates does not geometri.3. many adsorbates were randomly placed with . Formation of decyl (C10 H21− ) adsorbates and a certain part of terminating Cl atoms by decyl Grignard reagent on H:Si(111) must be left over in the space between was first performed by Boukherroub alkyl adsorbates.3 SAMs on Hg Electrodes and Si 167 the lithography resist layer but also cases of adsorbate formation on hydrogen- as the basis of nanoelectronic devices. [61] demonstrated that CH3 :Si(111). terminated Si surfaces have been re- The I–V characteristic curve of STM ported. tive insertion of R−MgX into Si−Si bonds (1 × 1) as an electrode in an aqueous just below the surface (called backbonds). Kim et al. was assumed. of residual Cl species is probably un. cally allow every Si atom to be terminated. This peak corresponds to cluded a quenching procedure with acetic the electronic state that contributes to acid after the Grignard reaction.5 eV in the occu.

D. More varieties 1. Niwa. The C signals of AES [26] Although this analysis was not com- and XPS [55] indicating the saturation pleted. 7057. stability. Yamada. However with HREELS. In nearly all the cases. 4085. Technol. the Si surfaces within the precursor Chem. indicating that the adsorbate-wise open a new route to organic deposition areal density is constant. Recently Fellah frared spectroscopy. Okiguchi. regardless of the on Si. Nakagiri et al. J. M.. Careful Grignard reagents without isomerization use of D:Si(111) and HREEL showed and component detachment. elucidated on the basis of concrete ex- bates and terminating hydrogen by in. the lution [69]. J. 39. J. Technol. et al. Sci. atoms. Phys. hydrocarbon groups are transferred to 4. chain length. can be deposited with adequate 3. and Si. A 2002. Chem. The H−Si stretch. 106. B 2004. such as branched or et al. T. C. or that Grignard reaction cannot completely even in a Cu-plating solution containing remove original terminating hydrogen F− for a short period [9]. Lie. we can expect the application of coverages are proportional to the chain alkyl halides as the alkylation reagent to length.[5] This fact cyl bromide yielded a finite amount of influences the interpretation of spectra alkyl adsorbate and a significant amount of CH3 :Si(111) formed by electrochemical of SiO2 . Sugimura. S. 3240. unsaturated hydrocarbon moieties [26. 1996. 108. B14. H. 4140. chain length.. proposed a mechanism involving ing signal at 2090 cm−1 became invisible a trace amount of alkyl halide residue to IR as the coverage of organic in. and p-type silicon. B14. H. . D. RMgX. alkali solutions [64]. Whelan. Sci. be more affected by adsorbate screen- Treatment of H:Si(111) in pure tetrade- ing effects than HREELS. N. 68]. The mechanism of H:Si(111) replace- At the same time. hydrogen mixed adlayers are strongly The HREEL spectra always contain hydrophobic and resistive toward dissolved H(D)–Si stretching signal. J. Vac. Fedorov. reagent. Vac. contained in the Grignard reagent so- creased [26]. The effects of alkyl halide were The Grignard reaction on H:Si(111) is scrutinized by voltammetric electrolysis probably the most useful method to obtain of Grignard reagent. G. Hirao. Infrared spectroscopy seems to celerated deposition of decyl groups. The chance of unwanted substrate oxidation during the fabrication References process can be minimized. Craighead of hydrocarbons. by using n-type robust Si surfaces for practical purposes. a limitation was ment by Grignard reagent has not been recognized in detecting organic adsor. 65]. Homma et al.. W. indicating oxygen in water [9]. 2. G. the Phys. Y. 1996.168 1 Preparation of Monolayer Modified Electrodes a significant open area [66]. J. that 100% methylated surfaces were the reaction kinetics with the Grignard obtained [67. The alkyl- C−Si stretching signal at 678 cm−1 [5]. perimental evidences. It was difficult to compare anodization in a Grignard reagent solu- tion. K. Lercel. compared to the case for Cl:Si(111). Decyl bromide intentionally H−Si signal was apparently detected on added in a diethylether solution of de- surfaces prepared under the same con- cyl magnesium bromide significantly ac- dition. K. and by consider- The adlayers formed are constantly a ing the electronic and thermodynamic mixture of alkyl and H regardless of the energy levels of RX.

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and J. Such a molecule. Yokohama. Such of molecules in energy-rich interfacial po- built-up monolayer assemblies are now re.4 Langmuir–Blodgett (LB) Films on Electrodes 171 1.F. A self-assembled monolayer (SAM) was Masaru Sakomura introduced as a possible alternative to the Yokohama National University. Edited by A. Yokohama. 1). 1. the number water surfaces to solid supports. therefore. molecules surrounding it.Fujihira. 10 Modified Electrodes. has higher energy than the Miss Katharine Blodgett had succeeded in molecule in the bulk phase. ISBN: 978-3-527-30402-8 .1 began their stimulating experiments Photoelectrochemistry on monolayer organization [5].1 History of the Langmuir–Blodgett Gaines’ book mentioned earlier. Considering such a situation as on water by Benjamin Franklin in 1774 illustrated in Fig.4.1.1. such as fatty acids. with increasing the surface area by a small while floating monolayers at the air–water amount dA in a reversible way is propor- interface are called Langmuir films. Weinheim. Stratmann Vol. The materials forming the so-called bulk phase is bound to the neighboring insoluble monolayers. because optoelectronics and molecular electronics Masamichi Fujihira have become areas at the frontier of Tokyo Institute of Technology. The LB method was f the first technique to provide a chemist γ = (2) 2L Encyclopedia of Electrochemistry. I. the reader is referred to a relevant textbook [7] as well as to the 1. Hans Kuhn et al. 2. For more details of Japan the historical aspects. In sur- early investigators.Rusling Copyright  2007 Wiley-VCH Verlag GmbH & Co.J. Edited by M. Bard and M.4. A series of their pioneering works are introduced in the book by Gaines [2] The proportionality constant γ is called together with the contributions of other surface energy or surface tension. (LB) Film Surface films of materials that have very 1. materials science [6]. have been recognized for cen. In the mid-1960s. By 1919. we can empirically [3]. The tional to dA: first formal report describing the prepara- tion of built-up films did not appear until dG = γ dA (1) 1935 [1]. KGaA.Rubinstein. neighbors on top (Fig. The LB and SAM films have Japan attracted much attention recently. 1.2 Basic Principles of Surface and poor solubility in the supporting liquid Film phase but exhibit interesting and useful properties. γ is the most fundamental scientific paper on the effect of oily films quantity. When increas- transferring fatty acid monolayers from ing the surface of a liquid. under Langmuir’s guidance. Surface Tension A molecule in a liquid turies.4 with the practical (and still the most exten- Langmuir–Blodgett (LB) Films on sively used) capability to construct ordered Electrodes molecular assemblies. sitions increases. But a molecule are essentially insoluble in water but are at the surface misses the contact with the still surface active.4. LB films. including the earliest face science. define γ by the following equation: layers at the air–water interface by Agnes Pockels in 1891 [4]. The free energy change ferred to as Langmuir–Blodgett (LB) films. and the preparation of the first mono.

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

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

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

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

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

is stearic acid. 8.g. especially in the design of Molecules and Subphase We confine amphiphiles with functional groups such our discussion here to the most popular as chromophores. Many researchers choose an ultrapure LB Deposition Although many differ- water system. doubly charged cations (e. of prime importance to the LB studies. see the relevant that is. supplying water of techniques).4 Langmuir–Blodgett (LB) Films on Electrodes 177 After passing a plateau of the first-order amphiphile. Here. 14] photooxidation unit. Today. acceptors. which includes mixed anion ent techniques for transferring a floating and cation exchange resins. water. Ca2+ . through the monolayer/air interface. gett [1.3 Preparation Methods for LB Films purposes. Such molecular engineering is very important. ultraviolet sterilizer. and then. The water . we will concentrate on the high specific resistance (1. The effect of phase is reached. pH. a glass slide) is first low- carboxylic acid head group (−COOH) ered through the monolayer so that it is hydrophilic. stearic acid behaves The value of surface pressure that gives like a neutral molecule. the best results depends on the na- the carboxylic group dissociates to form ture of the monolayer. The quality of water is textbooks [5–7]. and the substrate (e. Ba2+ .1. [15] and applied extensively by Blod- A classical example of an amphiphile. are linear and its extrapolation to zero sur. many scientists use organic synthesis to construct amphiphiles for different 1. donors. and (e. acting as counterions. In where the long hydrocarbon tail group the most commonly used method. 1. At higher pH. first introduced by Langmuir the ppb (parts per 109 ) level. a reverse monolayer to a solid plate have appeared osmosis unit. so on. facilitate monolayer phase transition.g.4. the (CH3 (CH2 )16 −) is hydrophobic. In order to secure the Solid (S): The films are rigid and densely reproducibility of the π − A isotherms. a liquid-condensed (LC) transfer on solid surfaces. the amphiphiles the ion binding to reduce the extent of exhibit a tilted phase with a decreasing tilt electrostatic repulsion between charged angle. the monolayer. The film is relatively stiff but still head groups allows for close packing of more compressible. The ionization of the dips into the subphase and then with- carboxylic group will be suppressed at drawn under a constant surface pressure. low pH. deposition follows the sequence stabilize the monolayer of the anionic of events described in Fig. and supporting liquid for monolayer studies. For more details. and composition of the subphase at the ular to the surface. The presence of empirically. The it is crucial to keep temperature. The π − A isotherms constant conditions. This technique involves the which can form an insoluble monolayer vertical movement of a solid substrate on a water subphase. If the slide is used as a hydrophilic and Cd2+ ). molecules are oriented almost perpendic.8 × 105 m) and total organic contamination (TOC) in LB method. packed with high surface viscosity. and is established carboxylate ion (−COO− ).g. 16]. The reader can find a discussion of the face pressure gives an area per molecule properties of monolayer films of a variety that corresponds to the molecular cross. can surface. ‘‘touching’’ [12] and ‘‘lifting’’ [13. At pH 4. sectional area. of amphiphiles in Gaines’ book [2].

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

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

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

1. In a monolayer of dye I (Fig. After the compression. which absorbs at longer wavelength. They organized tadecane in a 1:1 mixture can be regarded a large variety of monolayer assemblies as two-dimensional crystals with a brick- to investigate intermolecular interactions. for example.4. 1. for studies on the adsorption between a back surface of a harvesting light energy and channeling the floating monolayer and a soluble mate. 13). As systems consisting of cooperative molecu. proposed by Kuhn et al. Since the . [5. host) 1. 27]. the surface pressure is mea- surable at any compartment. or in chemical nent in any proposed photoelectrical device reactions. When the film compression would be per- formed. as a spacer and contributes to the ar- As good examples of their research. 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. Such monolayer manipulation by the multicompartment trough may be applied. the monolayer formed between the two barriers can be transported to other com- partments with different subphases by the synchronized motion of the two barriers (Fig. A system chromophores is t = 10−13 s.4 LB Assemblies Designed for with traces of dye II (Fig. The energy migration The Langmuir trough technique enables in the layer of the host depends strongly us to construct simple artificial membrane on the interaction of the molecules. Much of the pioneering monolayers prepared by spreading the work in this field has been carried out by dyes and the long chain hydrocarbon oc- Kuhn and his colleagues. J aggregates in lar components. upper part of one of the movable arms. stone arrangement of the chromophores and photophysical and photochemical pro. 14. is Energy Transfer in Monolayer Organization trapping the energy.4 Langmuir–Blodgett (LB) Films on Electrodes 181 Fig. 13 Monolayer manipulation using the multicompartment trough. 23]. octadecane acts cesses [24–26]. The film transfer onto a substrate has to be car- ried out only on a compartment in which a well for the LB deposition is provided. guest) the host Photoelectric Devices is harvesting light energy and the guest. for solar energy conversion. 14. It can the investigations of the energy transfer be demonstrated by a quantum mechan- from a sensitizing molecule to an acceptor ical calculation that the exciton hopping molecule within the complex monolayer time in this very compact arrangement of organization will be given here. energy should be of interest as a compo- rial in a subphase [22. therefore. In these films. rangement of the aliphatic region.

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

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

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

that is. structure and function of the molecu. 49. (12). Marcus where the free-energy barrier for phiphilic properties. 18(a). within LB tor/sensitizer/donor (A/S/D) type LB mul.4 Langmuir–Blodgett (LB) Films on Electrodes 185 0.5 C18 C20 −1. compounds tend to orient regularly in the Relationship (13) was first introduced by heterogeneous LB films due to their am. is another important factor in and squares. and D. and Systems A variety of electronic compo. the proposed by them. 1. Their ob- of the foresighted concept of molecular served dependence agrees in a qualitative diode by Aviram and Ratner [30]. For ex.5 3. M¨obius [28. (11). moieties. 16. sense with the other experimental [38–48] ample. that is. electron pump [32] on a gold optically the effect of the standard free energy transparent electrode (AuOTE) [33]. 37] have studied the distance nents with molecular dimensions have dependence of the rate of photoinduced been investigated since the introduction electron transfer in LB films. 35]. (11) and Eq. based on Kuhn’s idea of the light-driven In addition to the distance dependence.0 C22 2. 50]. where hydrophilic parts and hy. monolayers can be closely controlled at tilayer system as a molecular photodiode known values. S. Mezger and Panetta [31] have made and theoretical [29] results described by an effort to realize the molecular diode Eq. others [36. 34]. that is. case (b). As they did.0 d [nm] Fig. A. G∗ in Eq. fabricated the accep. distances between the three functional Fujihira et al. 17 Quenching of fluorescence of dye II (D) by electron acceptor III (A) in the arrangement of Fig. the difference between the energy lar photodiode of A/S/D are shown in levels of the excited (or ground state) donor Fig. and the ground state (or excited) acceptor drophobic units are indicated by circles [29. The difference G◦ for the electron transfer. 26. the reaction.0 C14 C16 Log {(I0/I ) −1} C17 −0. Log{(I0 /I) − 1} is plotted against the spacer layer thickness d for fatty acids with 14-22 C atoms. Acceptor/Sensitizer/Donor Multilayer Kuhn [24.0 2. is . Three functional determining the rate of electron transfer. respectively.

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

18b. (2) a Au wire counterelectrode. For example.A.D. S.A/S. (3) a saturated calomel electrode (SCE) with a salt bridge.S. 20) for constructing more efficient a rectifying ability as does a semiconductor molecular photodiodes [62. Yet. 61] for stacks of multilayers aromatic polyimide itself as A. films consisting of A. of polyimide LB films [64–66]. the hole-carrier property long alkyl chains are intervened between of the D layer was further improved by the the A and S and between the S and use of triphenylamine in place of ferrocene D moieties. The AuOTE is a metal elec.D and polyimide as S.D/S. 63].A.S. ening the distances between the functional and their coworkers used polyimide LB moieties is the use of synthetic molecular . electrons should rection is in accordance with the energy be more readily transferred. and 6 layers of a ferrocene D. The three kinds of functional am- phiphilic derivatives used for the first A/S/D-type molecular photodiode [33] are shown in Fig. They have electrode [38–41]. 18(a).D. thickness. for example. The directions of derivative with aliphatic polyimide as D is the photocurrents also agree with those enhanced about 10 times larger than those expected for the multilayered systems. reported the preparation and properties ability of the substrate electrode to rectify. profile across LB films in Fig. 18(c) together with por- phyrin sensitizer S2 used later. for photodiodes with conventional LB In such heterogeneous LB films. and D units trode and hence does not by itself possess (Fig. 0. in spite of the in. (4) a cell container. To Photodiodes Another approach to short- cope with this problem. the photoinitiated vectorial flow of electron is achieved and detected as photocurrents. Since the photocurrent in opposing directions polyimide LB films have no long alkyl depending on the spatial arrangement of spacer between the layers (monolayer A/S/D or D/S/A is detected [61]. The di.4 Langmuir–Blodgett (LB) Films on Electrodes 187 Fig. vii) LB Assemblies of Synthetic Molecular without quenching by electron transfer. 1.4–0. 19) 4 [38–41].6 nm). in of a porphyrin derivative with aliphatic the form of A. the films [62]. As a result. 2 layers of each component.A. 18(b). Later.S/A. 3 the pair across the large separation by LB film (process (vi)) is hindered by the distance dependence. the photoelectrical conversion efficiencies Much higher photocurrents can be of AuOTEs coated with 6 layers of observed [33.S. as shown in Fig. Kakimoto. parts of the as the D moiety [63]. excited sensitizers were deactivated by the emission of photons (Fig. and by the use of the resulting electrode as a working electrode 2 1 in a photoelectrochemical cell (Fig. 19 A cell for photoelectrochemical measurements: (1) an LB modified AuOTE. Imai.S/D.S. By deposit- ing these three amphiphiles on AuOTE.

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

in visible light. donor (D. the lived charge separation is still difficult and spatial arrangement of the three moieties has only been reported in a few works in the order of acceptor–sensitizer–donor [89. the triad forms give long-lived charge-separated states in stable mixed monolayer with arachidic high yield have been realized with some of acid. the S–A–D triads were called the triads [33. 21. was expected (Fig. into the air. 91] are shown in Fig. At tron transfer from excited singlet states to an air–water interface. The early amphiphilic surface. 22a) under high surface pressure. 1. and photoinduced elec. mimicry A moiety of the triad is oriented toward of the farther aspects of photosynthesis in. three functional folded-type S–A–D triad. However. ferrocene (Fc)). a neutral sensitizer be initiated through light absorption of . Fujihira’s group has been C11 or C16 ) linking A to S and D. in which the dicationic hydrophilic these artificial systems. two steps of moieties. In this highly ordered these amphiphilic triads. 90]. The (S. water and two hydrophobic alkyl chains cluding chemical processes driven by the terminated by S and D subunits extend chemical potential in the form of the long. In such monolayers. many of the reaction center models. Because of the folded form can spread and form monolayers on of the oriented molecules on a water water surfaces. singlet energy transfer be. viologen (V2+ )). by sigma-bonded tunneling bridges. In folded-type triad. which the active components were linked tween pigments. owing to the difference in the A–S–D Triad Monolayer Systems Since length of the two alkyl chains (C6 and 1985 [33]. studying amphiphilic triad molecules that respectively. 21 Structural formulae of the folded-type triads. and a neutral electron primary event of photosynthetic solar en.4 Langmuir–Blodgett (LB) Films on Electrodes 189 S−A−D C11 S−A−D C16 Fig. a dicationic electron acceptor intramolecular electron transfer would (A. pyrene (Py)). were combined ergy conversion including absorption of in the order of S−A−D (Py–V2+ –Fc).

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

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

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

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

28 The change in the surface potential by step illumination for ca.194 1 Preparation of Monolayer Modified Electrodes Tip for SSPM + D D S S − A A a Au-coated quartz plate hn Laser off Laser on Fig. . Light off 60 S D S D A A S D S D A A 40 30 layers 20 Surface potential change 0 Light on [mV] 0 Light on −20 D S D S D S A A A −40 D S D S D S A A A 30 layers −60 Light off 0 10 20 30 40 50 Time [s] Fig. 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. 2-3 s with a He−Cd laser light in a total reflection mode.

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

an acylated perylene of anodic photocurrents at ca. Thus. Figure 33 [93]. 32). For the light-harvesting (H) antenna shows the photocurrent spectrum of the pigments. 32). as the A and the the adsorption maxima of pyrene and acy- D units. The A–S–D mixed monolayer consists of A–S–D (V) and 22-tricosenoic acid (1:5). These correspond to cylated ferrocene moieties. the molecules are efficiently transferred to the monomolecular layer assembly including sensitizer moiety of the triad. As illustrated in Fig. the a triad and a synthetic antenna molecule excitation energy of the perylene moiety is designed to mimic the two successive should be converted to electrical energies aspects of a primary process in natural pho. Maxima linear triad molecule. 30 Photoinduced surface potential change under step illumination by He−Cd laser (441. self and with the pyrene antennas followed light energies harvested by the antenna by the energy transfer. 470 nm are found. challenges. The the good overlap of the emission spectrum result indicates that charge separation in of the antenna pyrene moiety (Py) and the triad molecules was initiated by light the absorption spectrum of the sensitizer absorption both with perylene sensitizer it- perylene moiety (Pe) of the triad (Fig. .6 nm) for the LB assemblies (a) without and (b) with a pure D bilayer. via multistep electron transfer across the tosynthesis: antenna and reaction center monolayer as described above. 350 and moiety. are used. 31. respectively. an amphiphilic pyrene deriva. and viologen and dia. as the S unit. Because of lated perylene (solid curves in Fig. mixed monolayer of the triad and the an- tive [121] is used. For the amphiphilic tenna with a molar ratio of 1:4.196 1 Preparation of Monolayer Modified Electrodes 15 A−S−D system 10 D D S S A A Surface potential change 5 2 bilayers (a) 0 [mV] 200 A−S−D/D′ system D′ D′ D′ D′ D′ D′ D′ D′ D′ 150 D′ D′ D′ D′ D′ D′ D′ D′ D′ D D D′ S S A A 100 2 bilayers 50 (b) 0 −2 0 2 4 6 8 10 Time [s] Fig.

and charge separation via multistep electron transfer.4 Langmuir–Blodgett (LB) Films on Electrodes 197 Triad V A−S−D Antenna dye H hn on ig rati ym erg ral en ate r S fe L to ns H tra hn m gy fro ner E Charge A separation H D H H S Electron transfer Lateral across the membrane energy transfer Fig. 1. the dependence of also examined [122]. energy migration and transfer. The result indicates sensitized emission intensity on the ratio that the most efficient energy transfer . To focus only on the energy transfer of H with an energy acceptor molecule is process from Py to Pe. 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.

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

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

Am. P. A. 325 and 441. R.6 nm. distances suppress lateral charge migra. Chem. Normally. Jpn. Roberts. P. Chem. 78. 25. T.6 nm of L1377–L1380. 1990. 26. Chem. Barraud. J. Srivastava. P. is ca. J. Langmuir. Biochim. J. 356. 64. that the light energy harvested by the 225. Trans. antenna molecules is mostly funneled to 49. 1975. system. Fromherz. Kuhn. Rev. G. 382–387. The number of the 19. Kuhn. Ulman. Am. The pyrene absorbance of Interface Sci. perylene in the grand state under illumi. 1987. 77–95. Roberts. which acts as charge diffusion layer. 43. 83–88. Fromherz. V. Blodgett. Marcheva. 60. illumination of 441. 3. W. 13. B. hole diffusion (iv) via hole migration 1007. 1979. H. Palacin. Thin Solid photons of the incident light at 325 nm Films 1985. B. the 8. A plane are expected to occur in this 1966. New a D bilayer. B. molecule. B. Nature 1891. Colloid alone because prolonged intermolecular Interface Sci. Ple- and 325 nm (a dotted curve) [124]. Chem. Thin 25 times larger than that of perylene at Solid Films 1985. Schaefer. M¨obius. J. Langmuir. Vinograd. A. J. J. 1956. London 1774. L. 57. 46. 1–9. H. B¨ucher. Ford. 18. 577–702. 1/35 against that at 441. H. Academic Press. New York. Soc. 117–123. Insoluble Monolayers at electron accumulations in the D and Liquid Gas Interfaces. D. in the second donor layer and hole and 2. similar to fatty acids. R. G. R.6 nm. Weissberger. Vol. 1 (Eds. in the mixed A–S–D monolayer with H with Techniques of Chemistry. J. 53. 17. I. Leloup. of the Py−Pe system mentioned above. 20. perylene sensitizer in A–S–D is directly 9. 1937. the film at 325 nm is estimated to be ca. Soc. the change Spink. Fukuda. But the film added by D bilayer. B. 1920. J. excited and H contributes as a diluent VCH Publishers. Rossiter). 6. Nakahara. 133. Appl. Holcroft. 1863. Biophys. J. B. McBain.6 nm [95. pp. Interfaces and Colloids. Petty. 1981. Philos. J. in surface potential would not be de. McBain. G. K. 437. Pure Appl. Langmuir-Blodgett Films. Phys.200 1 Preparation of Monolayer Modified Electrodes harvesting (ii) and successive charge References separations (iii) proceed similarly as in the former monolayer of A–S–D and 1. New York. transfer from excited pyrene of H to the 11. 1351–1360. J. J. K. 1975. 1976. New York. 146. D. the light illumination at 441. difference between the resulted signals at 1380–1385. On the basis of the energy transfer study 4. 10. Wiley. Blodgett. M. 111. Chem. perylene sensitizer is induced by energy Kolloid-Z. H. Wilson. H. 430. T. G. Soc. 119. D. Phys. A.6 nm (a solid curve) 7. Wiley. 1991. D. A. L. 441. 1940. Instrum. 134. H. Trans. Pockels. Kolloid-Z. the He−Cd laser used. Colloid wavelengths. it can be concluded 22. 14. Schulman. Photochem. 121]. Kapil. Franklin. 244–249. Soc. W. A. 15. tectable with such diluted A–S–D layer Soc. 1972. 12. W. Gaines. Fromherz. J. A. J. H. Chem. C. A. large surface potential change at both 495. tions. 1938. Myers. Surfaces. Figure 35 shows the change York. S. 342–343. 1991. I. Kuhn. Am. 54. . Wilson. Kato. T. Faraday Soc. 2105. An Introduction to Ultra Thin in surface potential measured with the Films from Langmuir-Blodgett to Self Assem- (A–S–D + H)/D system under the step bly. K. 1979. 62–74. nation at 325 nm. Am. 72. 1935. FEBS Lett. K. New York. V. J. Acta 1971. Considering the 21. Sci. 1934. D. gave 16. 62. F. Waterhouse. 5. Kato. 445. With num Publishing. 23. 177–217.: the molar mixing ratio 1:30 is added by A. the sensitizer moiety of the A–S–D triad 24. 329–333. whereas excited 10. Ann. J. 56. K. Wilhelmy.

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devices. to hexa- The use of electrodes modified with cyanoferrate(II) ([Fe(CN)6 ]4− ) in solution immobilized redox-active molecules pro. and thermal properties. Japan ‘‘Molecular Wires’’ and Phthalocyanines It is known that LB techniques can be Naotoshi Nakashima applied for the construction of thin film Kyushu University. lar electronic devices. and electrodes as thin films [8–10]. chemically active quinolinium complexes cial lipids. 1) on electrodes by monolayer and LB films of enzymes. scanning tunneling spectroscopy (STS) teins. respectively. pro. Ultrathin films of electrochromic lipid hybrid and fullerene-lipid composite molecules such as multireducible double- bilayer membranes is of interest both from decker phthalocyanines are one important a fundamental and practical application possible component of color display point of view.4.2 Electrochemistry of LB Films of (NIMS). through the LB monolayer. fer. 1. 3]. 7]. The are of interest since their study allows the fifth reduction had been theoretically . Multiwalled carbon nano. Potential-step chronocoulometric re- vides a simple methodology by which to sponses revealed that the LB monolayer study the ultrathin film electrochemistry acts as an organic ultramicroelectrode ar- of water-insoluble redox-active molecules. [6. phthalocyanines. amphiphilic matrices and cast on mechanical.1 Introduction wires’’ and are expected to be a conve- In this chapter. Japan electronic devices and molecular recti- fiers [1–5]. Metzger et al.4. rectification systems using LB monolayers niques to biomimetic membranes in of substituted quinolinium tricyanoquino- aqueous media. proteins and fullerene deriva. We describe here Electrodes (B) Electrochemistry how to make ultrathin films of nanotubes on substrates. 2) were mixed with terials that have remarkable electronic.2. ray. alkyl chains (Fig. The formation of electrode devices [1–5]. The double-decker lutetium(III) tubes (MWNTs) and single-walled carbon phthalocyanine molecules having long nanotubes (SWNTs) are novel nanoma. phthalocyanines undergo up to five otubes in aqueous and organic systems reductions at the modified electrode. constructed electrical encouraging the application of such tech. Soluble carbon nan.4 Langmuir–Blodgett (LB) Films on Electrodes 203 1. and antibodies as biosensors or [1. artifi. The unimolecular electrical recti- biomolecular switches because of their fiers prepared by using LB techniques are high sensitivity for their substrates and useful for the construction of molecular antigens. Tsukuba.2 chemical and biochemical design of func- Langmuir–Blodgett (LB) Films on tional carbon nanotubes. It is of interest to use dimethanides (Fig. transferred on to gold electrodes show tives. Conjugated redox-active com- pounds are candidates for ‘‘molecular 1. Fukuoka. Takashi Nakanishi National Institute for Materials Science 1. the electrochemistry of nient tool for the construction of molecu- Langmuir–Blodgett (LB) films of func. thin fullerene films including fullerene.2. We have reported tionalized molecules including ‘‘molecular that LB films of π-conjugated electro- wire’’ compounds.4. These specific functions. and carbon nanotubes (CNTs) is rectified transmembrane electron trans- described.

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

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

206 1 Preparation of Monolayer Modified Electrodes Fig. the lipid tail extended to the air [37] which may create a novel field in the chem. the electronic of 0. heating over 47 ◦ C. chemistry of lipid bilayer membranes. the fullerene moieties can be controlled spectively [32]. suggest. 36]. synthesis. is an electronic interaction between the This lipid forms stable Langmuir mono. damental property of the self-assembled ture of the fullerene-lipid monolayer on bilayer membrane film is maintained in water. 36. there chain lipid [28. 4). 32. interaction of the fullerene moieties is loos- ing the formation of monolayers with ened. (Fig.0 nm Water rwater = 1. 33. the fullerene moiety was the LB film prepared in the dark.0 Fig. 5). fullerene moieties in the LB film. indicating in contact with the water surface and that the molecular orientations of the Air rair = 0 rlipid = 0. Upon layers at the air–water interface [32. 5 Schematic illustration of the nanostructure of the monolayer of the fullerene lipid on water revealed by in situ X-ray reflectometry measurements. istry and biochemistry of fullerenes. We The LB film prepared in the dark shows have reported the design.2 nm rC60 = 1.78 and 0. .98 nm2 /molecule. and temperature dependent UV–vis absorp- characterization of a C60 -bearing triple. 37]. At lower temperatures. re.3 dC60 = 1. In situ X-ray reflectometry by the phase change of the film. 4 Chemical structure of the fullerene lipid. that is. 37] (Fig. which is the subphase The surface-pressure–area isotherm of transition temperature of the cast films of the fullerene lipid gives limiting areas the fullerene lipid [28. tion spectra. The fun- (XR) techniques revealed the nanostruc. The electronic interaction between hexagonal and simple square packing.9 dlipid = 1.

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

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

Sagara et al. 1995.). 166. Soc. B 1998. 1996. Sagara et al. R. Y. T. 1641.. et al. S. 6. Chem. S. Langmuir 2001. Phys. Aoki et al. Nature 1996. 12. Y. K. 2272. Langmuir 2002. M. Nakanishi. Chem. F. Chem. Matsui. 20. I. M. Chem. 11. 340. Physics and Astrophysics and molecular-information transducers of Carbon. Manabe et al. Phthalocya. 2001. Langmuir 2003. 1766. Kunitake. 7754. (Eds. 103. I. L.. Gorbunova. 2267. 34. H. Langmuir 1998. Nakashima.. 14. 4. Chem. J. 37. M. B 2001. Campbell. A. 2000. Narikiyo et al. Thin Solid Films 1995. Nakashima et al. K. R. G. 9043. Sluch. G¨urek et al. Nakanishi 8. 17. 27. 67. J. Jaiswal. B 2003. lands.. M. proteins 19. The construction of such From Synthesis to Optoelectronic Properties. 633. D. J. G¨urek et al. 1021. Shigehara. Angew. M. T. Soc. Zhou. 10... Gorbunova. 1955. Murakami et al. 1991. 7. 1219. J. Kroto. Beeby et al. 23. K. 2671. Chem. Bull. 7.2. V. Chem. 10. Nakashima. Lang.. 2002. E. Chem. Rodr´ıguez-M´endez. Noda. J. Phys. Billups.4 Langmuir–Blodgett (LB) Films on Electrodes 209 1. 29. Ed.. 3386. Y. Engl. Nasu. 1998.. Fullerenes. J. H. tures on substrates should be promising 21. 26. K. T. Chem. 30. Ed. Bull. including ‘‘molecular wire’’ compounds. 1993. 19. M. M. and carbon nan. Nonaka. Murakami. F. Samuel. et al. 257.. A. N. 3803. 13. Ohwaki. 8. Faraday Trans. 36. Ebara. Cambridge University Press. T. 3343. L. Porphyr. D. 105. M. Ultrathin films with ordered struc- minsterfullerenes. 3. 9. Chem. Bard. 22. J. 108. Qiu et al. Zorin. 14. Azumi et al.. 105. Nakashima. 12. J. mus. Phys. 28. with controllable and fine structures at the Cambridge. Nakashima. H. L. Amaresh. T. A. Echyegoyen 3. 68.. Laksh. Martin. K. Ishii. Funct. Cliffel. Watanabe.6 Conclusions 16. Y. Eur. J. VCH. W. H. Nakanishi. 227. E. Ebato. I. 382. 2002. D. 32. T. mikantham et al. 18. 11. 1998. P. As- 1994. K. 37. Luengo. Xu. phthalocyanines. Buck- otubes. Ciufolini. and fullerene derivatives. Langmuir 1998.. M. J. Chem. 2002. 304. 327–329. 12789. T. Nakanishi.. E. 1998. Chem. We have reviewed a recent progress on Thin Solid Films 1998. W.. K. T. Langmuir 1995. T.. J. 9560. Lett. 107. Int. Y. 2. Phys. T. 7. 10042. Liu. Soc. Ijiro et al. Soc. Soc. 113. C. 2003. A. Guldi. M. Murakami. Chem. H. F. A. Kadish. 14. Int. K. 65. T. 35. A. B 2004. Chem. muir 1988. A. A. T. Morita. 1997. Rev. 7280. H. Yilmaz. Angew. 1. R. N. Am. de Saja.. Chem. H. M. Y. B 2001. T. 4484.. Sagara et al. I. 91. M. Katagiri et al. 31. Y. 1995. Phys. W. Nakanishi. Langmuir 39. Langmuir 2001. Srdanov 1. 118. Abe. Tachibana. 115. K.. T.. Phys. Mouri. Chem. Y. Jpn. Chem. Nakashima et al. Kunitake. 1775. Diederich. et al. Hungerb¨uhler. Nakanishi. artificial nanomolecular devices is a great Kluwer Academic Publishers. J. Hirohashi et al. H. 15. New York. Nonaka Chem. Y. References 24. M. Tsuruta.. 639. 103. Am. N. V. 4. Nakanishi. Narikiyo. B 1999. Nassar. 5004. K. 9817. H. J.. Chem.-D.-E. 1994. Nakanishi. R. 2003. Lett. Nasu. T.. Rodr´ıguez-M´endez. Am. N. Tokunaga 5. 102. Okahata. Ariga et al. W. Phys. Tanaka. N. N. O. 42. J. Cardullo. Murakami. molecular level. 440. Murakami. R. N.. N. Nakashima. 25. Phys. M. Mater. A. I. 33. The Nether- challenge in the near future. Lett.. The Fullerenes. 660. Nakashima. M. et al.. R. the electrochemistry of LB films and re- Chem. I. M. Y. 17. J. D. 2497.. Soc. T. 7328.). Kuriyama. Lett. M. K. Eur. 1993.. et al. Shirakusa et al. 520. Y. Kalashnikova et al. Hara et al. N. Chem.. Yilmaz. H. Nakanishi. H. 1993. Nakanishi.. Nakamura et al. Tokunaga. . Peterson. Liu. T. Chem. J. Matsumoto. Metzger. Tanaka et al. N. Adv. 375. 18. 38. (Eds. N. Guldi. Engl. 1373.. T. Chem. K. 2001. Nakashima. Mitsuishi. I. New Horizons nanomaterials for future nanoelectronic for the Chemistry. 3442. lated films of functionalized molecules 18. A.. J.4. Jpn. T. artificial lipids. Chlistunoff. T. Ariga. Metzger. 2003.

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

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

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

5 Schematic illustration of the nanostructure of the monolayer of the fullerene lipid on water revealed by in situ X-ray reflectometry measurements. the fullerene moieties can be controlled spectively [32]. indicating in contact with the water surface and that the molecular orientations of the Air rair = 0 rlipid = 0. the lipid tail extended to the air [37] which may create a novel field in the chem.78 and 0. . 37] (Fig.3 dC60 = 1. synthesis. heating over 47 ◦ C. chemistry of lipid bilayer membranes. there chain lipid [28.206 1 Preparation of Monolayer Modified Electrodes Fig.9 dlipid = 1. suggest.98 nm2 /molecule. 4 Chemical structure of the fullerene lipid. 36. re. 4). Upon layers at the air–water interface [32. is an electronic interaction between the This lipid forms stable Langmuir mono. and temperature dependent UV–vis absorp- characterization of a C60 -bearing triple. that is. 32. 33. istry and biochemistry of fullerenes. the electronic of 0. damental property of the self-assembled ture of the fullerene-lipid monolayer on bilayer membrane film is maintained in water. At lower temperatures. interaction of the fullerene moieties is loos- ing the formation of monolayers with ened. which is the subphase The surface-pressure–area isotherm of transition temperature of the cast films of the fullerene lipid gives limiting areas the fullerene lipid [28.2 nm rC60 = 1. The fun- (XR) techniques revealed the nanostruc. 5). tion spectra.0 Fig. 37]. The electronic interaction between hexagonal and simple square packing. the fullerene moiety was the LB film prepared in the dark. fullerene moieties in the LB film. 36]. In situ X-ray reflectometry by the phase change of the film. We The LB film prepared in the dark shows have reported the design.0 nm Water rwater = 1. (Fig.

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

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

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

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

For spread on the water surface as a func. and analyzed as the disk microelectrode ods in the studies of Langmuir films is. Current characterize the surface monolayer film. the main subject of this review. Its type and design reflect a particular type of electrochemical experiment to be carried out to characterize monolayers on the air/water interface. is slowly brought into a close proximity indeed. of a Langmuir monolayer film. 3. the sake of completeness.5. ments have been developed: (1) horizontal touch (HT) experiments involving a pla- 1. and a Brewster adding that scanning electrochemical mi- angle microscope (BAM) [12. Several The use of electrochemistry to character. 1 A schematic drawing of a Langmuir trough instrument. in Volume 3.8. versus distance dependence is recorded Application of the electrochemical meth. In the follow- of the surface normal component of an ing sections. examples of this approach to the stud- ize Langmuir films directly at the air/water ies of Langmuir films were reported by Unwin and coworkers [14–17].2 nar working electrode held directly above Horizontal Touch Electrochemical the air/water interface and contacting Characterization of Monolayer Films at the a monolayer film spread on the water Air/Water Interface surface. rect method of probing charge transport The potentiostatic setup shown in Fig. directly ter surface are used to electrochemically underneath the water surface. it is worth tion of their MMA [11]. we discuss these approaches average dipole moment of the molecules and present key experimental results. 1 in Langmuir films involves a disk micro- and a working electrode touching the wa. Scanning interface was introduced in the mid- Electrochemical Microscopy (SECM) is the eighties.2. Since then two classes of experi- subject of Sect. The latter croscopy (SECM) has also been applied technique allows one to image morphol.212 1 Preparation of Monolayer Modified Electrodes Potentiostat Kelvin probe Surface Brewster microscope balance La m D se a ca CC er r Barrier W C R R a Fig. and (2) two-dimensional (2D) elec- trochemical measurements involving line Horizontal touch is a term that can be microelectrodes positioned in the plain attributed to Langmuir and Schaefer who . The working electrode resides at the air/water interface. potential that can reveal the dependence of the air/water interface. 13]. electrode held in the subphase. to investigate Langmuir films. This indi- ogy of surface films during compression.

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

The summary of these results is were in agreement with their surface ten. Malec and coworkers mod. the the liquid alkane/water interface are sim. Indeed. These experiments involved of a Langmuir trough [30]. 1 pmol. the formation of small micelle-like aggre- coulometry. surface pressure becomes zero. Integration respreading at the metal/solution interface of the charge versus potential data yields at less negative potentials [30]. aggregates near the metal surface were in- fined as the difference between interfacial vestigated by reflectance spectroscopy and tension in the absence and in the pres. The authors The HT voltammetry with gold elec. conclusively demonstrated a direct rela- trodes was also recently used to measure tionship between the electrode potential the surface partitioning constant of a solu. and that the pro- charge density at the metal solution inter. 2. and corresponds self-assembly of short alkane chain thi.214 1 Preparation of Monolayer Modified Electrodes ca. and the surface pressure of the surfactant ble. light scattering measurements [29]. redox-active surfactant at the air/water monolayer on the metal/solution interface. Surface pressure is de. The subsequent electrochemi. The surface single crystal gold (111) electrodes flamed prior to each HT experiment and then pressure of a monolayer at the water/air suspended slightly above the water surface interface and at the metal/solution inter- (the hanging meniscus method) trapping a face is the same only at the potential of Langmuir monolayer at the metal solution zero charge. It then decreases with an increas- properties of the air/water interface. the HT measurements of a complete desorption of the monolayer the Gibbs monolayer formation constant film. The latter technique allowed gates of the surfactant desorbed from the the authors to precisely measure the metal/solution interface. negative charge at the metal/solution inter- sions of the air/water interface and of face. kowski’s research is a discovery that the ap- cal experiments involved measurements plication of a negative potential results in of the interfacial capacitance and chrono. The first one concerns the ef- Langmuir apparatus were to be used. At a sufficiently negative potential. indicating ilar [8]. The exis- plots of the surface pressure versus the tence and the structure of the surfactant electrode potential. therefore to the highest monolayer packing ols in order to mimic the thermodynamic density. Lipkowski’s mea- siometry and Brewster angle microscopic surements demonstrated that in the HT measurements [25]. Overall. interface [25]. The surface pressure is at a maximum at a ified the surface of gold electrodes by potential of zero charge. The second conclusion of Lip- interface. They ing negative potential and thus increasing relied on the fact that the surface ten. experiments the electrode potential is the Lipkowski and coworkers used the HT parameter controlling the surface pressure electrochemistry to study electrochemi- of a monolayer film at the metal/solution cally inactive compounds such as oc- interface just as the surface pressure of tadecanoic acid in Langmuir monolayers a Langmuir monolayer is controlled me- under controlled surface pressure condi- chanically by adjusting the surface area tions [26–32]. Addi- ence of the surfactant. cess is reversible resulting in monolayer face as a function of potential. shown in Fig. Lower detection limits were following two conclusions of fundamental anticipated if much smaller electrodes and importance. The results of these tional electrochemical and spectroscopic experiments can be summarized in the work probing the questions of monolayer . fect of the electrode potential.

2 0. It appears that a lateral monolayer formation of a lipid bilayer structure at flow from the air/water interface to the the metal/solution interface in which the metal/solution interface is possible in bottom half of the bilayer constituted a cases of liquid films. An entirely different application of elec- active Langmuir monolayers raised the trochemical methods involving a horizon- question of whether monolayers at the tal touch approach was developed recently metal/solution interface could respond to by Miller and coworkers [37. As discussed next. desorption and aggregation was reported surface pressure gradient as well as on the by Bizzotto and coworkers [33–36]. and metal/solution (MS) interfaces investigated by the HT electrochemical methods. 1. Langmuir film on the water surface. Un- surface pressure changes at the adjacent like the previous authors. The HT step led to the [38].5 Electrochemistry of Monolayer Assemblies at the Air/Water Interface 215 50 45 40 35 30 [mNm−1] pMS 25 20 15 10 5 0 40 30 0. The HT investigations of redox in. structure dependent monolayer fluidity. 39–41]. represents conditions under which the surface pressure of the C18 OH film is the same at both interfaces (from Ref. gold electrode coated with a monolayer of fered independently first by Miller [37] long alkyl chain molecules.2 −2 Nm S [m pG −0.6 10 8 − nal 0 −0.4 0. typically oc- and coworkers and then by Lipkowski tadecane thiols. E Ratio] . drawn at E = Epzc . Sev- the rate of this transport depends on the eral different variations of this general . V 0 −1 [ Fig. The straight line. Miller used a air/water interface. 2 Thermodynamics of the octadecanol (C18 OH) monolayer films at the air/water (GS). 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).0 ] 20 −0. 28). and the electrode potential. The answer was of.

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

41]. in the limit of long time equilibration layer assembly was also discovered and in. The effect of measurements. the Langmuir film flows across the triple phase boundary into the SAM/water interface forming a bilayer. The lateral flow is completed when the entire electrode/solution interface is coated with a bilayer (from Ref. The inset shows the Au-coated glass slide working electrode modified with a self-assembled monolayer (SAM) of dodecanethiol. Using in situ neutron reflectivity molecular structure [37. 37). C15 –Py molecules as it crossed the triple 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. the pyridine head group to be oriented pentadecylpyridine (C15 –Py) monolayer toward the gold surface. This led the authors to develop a bilayer of C15 –Py is formed on the a chemical sensor in which measurements gold/solution interface. The tail-to-tail from the air/water interface to the type bilayer is then formed. A compound that forms a Langmuir monolayer is deposited on the water surface. and Cd2+ ions [40]. 1. documented by Lipkowski and cowork- velop correlations between FP and lipid ers [38]. structural features were investigated to de. surface pressure driven flow of 4. The former in- of the FP were related to the concentration volved a change of orientation of the of H+ . It immediately spreads to cover the entire interface. We also point gold (111)/solution interface was also out that electrochemically induced surface . first a monolayer and then vestigated. these authors showed that molecules and ions partitioning into the bi. a phase line of gas/liquid/metal to allow slow. (10–19 h). Ca2+ .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. Subsequently. The working electrode is touching the air/water interface.

in which a ‘‘line’’ microelectrode is ing different methods [42–44].60 1.80 1. or 2D ena (referred to as Marangoni effect) were electrochemistry refers to the methodology investigated by Abbott and coworkers us. The solid line is the best fit through the linear portion of the capacitance drop used to calculate the flow parameter (from Ref. 37). water surface.80 0 120 240 360 480 600 720 Time [s] Fig.40 1.3 processes that are evolving in a Langmuir Two-dimensional Electrochemistry monolayer near the line microelectrode [45].5. 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. two-dimensional. Inset: the capacitance data for oleic acid are plotted versus the square root of time. Just as . there is a direct analogy Unlike in the case of HT electrochemistry. between 2D electrochemistry and classical where a planar electrode touches a large electrochemical measurements. 4 Lateral flow measurements of oleic and stearic acids at a 1-dodecanethiol modified gold electrode.20 Capacitance [mF cm−2] 1.00 0 5 10 15 20 25 Time1/2 [s1/2] 0.20 1.00 0. Thus.40 Capacitance/mFcm−2 1. placed in the plane of the air/water interface to probe the dynamics of lateral 1. pressure gradients in Gibbs monolayers section of a Langmuir film on the and the resulting monolayer flow phenom.60 1.218 1 Preparation of Monolayer Modified Electrodes A 1.

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

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

the polarity of the group is also commensurate with the geometric linking the redox moiety to the alkane cross-sectional area of the Au microband chain. Thus. We point out that by generating of the entire Langmuir apparatus.5. the necessary parameters of the spreading solvent and monolayer to interpret voltammetric current in terms samples.5.6-tetramethyl- subphase in a 100 mV s−1 voltammetric 1-piperidinyloxy free radical [25] were in- scan is typically 10 pA [49]. however. the lateral diffusion constant was found to decrease with the increasing surface con- 1. The charge due vestigated as a function of their surface to the underpotential deposited Pb ad-layer concentration. and monitoring current air/water interface is reproducible for as limited by the resulting lateral diffusion.2. offers accurate and precise means of con- layer spreading and solvent evaporation. due to adsorption of impurities. Those Fc derivatives with more 2D electrochemical methods continues. [48].3.3. Thus. and the chain length. 2 given in the plane of the water surface. This 5.2. The earlier and the related discussion).2 2D Electrochemical Investigations centration suggesting that the monolayer of Langmuir Monolayer Films viscosity is an important parameter. sim.5 Electrochemistry of Monolayer Assemblies at the Air/Water Interface 221 microband.6. as well as on the cleanliness of D. surfactant [2. lateral diffusion coefficients (D) of the elec- functions as the line electrode. While the learned from these results that the head list given in the following is perhaps group polarity is the second important pa- not complete as the development of the rameter. the 2D electrochemical measurements their performance begins to deteriorate are analogous to the fluorescence photo- recovery after photo-bleaching (FRAP) [4. biological membranes [53]. In all cases. 1. Well-behaved phospholipids in Langmuir monolayers line microelectrodes exhibit characteristics [52] and in supported lipid bilayers and consistent with their nominal dimensions. long as 30–60 min. 7 featuring air/water interface opened the possibility data for several Fc-dodecane amphiphiles of investigating phenomena intrinsic to with different polar groups [54]. 51]. 7]. To this placement of the line electrode at the end. We also this class of chemical systems. The latter has been used to probe lat- process tends to be irreversible and the eral diffusion of the fluorescently labeled electrode must be discarded. trolling the surface concentration of the Depending on the purity of the water. between the hydrophilic gold 1. stable a gradient of redox species in a Lang- performance of each line electrode at the muir monolayer. it polar groups such as amide diffuse slower outlines the main areas of research and than Fc ester derivatives carrying the least suggests some future directions. 54] and 2. This The ability to place a line microelectrode in behavior results in linear plots of D ver- the plane of a monomolecular film at the sus MMA.1 Dynamics of the Lateral Diffusion cross-sectional area and the hydrophobic of Surfactants on the Water Surface The (OM-coated) front face of the gold strip. as shown in Fig. polar head group moiety in this group . charging current recorded with a Several amphiphilic derivatives of fer- 500-µm long electrode on a 50-mM HNO3 rocene (Fc) [48. trochemically active amphiphiles can be ple wetting of the gold microband results readily measured using 2D chronoamper- in self-positioning of the line electrode ometry or voltammetry (see Eq. the Langmuir monolayer technique air/water interface should follow a mono. Inevitably.

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 × 10−6 2.222 1 Preparation of Monolayer Modified Electrodes O O Fe (a) O Fe (b) HO Fe (c) O N H Fe (d) 3.5 × 10−6 [cm2s−1] 2.0 × 10−6 C D 5. 54).0 50 60 70 80 90 100 Mean molecular area (Å2/molecule) Fig.5 × 10−6 A 3.0 × 10−7 0.5 × 10−6 1.0 × 10−6 B D 1. .

50–100 A˚ 2 /molecule. This calculations to liquid densities [58]. we invoked the Saffman and ture of the Tempo surfactants (see . The treatment of the experimental data also latter approach was particularly successful.2. a surface inactive com. The latter observation also Delbr¨uck theory [60–62]. the effect of the alkane chain as discussed in Sect. those Fc-amide derivatives with (Tempo) derivatives. but it was also used proven by observing a linear correlation to analyze lipid diffusion in membranes of D values with the inverse of the sub. a factor not at lower surface concentration was related included in the Enskog theory.6- 16 carbon atoms (see Fig. Similar observation do not undergo a L/G phase transition [49. and that the immersion depth is a certain viscosity bounded by a medium yet another parameter influencing lateral of a different viscosity. relative free area. of the lateral mobility of Fig. The latter was varied anomalous chain length dependence of by adding glycerol. To account for The discovery of the supercritical na- these results. Fig. height. to the subphase solutions. and A0 is the molecular the monolayer’s hydrocarbon region. The notion that the polar groups developed to treat protein diffusion in of surfactants are immersed in water was lipid bilayers [60]. 7 was our data analysis yielded the immersion analyzed in terms of the free-volume depths of the C16 –Fc-amide and C12 –Fc- theory of hard sphere liquids of Cohen amide to be 4. 56].4 A. which are supercrit- longer chain length exhibited slightly ical fluids at room temperature and thus larger diffusivities. 1.) viologen surfactants [59]. Finally. Af /A0 . showed that over 90% of the viscous It revealed that the lateral diffusion drag experienced by a surfactant molecule constant of the Fc amphiphiles does follow diffusing in a Langmuir monolayer is due the expected linear dependence on the to its immersion in the aqueous subphase. in a slab of the same height and phase.3.5. [63]. It also expected. complete picture regarding surfactants lat- amide series covering the range of 12 to eral mobility was obtained for the 2. of the amide group immersion depth The surface concentration dependence by chain–chain interactions.6. which is expected to inversely depend on The data discussed earlier concerned the molecular mass of a diffusing particle. was reported recently in the case of 64. The theory was mobility.0 A˚ and 6. where Af = A − and only a small fraction originates in A0 . Our due to the effect of the viscous drag of the inability to probe surfactants’ mobilities polar head groups in water. 8) [54]. Specifically. A far more length was also investigated in the Fc. ˚ respectively. this discrepancy is of MMAs of ca.5 Electrochemistry of Monolayer Assemblies at the Air/Water Interface 223 of compounds. the former does decrease slightly revealed that the slope of this dependence with increasing MMA. 1. Clearly. the phase viscosity [54]. as well as in view These values depended neither on the of the Enskog theory of dense gases [57] surface concentration of the Fc surfactants extended by Alder’s molecular dynamics nor on the viscosity of subphase. the lateral mobility in the liquid region was more than 3 orders of magnitude of the Langmuir films spanning a range smaller [54]. (See the structure of C 16 Tempo. It concerns quasi suggests that surfactant’s polar group is 2D diffusion of a cylinder-like particle of at least partially immersed in the sub.2. h. and Turnbull [55. to the liquid/gas (L/G) phase transition. 65]. As area of a surfactant molecule. Using this theoretical model. 8 was related to the modulation pound. Counter tetramethyl-1-piperidinyloxy free radical intuitively. A = MMA.2.

0 × 10−6 C12Fc A 1. MMA measured on the 0. 8 Plots of the lateral D values of the ferrocene-amide derivatives (see structure D in Figure 7). 65]. 9. lateral mobility [25].2) allowed us to measure their Comparison of the data obtained for lateral mobility in a far broader range of three different Tempo derivatives with surface concentrations. 1. as shown in Fig.7 cP.5 × 10−6 [cm2s−1] D 1. O N O N H Sect.0 × 10−6 C 5.5. (B) 20.9.05 M HClO4 subphase containing (A) 0. and (C) 40 wt% glycerol. 1. The viscosities of these solutions were 1.1.224 1 Preparation of Monolayer Modified Electrodes 2.5 × 10−6 A C16Fc 2.0 × 10−6 B C 5.2.5 × 10−6 B D 1. C16 Fc and C12 Fc vs.0 × 10−6 [cm2s−1] 1.0 50 60 70 80 90 100 Mean molecular area [Å2/molecule] 2. 54). We concluded that . respectively (from Ref. and 3.0 × 10−7 0.3.0 × 10−7 0.0 50 60 70 80 90 100 Mean molecular area [Å2/molecule] Fig. the chain length ranging from C8 to C18 This range is extended to MMAs as high shows essentially no differences in the as 800 A˚ 2 /molecule [25.

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

6.226 1 Preparation of Monolayer Modified Electrodes Model 1 Model 2 89 137 Electrons Electrons O N O C NH 156 108 Electrons Electrons N N C H O O Fig. Within each model. offers a significantly bet- sponding to an MMA of 52 A˚ 2 /molecule). These were proposed assuming that either the amide group (Model 1) or the nitroxy group (Model 2) is hydrated.1). X-ray reflectivity is single water molecule hydrogen-bonded to a technique sensitive to the gradient of its oxygen atom. ter agreement with the measurements as and present the key result that allowed quantitatively reflected in a much smaller us to distinguish between two opposing χ 2 value (6. The com- elsewhere [65]. A large lateral diffusion the electron density in a molecular film constant of Tempo (1. It is clear on the X-ray reflectivity measurements at that Model 1. Tempo it- Fig. While this result . 65).2 vs. inance of the amide group and Model 2 Our investigations suggested that. water-soluble surfactant [70]. we report here parison is shown in Fig. 26. Briefly. 10 into a stack of two boxes than the bulk water [70]. us to simulate the X-ray reflectivity re- count of these measurements is beyond sponse and to compare the two models the scope of this review. amide group. the dotted line separates the molecule into two ‘‘boxes’’ with different numbers of electrons shown in the figure (see text. confirmations of C18 Tempo on the water Recently. These are shown schematically in tetramethyl-1-piperidinyloxy. assuming immersion of the a single pressure of 21 mN m−1 (corre. we have also examined 2. 10 where Model 1 assumes the dom. 11. we indicated that the air/water interfacial re- deconstruct the two C18 Tempo conforma. is likely energetically too costly. Consequently. Tempo group as the polar fragment immersed in is coupled to the interfacial region via a the aqueous subphase. gion is as much as four times less viscous tions of Fig. self. a weak. from Ref. Thus.2. 10 Schematic representation of two different conformations of C18 Tempo at the air/water interface at 52 A˚ 2 /molecule.5 × 10−4 cm2 s−1 ) at an interface [68. 69]. as it dif- assumes the dominance of the nitroxide fuses along the air/water interface. and are presented with the experimental results.6- surface. This allowed fragments is immersed. we containing a different number of electrons postulated that only one of the two polar (also shown in the figure). The detailed ac.

1 The solid and the dashed lines R(qz)/RF(qz) are fits to the data using the box 0. and gaseous monolayer states Using this new 2D electrochemical capa- and the related phase transitions and bility. c2 = 26.3 0.1 models discussed in the text and shown in Figure 10 (from Ref. Recent phase and results in loss of electrochemi- work involving monolayer X-ray diffrac. it gives the behavior is illustrated in Fig.5 ◦ C [49]. panded (LE). the position of the LE/G phase transition.2 Measurements of the LE/G Phase trode functions as the monolayer gas Transitions and their Critical Temperature phase nucleating site. 12. 1. apparently involves preferential relationship to the lipid’s molecular struc. Brewster angle microscopy ing in the plane of the air/water interface was employed to verify this measurement. Johnson and coworkers transition to be 98. 23. is a sensitive sensor of the onset of an A set of BAM micrographs recorded near LE/G phase transition [64]. In comparison. Johnson and coworkers determined critical phenomena have not been system.3. cal signal. producible sensors capable of indicating cerned with liquid. 0.7 qz (Å−1) is still somewhat preliminary. This sensing the LE/G transition of C22 Tempo is shown .5 ± 0.4 0. not Characterization of the phase behavior of unlike the well-known ‘‘boiling chip’’ phe- Langmuir monolayers.6 0.5 Electrochemistry of Monolayer Assemblies at the Air/Water Interface 227 Fig. 13] led the amphiphile’s concentration in the gas to a rapid progress in the structural char. wetting of the line electrode with the ture.5 0.5 A˚ 2 /molecule at reported recently that a line electrode resid. This and later experiments carried out with the Tempo surfactants [49] showed that a line elec- 1. phase is much smaller than that in the acterization of ordered condensed phases corresponding LE phase. ferroceneketone (C14 Fc) was observed dur- trate how 2D voltammetry of shallowly ing its monolayer expansion over just immersed surfactants can contribute to the 3 A˚ 2 /molecule near LE/G phase transi- investigations of this important interfacial tion. is of fundamental importance to the freshly nucleated bubble of the 2D gas understanding of their behavior.001 0 0. The phenomenon is reversible upon system. 65). these results illus.5.1 0.2 0. specifically liquid ex. monolayer recompression. and particularly its nomenon. 11 X-ray reflectivity data for C18 TEMPO at 21 mN m−1 at 1 Model 2 21 ◦ C (points with error bars). This property.2.01 Model 1 c2 = 6. Furthermore. the position of the C22 Tempo LE/G phase atically studied. The latter is due to the fact that tion methods [71] and BAM [12. where first direct experimental assessment of the sudden disappearance of cyclic voltammet- dynamic nature of the aqueous interfacial ric signal due to oxidation of a tetradecane region. the issues con. Line electrodes of Langmuir films of numerous types were found to be very sensitive and re- of lipids.2 0.

67. and where shortening of the effective length of its the electron hopping transport is most hydrocarbon chain and thus in a decrease effective. where the rate of the Fc translational during monolayer expansion results in the diffusion is at a minimum. Johnson film is an alternative mechanism of the and coworkers also measured the critical lateral. diffusive charge transport. respectively.5 Fig.2.5.9 0. transition. we showed that the ferrocene rate con- lated to involve rotation of the Tempo head stant of self exchange is not high enough group leading to an increase of its cross. in comparison with BAM. no increase of of the cohesive van der Waals interactions the voltammetric current due to transla- normally associated with a LE/G phase tional diffusion was observed rendering . The molecular origin of this example.1) even under other words.228 1 Preparation of Monolayer Modified Electrodes −0. and convenient. This hypothesis was supported the texture of a Langmuir monolayer at by the surface potential measurements each stage of its gradual expansion allows [49] and by recent X-ray reflectivity data one to determine the position of the phase [72]. Elec- temperature of C20 Tempo to be 28 ◦ C [49]. In diffusion (see Sect.8 0. rather unusual phenomenon was postu.5 line microelectrode at 0.2.3. careful observation of transition. All shorter chain Tempo derivatives were tron hopping may proceed in parallel and found to be supercritical at temperatures compete with translational diffusion.2 V s−1 .5.7 0. 2D electrochemistry was proven to 1. For down to 0 ◦ C. 64). 12 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. SCE [V] in Fig.3 Kinetics of Electron Hopping in be not only equally accurate but more pre- Langmuir Monolayers Rapid electron ex- cise. The 0 mean molecular areas corresponding to the voltammogram 1–4 are: 65. The disappearance of the voltammetric 2 signal at 66–67 A˚ 2 /molecule is due to the onset of the LE/G phase transition 1 1 (adapted from Ref. 66. 4 and 68 A˚ 2 /molecule. It is also free change between adjacent molecules of of false negative type measurements in- different oxidation states in a Langmuir trinsic to the BAM observations.3.3 0. Indeed.2 Potential vs. 1.6 0. However.4 0. 1. for the electron hopping process to com- sectional area. in the case of Fc surfactants. Consequently. 13. reliable. The i-E curves were recorded with a 500-µm Current 3 [nA] 0. the ability of Tempo to change the conditions of high surface concentra- its orientation at the air/water interface tions. and the resulting decrease pete with the observed surfactants lateral of the chain–chain interactions [49].5 0.5 0.

tem. that when line electrodes with a length Electron hopping was unambiguously comparable to the aggregate size are used. 49). are Fig. 1.10-phenan. observed in solid monolayer films of os. Upon compression of the solid aggregates of Os(DPP)3 . percolation theory is observed. 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. 15 [75]. on–off type behavior that deviates from the mium tris-4. on a 50-mM HNO3 subphase at 23. where 2D voltammetric current decreased with increasing surface con- centration in response to the increasing monolayer viscosity. Os(DPP)3 forms 2D solid aggregates that can be imaged by BAM (see Fig. Three such plots. . their mutual connectivity in- creases resulting in an increase of the extent of the electroactivity of the entire film. 15 versus the fractional surface concentration of Os(DPP)3 on the water surface. throline perchlorate (Os(DPP)3 ) [73–77]. It is interesting to note impossible [48]. 16. Unlike in the cases of Fc [54] and Tempo surfac- tants [25]. However. 79].5 ◦ C. by using line electrodes with lengths ter surface. The length of the horizontal edges of these images corresponds to 430 µm (from Ref. corresponding to the 2D experiments carried out with the line electrodes of increasing length. over sufficiently large areas of this 2D sys- phiphilic osmium complex on the wa. as can be seen in Fig. 13 Brewster angle micrographs of C22 TEMPO monolayer recorded at (from top to bottom) 99. This effect was conclusively related to the electron hopping percolation [78. 14). when the hopping dynamics is averaged Upon spreading of this large. the opposite effect of the monolayer compressing was observed in this case.7-diphenyl-1.5 Electrochemistry of Monolayer Assemblies at the Air/Water Interface 229 characterization of the hopping process shown in Fig. 105. nonam. The onset of 2D voltam- metric activity coincides with the rise of the surface pressure during compression of the Os(DPP)3 monolayer. and 130 A˚ 2 /molecule.

we first carried out structural to compare the 2D crystal structure of . that are large compared to the average ag. The value of the lateral diffusion constant lattice spacing of 10. characterization of the Os(DPP)3 films by gregate size. These measurements showed that [75]. the Os(DPP)3 forms a hexagonal lattice In order to interpret the maximum in the plane of the air/water interface. 75).57 A˚ [75].89 A˚ gave the Os−Os in terms of the electron transfer–rate distance of 12. It is interesting constant. The length of the vertical edges of these images corresponds to 730 mm (from Ref. the system’s behavior reflects grazing incidence angle X-ray diffraction predictions of the 2D percolation theory [71]. 14 Three Brewster angle microscopic images of Os(DPP)3 monolayer on a 50-mM HClO4 subphase recorded at 360 A˚ 2 /molecule showing typical shapes and sizes of 2D aggregates formed on the water surface upon spreading.230 1 Preparation of Monolayer Modified Electrodes Fig.

085 to 16. was obtained with a D = 14 k1 r 2 (3) novel 2D electrochemical technique rely- ing on a tandem of two collinear 40 µm This gives k1 = 4. D = 1. 81]. which constant. 14 likely results value of the electron hopping diffusion in defects at the domain boundaries. Increasing current corresponds to decreasing mean molecular area of Os(DPP)3 from ca. The long line microelectrodes spaced by 10 µm latter corresponds to the bimolecular rate and acting as a generator probe and a constant of electron exchange kex of collector probe.57 A) layer. (12. the maximum aggregates imaged in Fig. ˚ electron hopping kinetics involved an as- Thus. referred . Os(DPP)3 with the isostructural Ru(DPP)3 2.6 0. can be may make that assumption uncertain.8 × 10−6 cm2 s−1 . 75).2 E [V vs. This assessment of the neighbors range from 13.5 Electrochemistry of Monolayer Assemblies at the Air/Water Interface 231 −2 icathodic −1 i (nA) 0 1 ianodic 2 1.4 0. Ag/AgCl] Fig. 15 A set of 2D cyclic voltammograms of Os(DPP)3 monolayer at the air/water interface recorded concurrently with the monolayer compression. It was obtained rely- complex described in the literature [80].0 0. compression of the 2D With these data in hand.7 × 108 s−1 [75]. ing on the precursor complex model in In 3D.8 × 108 M−1 s−1 . and adjacent Os(DPP)3 sites according to the of the related kex . However. 1.2 V s−1 .576 A. The CVs were recorded with a single 400-µm line microelectrode at a scan rate of 0. 120 to 90 A˚ 2 /molecule (from Ref. the 2D crystal structure features sumption of complete electroactivity of all a higher symmetry unit cell and shorter Os(DPP)3 sites in the Langmuir mono- ˚ metal–metal spacing. that did not require following equation: the assumption of 100% electroactivity of the Os(DPP)3 film. a precursor complex ‘‘equilibrium the distances between nearest Ru−Ru constant’’ [48. interpreted to yield the unimolecular rate A more accurate measurement of the constant (k1 ) of electron transfer between electron hopping diffusion constant. In this method.8 0. Ru(DPP)3 chloride crystallizes in which kex is expressed as a product of k1 a monoclinic space group P 21/c with and Kp .

0. one important advantage of this their diffusive arrival rate [77].2 0. one line electrode generated cess.0 (c) x(OsDPP) to as 2D electrochemical time-of-flight physically involved electron hopping pro- (2D ETOF).0 Fig.8 Dapp/Dmax 0.8 1.0 mm long line microelectrodes (from 0.4 0.8 1. Naturally. monitored review.4 0.232 1 Preparation of Monolayer Modified Electrodes 1.4 0.8 1.6 0.4 Ref.0 0.2 0.6 0.6 0.0 (b) x(OsDPP) 1. 2D ETOF are beyond the scope of this held at the reducing potential. X(Os(DPP)3 ) obtained on 0.0 0.2 0.4 mm electrode the basis of several series of 0. 0. method worth mentioning here is that it the diffusion of Os(DPP)3 (III+) species does not require surface concentration of .6 0.4 0. 1.0 0.0 6 mm electrode 0.8 Dapp/Dmax 0.6 with 0.0 1 mm electrode 0. and 6.8 cyclic voltammetric experiments as those in Figure 13 carried out Dapp/Dmax 0.6 0.4 0.0 0.4.2 0. 16 The plots of Dapp /Dmax vs.2 0. While the experimental details of Os(DPP)3 (III+) species and the other.0 (a) x(OsDPP) 1.0 0.2 0. 75).0 0.

Adamson. Chem. 1990. 1. 114–117. 54. 1985. A. Insoluble Monolayers at Liquid-Gas Interfaces. Annu. 3). Knobler. tal addition of aliquots of a polar.0 × 109 M−1 s−1 which is more frequency factor. Rashmi. ing a compressed Os(DPP)3 monolayer on 3. Lett. value forecasting a complete resolvation These experiments carried out by Wit. Phys. research. New York. Wiley-Interscience. [77]. C. C. 1982. M. of solvent additions and 2D voltammo. Annu. Physical Chemistry of Sur- its surface. Phys. C. increase of the electron hopping kinet- gued that the remaining. or in other words. of the Os(DPP)3 molecules. between Os(II) and Os(III) relative to those prevailing when these ions collide and Acknowledgments exchange an electron in a homogeneous solution. Deutsch. Rev. 1992. 870–874. solvent exchange experiments [74]. L. P. We obtained a good correlation between the nuclear kex = 1. This ment of the electron-transfer kinetics in a correlation is consistent with a highly solid Os(DPP)3 monolayer could be due to adiabatic character. (2) The reorganization energy of The author gratefully acknowledges donors the Os(DPP)3 molecules in a monolayer at of the Petroleum Research Fund. A. rate constant achieved a new constant terpret the experimental i –t transients. Rev. New equilibration. Phys. laxation time of the solvents used in the tion [82]. This rather substantial enhance. Knobler. D. solvent to the aqueous subphase support. J. H. Braslau. 1966. Science 1990. M. Pershan et al. S. was investigated. 1. Additional support has been pro- Solvation of the Os(DPP)3 molecules vided by the National Science Foundation. nonactive sites ics. Chem. We ar. Other solvents such as benzonitrile are in the regions near grain boundaries had the opposite effect. gram recordings was continued until the 41. organic 2. G. 441–476. W.. a 2D voltammogram was York. Addition of some sol- chemically active and participate in the vents such as acetonitrile resulted in an electron hopping process [77]. in terms of Marcus theory.5 Electrochemistry of Monolayer Assemblies at the Air/Water Interface 233 redox species as an input parameter to in. 4th edition. John Wiley & Sons. 207–236. This sequence 5. 43. periments [74]. 6. The effect of tek and coworkers showed that only 73% five solvents on electron-transfer kinetics of all the Os(DPP)3 species are electro. Following each addition and faces. in its Langmuir monolayer and the dy- namic solvent effects on electron hopping References kinetics were investigated by Charych and coworkers in a set of solvent exchange ex. one or both of the following factors. extracted from the mea- than 1 order of magnitude higher than sured values of the electron-transfer rate a literature value obtained for Os(DPP)3 constant and the inverse longitudinal re- (III+/II+) couple in an acetonitrile solu. . Rev. This revealed stant of electron hopping. recorded to measure the rate constant of 4. M¨ohwald. Charych and of the 2D aggregates. adminis- the water surface could be smaller due to tered by the ACS for partial support of his a partial solvation. M. These involved incremen. Gaines. (1) The a strong electronic coupling existing be- distances between the osmium centers and tween the Os(DPP)3 molecules in their a particular alignment of the DPP ligands 2D solid aggregates discussed by Wittek could result in a higher electronic coupling et al. This measurement coworkers analyzed these measurements allowed us then to recalculate the rate con. electron transfer (see Eq. 249.

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