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Center for Advanced Materials Processmg, Clarkson University, Potsdam, NY 13699-5814, USA
Abstract- Colloid chemical methods for the preparation of nanoparticles and their self-assembly and olgallization
into 2-dimmlsional an~ys and three dimmlsional networks are sut-veyed. Potential applicatioils of nanoparficles and
nanostmctured materials, fabricated by the wet colloid chemical approach, are also illustrated.
Key words: Colloids, Nanoteclmology, Nanostructured Materials, Self-assembly, Nanopartides
NANOPARTICLE PREPARATIONS
rate. The gold pmtides formed me coated by an dectfical double
layer (composed ofbuhky citrate ions, chloride ions mldthe cations 1. Precipitations hi Homogeneous Solutions
attracted to them) responsible for the Coulombic repulsions ~hich Precipitation involves file nucleation of crystalline centers and
decays exponentially with increasing interpartide sepm'ations. There subsequent growfll of the incipient crystallites. In the absence of
is aweak minimmn hi the van der Waals energy at an interparticle intervention bulk amorphous or crystalline materials are produced
separation which approximately corresponds to the dimneter of the upon chemical precipitation. Control of the nucleation and growth
stabilized gold nanopmticle. This minimum (where the attractive is the requirements of forming monodispemed nanopatticles by pre-
van der Waals forces are overcompensated by the repulsive elec- cipitation [Matijevic, 1994]. In homogeneous solution this is ac-
trostatic interactions) is responsible for the elecWostatic stabiliza- complished by thejudidons adjumnent of the precipitating condi-
tion of the gold colloids. However, compression of the electrical tions (type, concentration, oider and rate additions of the reagents
double layer (by increasing the ionic strength of the medium, or and stabilizers or capping agents, stoichiometty, temperaute, and
displacing the added ionic stabilizers) results in particle aggrega- solvent). Many submicron sized stable particle dispersions have
tion. been prepared by using the cotgrolled double (or multi)jet precipi-
Steric stabilization is accomplished by adsclbing polymers mid/ tation proces~ Advantage has also been taken of ultrasonic power
or surfactants onto the surfaces of colloidal particles. Intertwining to fotln nanoparticles [Peters, 1996; Matai et al., 1999; Zhu et al.,
of the adsorbed polymers (and/or surfactant) hi the intetparticle 2000; Kumar et al., 2000]. It is increasingly realized that the shapes
space restricts the confotmational motion (entropy effect) and in- as well as the electronic properties of the nanopmticles depend on
creases local polymer concentration (which has to be compensated the stmctlwe(s) of the capping (stabilizing) agents [Chemseddine,
by solvation=osmotic effect) which, in tmn, results in the stabiliza- 1999].
tion of the pmticle It should be pointed out that stabilization of col- 2. Precipitation hi and/or Incorporation onto (or Into) Slw-
loidal particles by long chain surfactants and/or polyelectrolytes in- factant Aggregates and Tentplates
volves both elecWostatic and steric effects. Such surfactant aggregates as aqueous micelles, reversed m i-
Coating (capping or derivatization) by molecules which form celles, microemulsions (both oil-in-water, OAV and water-in-oil,
chemical bonds with or chemisorb onto the pmticles provides an W/O), surfactant vesicles and polymerized sm-factant vesicles have
extt~nely useful method of stabilization [Veinot 1997; Henglein been fruitfully employed as templates (and/or nanoreactors) for the
and Meisel, 1998]. Thiols mid dithiols have been demonstrated to z,~,~'~ generation ofnanopatticles [Fendler, 1982, 1992; Fox, 1991].
be highly suitable capping-agents for metallic (particularly gold and Alternatively, preformed nanopatticles have also been incorporated
silver) mid semiconducting (CdSe, for example) nanot~ficles (Fig. into suffactant aggregates. Aggregates referred to as aqueous mi-
January, 2001
Colloid Chemical Approach to Nmlotedmology
long hydrocarbon tails This versatility pelmits a l~ge variety of tally occmring (zeolites, clw minerals, for example), naurally oc-
diflh~nlt apIn~oaches to the bn situ generation ofnanop~ticles in ctming but modified (pillared clay, for example) and artifical (po-
SUV. Large (giant, c a . I gm diameter) Unilmnellar Surfactant ves- rous glass, for example) have bern employed. An interesting ex-
icles (LUV) have also been prepared. ample is provided by using liquid oystal templating to form syn-
SUVs have been stabilized by polymerization. Vesicle forming thetic ls~ge pore zeolites (Fig. 5, Kresge et al., 1992): in the pre-
surfactmlts have been functionalized by vinyl, methaclylate, diace- sence of silicate ions hexagonal arrays of cylindrical micelles m'e
tylene, isocyano and s ~ n l e groups ha their hyd'ocarbon tails or formed from surfactants with thek polar groups in the exterior of
head/groups Accordingly, SUV could be polymerized in their bi- the cylinders which are covered by silicates. Calcination results in
layers or across their headgmups. In the latter case, either the outer the burning offthe organic surfactants aid leaves the inorganic sil-
or the imler or both the outer and inner surfaces could be polymer- icate in the form ofMCM-41 zeolites.
ized. Surfactant vesicles and polymerized vesicles have been ex- It should be remembered that rigid compartments and partial en-
tensively employed as compartments for the in ,sztu generation of happing ofnanoparticles therein obviate the need for surface cov-
nanoparticles [Fendler, 1992; Kennedy et al., 1998; C~rea et al., erage (ie., modification). Nanoparticles can be, therefore, examined
2000]. (mad employed) in their pristine states.
Cadmium sulfide nanoparficles have also been generated in bac- 3. SoR Solution Processing-Hydrothelnal Synthesis
terial S-layer proteins [Shenton et al., 1997]. Nucleation was found Preparation ofnanopmlicles by Soft Solution Processing (ie., di-
to occur within the subunits in the and the resultant CdS nanop~ti- rect fabrication ha aqueous solution at moderate temperatures and
cles anarlged themselves in two-tier stacks. The ~uctmal diversity pressures) has increasing been gaining acceptance [Yoshimura and
of the S-layer proteins opens the door to fabrication of a wide va- Livage, 2000]. Hydrothermal synthesis (hy~othennal technique)
riety of 2D and 3D nanostrucmred materials. is a Soti Solution Processing which involves the heterogeneous re-
Polymers have also been used as templates for the zn sz~ gen- action between powdered solids and water above ambient temper-
er~ion or incorpot~ion of nanopmficles. Particularly significant is atlre mad at pressure greater than 1 alm in a closed system [By-
the versatile use ofdendrimers [Tomalia et al., 1990; Frechet et al., rappa and Yoshimura, 2000]. The relative ease (appropriate pow-
1996; Percec et al., 1998; Sooklal et al., 1998; Fischer and Vigtle, dered reagmts and water are placed in a teflon-lined autoclave and
1999] and di- and Wi-block copolymers [Bates et al, 1999; Leclere heated without stin'ing at moderate to high temperatures and pres-
et al., 1998; Kane et al., 1999; Wang et al., 1999; Schrock et al., SlWeSfor the desired time) and the possibility of predicting opti-
1999; Spatz et al., 1996; Stupp, 1998; Rudoy et al, 1999; Colfen et mum reaction conditions by electrolyte theimodynamics (in toms
al., 1999; Selvan et al, 1999; Nardin et al., 2000, Underhill and of phase diagrams) are the advantages of the hydrothennal synthe-
Lin, 2000]. Judicious selection of appropriate block copolymers in sis [Lencka et al., 2000]. Hydrothennal reactions have also been
appropriate concentrations have t~ulted in the formation of large carried out under mioowave heating, ultt~onication, and applied
variety of self-assembled s~ucttmes including those which resem- eleclrical potential as well as employing solvent(s) under supercrit-
bled aqueous micelles, reversed micelles, microemulsions, suffac- ical ornear supereritical conditions [Yoshimura et al, 2000]. BaTi03,
tant vesicles and. All of these structure can, ha principle, be used as SrTiO3, LiNbO3, LiNiO2, LiCoO2, and PZT nanoaystalline thin
templates for nanoparticle generation or incorporation. films have been prepared by the hydrothennal synthesis [3~bsh-
The range of templates and/or compliment available for the zn imtwa et al., 1999]. Remarkably, carbon coatings mad carbide fibers
sz~ generation or incorporation of nanopartMes in controlled (or [Gogotsi and Yoshimura, 1994] and even diamond [Zhao et al.,
controllable) sizes and morphologies is limited only by the imagi- 1997] have been prepared by this method.
nation and diligence of chemists and material scienfist~ Both natu- 4. NanopmTtide Formation in Aerosol Reactors
The term aerosol ref~s to a colloidal suspension of solid parti-
cles ha a gas. Reacting nanoparticle precursors as aerosols at ambi-
ent aid elev~ed temperature as well as in flames (flame pyrolysis)
has been shown to be a suitable technique for the industrial pro-
duction of metallic, semiconducting and ceramic particles mad thin
films therefi'om [Pratsinis, 1998; Vallett-Regi et al., 1997; Valle-
tregi et al., 1997; Kruis et al., 1998; Chow et al., 1998; Briesen et
al., 1998; Jang and Friedlandei, 1998; Kiln and Park, 1999; Su and
C]loy, 2000]. Aerosol reactors have also been onployed for the sta-
bilization ofnanoparticles by surface coating [Satoh mad Kimum,
1989; Powell et al., 1997].
5. Elecla'odeposifion
Electrochemical deposition of nanopaticles (or nanosiructured
films) is attractive since a high degree of control can achieved by
the judicions employment of Fmuday's laws (96,500 x n Couhmb
Fig, 5. Schematics of MCM-41 zeolite formation by the caidnation results in the deposition of 1 glare mol of materials, v~lere n is the
of the s~icate ions attached to the outer surfaces of hexa- number of electrons passed in depositing one mole of the deposit).
gonal arrays of sm'factants functioning as templates (modg Furthermore, composition, defect dlemi~y and shapes (along ~ith
fled front Kresge et al., 1992). thickness) is controllable at areasonable cost. Both anodic and call-
January, 2001
Colloid Chemical Approach to Nanoteclmology
odic electrodepositions have been demonsti-ated Anodic depositions into the closed syste~-n. Facilities are provided for detennitmag su~'-
are limited to metallic subslrates since the process involves the elec- face pressure vs. surface area and surface potential vs. su:face area
trolytic reduction of metal in the presence of the appropriate an- isothenus in the film balance placed under the glass cove1: Reflec-
ions. Cathodic process is more versatile since both components of tivities, angle-dependent reflectivities, Brewster-angle and fluc~'e-
the semiconductor nanoparticles ~e both deposited fi-om solutiort scence microscopic images and non-linear optical parameters can
Thus, for example, cadi-nium selenide nanoparticles were electro- also be raonitored &aing the nanoparticle formation under the rno-
deposited onto gold electrodes from hot dimethylsulfoxide solutions nolayer.
of Cadi-nium perchlorate, saturated by selenium at elevated tem- Nanoparticles have also been genel~ted electrochemically under
pei-atures [Hodes et al., 1998]. The method has been extended to monolaye~. A 1.0-im-n-diametel, 3-era-long silver electrode is im-
the fox-nation of composite Cd(Se, Te) and (Cd, Zn)Se nanocrys- mersed into the subphase (aqueous silver nilrate solution) and elec-
tals. Interestingly, the size of the nanocrystallites did not depend on trical connection is made tt~'ough a 20-t,un-diameter platinum elec-
the tempevattae or ctarent density but was related to mismatch in- b-ode, floated (subsequent to monolayer fonuation) on the water
duced strain [Golan et al., 1997]. Electrodeposition of MoS2 [Po- surface at the middle of the trough. Ten to twenty minutes subse-
nomarev et al., 1997], ZnS [Mahmnuni et al., 1999] nanoparticu- quent to monolayer fonuation, a potential of 1.8-1.9 V is applied
late films, and CdS nanowires [Xu et al., 2000] have also been re- across the electrodes (keeping Pt negative) by means of a DC pow-
ported. er supply. With time, silver particles grow conceImically, forming
Particularly sigmficant is the elecb-odepositic~l ofnanostructta-ed larger and larger circles at the monolayer-water interface. The rate
superlattices by pulsing either the applied current or potential of a of this two-dimeusicnal growth is typically 1-2 cm 2 per hour. Im-
solution containing precursors of both layers [Switzer, 1998]. Na- portantly, no silver particles are observed upon the application of
nometer scale PB-T1-O ceramic superlattice with a 0.3% l-nismatch the same potential to the water surface in the absence of surfactants
was electrodeposited fi-om aqueous solutions of 0.005 M, 0.005 M or to monolayeis prepared fi-om positively charged surfactants. Ne-
TI(I) and 0.100 M Pb(II) in 5 M NaOH, for example [Phillips et gatively d ~ g e d monolayers are essential to the eleca~achemical gen-
al., 1997]. The defect compositicn was a fovaad to be controllable eration of silver pm-ticles; they prove binding sites for silver ions
by the ove~potential; high ove~l~otentials favored oxygen vacan- which ~:e reduced at the cathodic surface. To-date, ca&nium-sul-
cies, low overpotential produced cation intel~titials [Switzel; 1998]. fide, zinc-sulfide, lead-sulfide, cadinium-selenide, and lead-selenide
semiconductor particulate and silver and gold metallic i~ancypartic-
O R G A N I Z A T I O N OF N A N O P A R T I C L E S I N T O 2D ulate flhns have been chemically grown, in situ, under monolayers
ARRAYS AND 3D N E T W O R K S in our laboratories [Kotov et al., 1993; Zhao et al., 1992; 5~ang et
al., 1994, 1995; Yi et al., 1994; Yang and Fendle~; 1 995]. The for-
1. Generation of Nanoparticles and Nanosh-uctured Materi- mation of nanoparticulate films ttqder monolayers by employing
als Under Monolayers similar methodologies has been reported by other research groups
Both chemical and electrochemical routes have been developed [Pan et al., 1997; Liu, 1997].
for the/n situ generation of nanoparficles under monolayers [Fen- Evolution of a nanoclystalline particulate film, as illnsb-ated by
dlel; 1992]. The experimental set-up used for the chemical genera- the formation of sulfide semiconductor particulate films (Fig. 7),
fion and in sqtu monitoring of nanocrystalline particulate ftlms is has been discussed in tenns of the following steps: (a) formation of
illustrated in Fig. 6. Typically, a surfactant l-nonolayer ks spread on metal-sulfide bonds at a large number of sites at the l-nonolayer-
an aqueous solution of the metal salt precursor of the nanoparticles aqueous interface; (b) downward growth of well-separated nano-
and crystallization is induced by the injection of the reactant gas crystalline metal sulfide particles; (c) coalescence of clusters into in-
terconnected arpays of semicc~lductor particles; (d) formation of
the "fu~t layer" of a porous sulfide semiconcklctor partictate film
composed of 20- to 40-~-thick, 30- to 80-~-diameter particles; (e)
diffusion of fiesh metal ions to the monolayer heat group area; (f)
fonuation of a "second layer" of the porous sulfide semiconductor
p~-ticulate film (by using steps a, b, and c); and (g) build-up of"suN
sequent layers" of the sulfide semiconductor particulate film (by
using steps a, b, and c) up to a platean thickness (ca. 300 ~ for CdS
and ca. 3,500 ~ for ZnS) beyond which the film cannot grow.
The presence ofa monolayer with an appropriate surface charge
is essential to sulfide semiconductor particulate film formation. In
the absence of a monolayer, infusion of H2S over an aqueous metal-
Fig. 6. Schematics of the Lan~muir through used for the/n situ ion solution results in the formation of large, irregular, and polydis-
generation of nanoparticlcs and nanoparticulate fihns pei~ed metal-sulfide particles which precipitate in the bulk solution
under monolayers. The aqueous phase contains a dilute
before settling to the bottom of the trough
aqueous solution of one of the precm~ol~ (cadmium per-
chlorate, for example) while the other precursor (H2S, for The oriented growth requires the matctmag of the crystal lattice
example) is injected by the syringe. The ~rowth of the na- of the sur~actants, constituting the monolayei~, with that of the in-
noparticles can be monitored/n s/tu (with Brewster angle cipient nanocrystallites. Such epitaxial matching has been achieved
microscopy using a laser, for example). by growing lead sulfide [12], leadselenide [13], and cadimum sul-
Korean J. Chem. En~(Vol. 18, No. 1)
6 J.H. Fenc~er
(aid historically the earlier, Sagiv, 1980) approach involved the self-
assembly o f a bifunctional monolayer onto a subsWate (ie., forma-
tion of a serf-assembled monolayer, SAM) and lhen file subsequent
attachment of the nanoparticles to the monolayers [Mel&um et al.,
1997; Sato et aL, 1997]. Nanopatticles lfiemselves were derivatized
by bifunctional molecules and ltien subsequently connected to each
oilier azldto soksWates [Bmst eta[, 1998; Baum et aL, 1999]. Thus,
the formation ofmtdtilayer films have have been reported upon the
deposition of 6 nm gold pmficles, stabilized by ~o)-dithiols onto
glass substrates [Fan and Lopez, 1997; Bmst et al., 1998]. Alterna-
tively, decomposition of AuCI (NH2R; R=CvHI:; Cl2H2s; Cleric)
complexes resulted in the formation of self-organized fibrous mat-
erial [Gomez et al., 2000].
5. Layw-by-layor ElecWostatic stir-assembly
Self-assembly of alternating layers of oppositely chmged poly-
electrolytes mad nmlopartides (or nanoplatelets) is deceptively sim-
ple (see Fig. 9). Self-assembly is governed by a delicate balance
Fig. 8. Schematics fltustpatiltg the contra of inteq~article distances between adsorption aid desorption equili'ori~ In the self-assembly
ha mouo-particulate thick Lmt~auw t-~ns by differeat cout- of nmloparticles, for example, the efficient adsorption of one (and
hags. only one) mono-pmliculate layer of nanopmficles onto the oppo-
sitely charged subsa'ate surface is file objective of file immersion
on file micron scale by Brewster-angle microscopy 03AM) mad at step. Desorption ofnanopmficles forming a second and additional
higher magnifications by transmission electron microscopy (TEN[). layers (mad preventing the desorption of the first added layer) is the
Absorption spectroscopy and steady-state fluorescence spectro- purpose oflhe rinsing pmcesg The optknization oflhe serf-assem-
scopy can also be applied where appt~opriate and reflectivity meas- bly in terms of maximizing file adsorption of nanoparticles from
urements permitted the estimation of film thicknesses on ~nter
suFfa~es.
4. Sdf-~LSsembly of NanopmTlides by Adsorption and Deriva-
tization
Adsorption (either by physisurption of dlemisorption) of nano-
particles onto s~ubstrate is the simplest method of fabricating self-
organized 2D arrays and/or 3D networks. Adsorption is accom-
plished by dropping a few drops of dilute nanoparticle dispersion
onto asuitable substrate (casting) mad ev~orating file solvent (usu-
ally slowly aid in a controlled environment) ['Bi~lker eta[, 1999;
Potter, 1999; Andres et al., 1996]. Alt~natively, file sub,'ate is im-
merged into a dilute nanoparticle division (for afime optimized
for file adsorption), with~awn, rinsed and dried Depending on the
slnface modifiers and on the dielectric constant of the medium TiO2
particles self-assembled into cubic arrays ['Brooks mad Cgatzel,
1998], or rodl~:e structures ['Rajh et al., 1999]. Silver nanoparticles
have been similarly deposited ctlto electrodes ['Bright et al., 1998].
Crystallization of suitably derivatized nanopmlicles into well or-
dered arrays have also been demonstrated [Chen et al., 1999; Yin
and Wang, 1999; Park mad Xia, 1999]. Differently sized akaneth-
iol derivatized gold nanopm*icles, depending on experimental con-
ditions, organized lhemselves into ordered bimodal anays, size seg-
regated regions of hexagonal close-packed monodispersed pm'd- Fig. 9. Schmtafics of spontaneous s d f - ~ s e m b l y of a nanostruc-
cles and random arrangements ofpsendohexagonal lattices [Kiely tlwed l-din. A well cleaned substrate is inunersed into a
et a]., 1998]. Advantage has also been taken of capillary forces dihlte aqueous cationic polydeclrolyte sohltion for a time
[Breen et al., 1999; Wei et aL, 2000], temperature control [Boal et optimized for the adsorption of a 2.0~0.5 thick polymer,
al., 2000] and dialysis [Adachi, 2000] to drive miUimeter scale ob- rinsed and dried. Next the polycation coated substrate is
nnmersed into a dilute disp ersion of negatively charged
jects and gold nanoparticles into three dimensional crystalline ar-
nanoparticles for a time optimized for adsorption of a
rays. monoparticalate layee, rinsed and dried to form an or-
Nanopm*icles can be capped (derivatized) mad tethered to a sub- gardc-inorganic sandwich unit. Subsecplent sandwich units
strate to form ordered two-dimensional networks and three dimen- are deposited analogously. The method is ameaable to
sional anays. Two different approaches have been usec[ The fLrst the fabricalion of more complex sup erlattices.
their dispersions and minimizing their desorption on rinsing re- tion permits patterning without a tenlplate [Higgins and Jones,
quires the judicious selection of stabilizer(s) and the carefial control 2000]. Simple robbing the surface results in patterns of well-aligned
of the kinetics of the process. polymer lines whose width is controlled by the ttfic!~less of the poly-
Forces between nanoparticles (or nanoplatelets) and binder nano- lne~" film.
layers (polyions or dithiols, for example) govern the spontaneous
layer-by-layer self-assembly ofultrathin films. These forces are l~'i- P O T E N T I A L APPLICATIONS
marily electrostatic and covalent (for self-assembled monolayers,
SAMs, of dithiol derivatives onto metallic surfaces) in nature, but Application of nanoparticles iNlges from catalysts to additives,
they can also involve hydrogen bonding, g-n interactions, van der surface modifiers and controlled delivery agents. Pe~'haps the great-
Waals attractions, hydrophobic and epitaxial or other types of in- est benefits of 2D and 3D self-assembled nanopamcles will be in
teractions. It is important to recognize that polyionic binders must the optical (and electro-optical) and information inchastiy. Well or-
have displaceable countelions in order to electrostaficaHy bind theln ganized 2D and 3D colloidal (photc~fic) crystals [Shen et al., 2000;
to the oppositely charged surface. The use of dithiols is only rele- Benisty et al., 2000] have been shown to function as periodic ma-
vant with building blocks which incorporate accessible metal atoms, terials [Ashei; 1994], Bragg diffiacting nanosecond optical switches
M (Au- and Ag-nanopattides, for example), or semiconducting na- [Pan et al., 1997], single domain spectroscopy [Vlasov et al., 2000]
noparticles (MS and MSe, for example where M Cd, Zn, Pb) in sensors [Holtz et al., 1998] and optical components [Halevi et al.,
which covalent M-S bonds can be fonne4 The properties of the 1999].
self-asse~nbled multilayers depend primarily on the choice of the The information industry comprises computing, communication,
building blocks used, their rational organization and integration measurement and data storage. According to industiy projections
along the axis perpendicular to the substrate. computers by 2010 should be 256 tirnes as capable as the curreilt
Sequential adsorption of oppositely charged colloids was report- genemtic~l. Feature sizes of this computer will have to be well be-
ed in a seminal paper in [Ilei; 1996]. Self-assembly was subsequent- low the 100 ira1 range. It is increasingly recognized that cun-ent tech-
ly "rediscovered" and extended to the preparations of multilayers nologies will not be able to scale to this level and that the colloid
of polycations and phosphonate anions [Lee et al., 1988; Decher chemical bottom up fabrication will become the only economically
and Hong, 1991 ; Lvov et al., 1993; Fendlei; 1996], as well as to feasible approach to components in the 10 nm range. Our approach
the layering of polyelectrolytes [Decher and Hong, 1991]. Con- using i~rloparticle self assembly for the fabricaticn of charge stor-
struction of electrodes coated by polyelectrolytes, clays and other age and electron bansfer devices have been recently reviewed [Cas-
materials often involved self-assembly [Brumfield et al., 1992; Bard sagneau and Fendler, 2001].
et al., 1992] albeit the method had not been called as such. Self-
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Colloid Chemical Approach to NanotecNaology
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