Research: Science and Education
Making Nanomaterials in Supercritical Fluids: A Review
Xiangrong Ye and C. M. Wai*
Department of Chemistry, University of Idaho, Moscow, ID 83844-2343; *cwai@uidaho.edu
Supercritical fluids, particularly supercritical CO 2
(scCO2), have been used in areas ranging from materials
cleaning, natural products extraction, chemical reactions,
sample preparation, and environmental remediation (1–12).
Generally speaking, a supercritical fluid (SCF) is any sub-
stance at a temperature and pressure above its critical point
and a density close to or higher than its critical density. A
fluid is considered near-supercritical when it is still a liquid
but has begun to show some of the properties normally asso-
ciated with SCFs. The most distinguishing feature of SCFs
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is that their physicochemical properties can be altered con-
tinuously between gaslike and liquidlike limits by adjusting
the system pressure or temperature. SCFs, like liquid solvents,
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can dissolve solid compounds yet they have low viscosities
and high diffusivities like gases. As a result of their high com-
pressibility, SCFs offer a convenient means of accessing a wide
range of solvent properties without physically changing the
solvent.
Physical or chemical transformations in supercritical or
near-supercritical fluids have been a subject of considerable
interest to material scientists particularly in nanoparticle–
nanowire generation and thin solid-film deposition (13–18).
Much of the impetus comes from the advantages of super-
critical fluid processes over conventional solution processes,
such as: (a) SCFs provide high diffusivity and low viscosity
and are therefore capable of attaining high uniformity and
penetration into small areas, (b) the solvent strength of a SCF
can be varied, thus allowing rapid separation of solute by ma-
nipulation of fluid pressure (density), and (c) some SCFs,
such as scCO2, are environmentally benign. Because of these
properties, the byproducts and the contaminants in SCFs can
be easily removed from the system; therefore, nanoparticles,
nanowires, and thin films of high purity can be obtained. In
Figure 1. Physical RESS apparatus applied for supercritical water. Inset: the RESS expansion.
198 Journal of Chemical Education • Vol. 80 No. 2 February 2003 • JChemEd.chem.wisc.edu
materials processing, a SCF can act as a medium either for
transporting solute species or for chemical reactions, or both.
In some cases, the supercritical fluid itself can also take part
in the reactions. This review summarizes recent developments
in physical or chemical processes for synthesizing
nanoparticles, nanowires, and thin solid films in supercriti-
cal or near-supercritical fluids.
Physical SCF Processes for Preparing Nanoparticles
Rapid Expansion of Supercritical Solutions
Rapid expansion of supercritical solutions (RESS) is a
physical process for synthesizing fine powders including
nanoparticles (19–28). Figure 1 shows a typical apparatus
used in RESS. In this process, solutes such as metal com-
pounds or polymers are dissolved in a SCF. When the SCF
solution is allowed to expand rapidly into a region of much
lower pressure, a significant drop in the solubility of the sol-
utes occurs, resulting in their precipitation. The precipitated
solutes form very small molecular clusters, ion pairs, or dis-
persed individual molecules. Usually aerosols rather than va-
pors are formed and the aerosol particles are much smaller
than those formed by the nebulization of ordinary liquid so-
lutions followed by desolvation, such as in spray pyrolysis.
Various morphologies and particle sizes can be thus produced.
Formation of composite materials, such as pharmaceutical or
polymer microcomposite materials for controlled drug releas-
ing, is also possible by precipitation of two different sub-
stances dissolved in the same SCF solution. The
distinguishing features of RESS are the fast attainment of
uniform conditions and high supersaturations in SCF, which
favor the formation of small particles with narrow size dis-
tribution. However, the disadvantage of this physical RESS
FR: fluid reservoir
R: pressure regulator
P: pump
OA: optional autoclave
V: valve
HR: heated region
EN: expansion nozzle
CS: collection surface
C: collection chamber
AR: adiabatic region
IsR: isentropic region
RS: RESS spray
BER: background expansion region

method is that the nanoparticle to be formed must be soluble
in the SCF because the particle is chemically identical to the
starting material. Many desirable materials, for example, semi-
conductors, metals, metal oxides, and mixed-metal oxides,
are insoluble in common SCFs such as scCO2 and scN2O.
SiO2 and GeO2 have been shown to be soluble in scH2O,
but the experimental conditions were rather extreme (445
⬚C, 800 psi) (29–30).
Physical Composite Processes without Expansion
A SCF can also be used as a solvent for dissolving and
dispersing desired materials within a matrix that is also soluble
in the SCF. After desolvation, nanoparticles of the desired
materials form in the matrix. For instance, metal-complex
nanoparticle–polymer composites were prepared by dissolv-
ing a metal complex in scCO2 and infusing it within an
scCO2 “swollen” low-density polymer matrix (31). These
metal complex–polymer composites can function as precur-
sors to surface-selective catalyst systems.
Supercritical Antisolvent Precipitation
Supercritical antisolvent (SAS) precipitation has been
applied successfully to make microparticles and nanoparticles
(32). Its application has been explored in a variety of differ-
ent fields including: explosives, polymers, pharmaceutical
compounds, coloring matter, superconductors, catalysts, and
inorganic compounds. SAS precipitation is based on the fast
dissolution of a liquid solution in a SCF. The addition of a
SCF leads to a lower solubility of the solute, thus forcing the
solute to precipitate into microparticles or nanoparticles. SAS
has unique characteristics that include very large diffusivities
when compared with those of liquids and one-step complete
elimination of the solvent from the precipitates. The most
commonly used SAS is CO 2 . By using scCO 2 as the
antisolvent, microparticles and sub-microparticles of
amoxicillin have been produced (33). Nanoparticles of yt-
trium, samarium, and neodymium acetates were precipitated
as precursors of catalysts or high-temperature superconduc-
tors with morphologies dependent on the different expan-
sion levels of the liquid solution (34–35). More recently,
scCO2 antisolvent process-based production of fullerene
nanoparticles has been reported (36).
Supercritical Drying Processes
Supercritical drying process is another important physi-
cal approach to nanoparticles (37). Nanoparticle powders for
Figure 2. Experimental setup for the chemical RESS method in the
preparation of nanoparticles.
JChemEd.chem.wisc.edu • Vol. 80 No. 2 February 2003 • Journal of Chemical Education
Research: Science and Education
a wide variety of applications, for example, pharmaceutical
compositions or high-performance ceramics, are produced
from sols by contacting the sol with the SCF. The sol is
sprayed into the SCF. All or a portion of the original solvent
system is separated by dissolution in the SCF, and the result-
ing SCF is filtered for recovery of the particles. The solids
are washed using fresh SCF and dried. Solvent-free inorganic
and organic particles can be thus produced with particle sizes
ranging from 20–500 nm.
Chemical SCF Processes for Preparing Nanoparticles
and Nanowires
Chemical Rapid Expansion of Supercritical Solutions
In the original RESS process, a supercritical solution is
expanded rapidly into a vacuum or air (Figure 1). A super-
critical solution can also be rapidly expanded into a liquid
solution to initiate a chemical reaction leading to the forma-
tion of a new product. Based on this concept, Sun et al. de-
veloped a facile and flexible method for preparing stable
suspensions of polymer-protected metal or semiconductor
nanoparticles, such as nickel, cobalt, iron, silver, Ag2S, CdS,
and PbS (38–41). Figure 2 is a schematic of the experimen-
tal setup. The nanoscopic metal ion “solute droplet” produced
in the RESS process is captured by a reducing agent or sul-
fide anions in the receiving liquid solution to form metal or
metal sulfide nanoparticles. The nanoparticles thus produced
have a reasonably narrow-size distribution and form solution-
like stable suspensions in the presence of a stabilization poly-
mer. Some of these nanocrystallines or nanoparticles exhibit
excellent nonlinear optical-limiting properties while others
are excellent magnetic materials.
Direct Chemical Processes without Expansion
Chemical reactions occurring within the SCF system can
also lead directly to nanoparticles. This direct method for
preparing polymer-borne metal clusters was reported by
Kryszewski (42). Depositing metallic nanoparticles in poly-
mer systems was achieved via dissolution of a metal precur-
sor in a SCF and its subsequent reduction or decomposition
during the polymerization step. Reactions using water in sub-
critical and supercritical states have been suggested as pro-
spective ways to synthesize nanocrystal oxide catalysts,
Ce 0.5 Zr 0.5 O 2 , Ce 0.1 Y xZr 0.9-x O 2 , Zr 1−x Y x O 2 , Zr 1−x In x O 2 ,
La 2 CuO 4 ; supported catalysts, Pd兾Rh兾ZrO 2 and
Pd兾Rh兾TiO2; and supports, CeO2, ZrO2, TiO2 (43). The
proposed technique is characterized by high productivity. It
is ecologically friendly and multicomponent oxide catalysts
are obtained with chemical and phase compositions and prop-
erties that can be changed within a large range.
More recently, Holmes et al. have developed a SCF so-
lution phase approach to grow nanowires and nanocrystals
of silicon. Bulk quantities of defect-free silicon nanowires with
nearly uniform diameters ranging from 40 to 50 Å were
grown to a length of several micrometers using sterically sta-
bilized gold nanocrystals as uniform seeds to direct one-di-
mensional nanowire formation (44). Figure 3 is a schematic
illustration of the nanocrystal-directed, nanowire-selfassembly
process. Dodecanethiol-capped Au nanocrystals were dis-
persed in supercritical hexane with diphenylsilane at 500 ⬚C
and 270 bar (or 200 bar in some cases). At this temperature
199
 Research: Science and Education
the diphenylsilane decomposes into Si atoms. Silicon and gold
form an alloy in equilibrium with pure, solid Si when the Si
concentration with respect to Au concentration is greater than
18.6%. Under the specific reaction conditions, the Si atoms
most likely dissolve into the sterically stabilized Au nano-
crystals until reaching supersaturation, at which point they
are expelled from the crystal as a thin, nanometer-scale wire.
Likewise, if hexagonal mesoporous silica is used as a tem-
plate instead of Au nanocrystals, quantum-confined silicon
nanowires can be formed within the 5-nm diameter pores of
the hexagonal mesoporous silica using this SCF solution phase
technique (45). If no template is utilized, robust, highly crys-
tallized, relatively-sized, monodispersed, sterically-stabilized
Si nanocrystals ranging from 15 to 40 Å in diameter could
be obtained in significant quantities in the presence of octanol
at 500 ⬚C and 345 bar (46).
Microemulsion Reactions
The poor solubility of many polar compounds in SCFs
limits their reactions for the purpose of nanoparticle prepa-
ration. One solution to this problem is using water-in-super-
critical fluid microemulsions to dissolve the desired polar
compounds and ions in the fluid phase (47). Figure 4 shows
the structure of a typical water-in-scCO2 microemulsion. The
surfactants are amphiphilic molecules containing a hydro-
philic head group and a CO2-philic tail where the molecular
size and shape of the head and tail are designed to favor ag-
gregation. When such molecules aggregate in a nonpolar SCF,
a reverse micelle is formed with the hydrophilic head groups
forming a core and the hydrophobic tails interacting with
the SCF phase. When water is present, it partitions into the
hydrophilic core forming microscopic water pools leading to
the formation of water-in-SCF microemulsions. These
microemulsions are optically clear, containing spatially-de-
fined, aqueous nanodroplets. They are thermodynamically
stable to flocculation when the density of the SCF is above
the cloud point of the surfactant tail in the bulk fluid. The
mean radii of these water droplets are directly proportional
to the water-to-surfactant mole ratio (W).
These microemulsions can be used as nanoreactors for
synthesizing nanoparticles. Since particle growth occurs
within the water droplet, the size of the water core can be
used to control the particle dimensions. Moreover, the cloud
point depends on density of the fluid phase, which can be
manipulated by varying the pressure and temperature, thus
providing a tunable medium for reaction and separation of
synthesized nanoparticles. Metallic copper nanoparticles (di-
ameter < 20 nm) were synthesized by the reduction of Cu
Figure 3. Nanocrystal-directed, nanowire-selfassembly process in
scCO2.
200 Journal of Chemical Education • Vol. 80 No. 2 February 2003 • JChemEd.chem.wisc.edu
ions from Cu(AOT) 2 (AOT: sodium bis[2-ethylhexyl]
sulfosuccinate) incorporated within AOT reverse micelles dis-
persed in compressed propane and supercritical ethane solu-
tions (48–49). Water-in-scCO2 microemulsions have been
formed by using an ammonium carboxylate perfluoro
polyether (PFPE) surfactant, which incorporates a “CO2-
philic” fluorocarbon chain with a hydrophilic polar carboxy-
late headgroup (50).
Recently, Wai and coworkers reported the synthesis and
dispersion of silver nanoparticles in a water-in-scCO 2
microemulsion made of AOT and a PFPE–phosphate cosur-
factant (51). The microemulsion system utilizing these two
surfactants is stable over a wide W range (up to 34 and 16
for AOT and PFPE, respectively) and with high concentra-
tions of electrolytes in the water core. The procedure for mak-
ing silver nanoparticles involves the reduction of Ag+ in the
water core of the microemulsion with a reducing agent so-
dium triacetoxyborohydride dissolved in scCO2. This was the
first report of the stable suspension of nanometer-sized me-
tallic particles in scCO2 and represented a significant advance
for the future application of CO2-based systems for a wide
range of particle synthesis.
In another report, Wai and coworkers showed that sil-
ver and copper nanoparticles could be synthesized in the CO2
microemulsion made of AOT–PFPE–phosphate surfactants
using more CO2-soluble reducing agents such as sodium
cyanoborohydride and N,N,N´,N´-tetramethyl-p-phenylene-
diamine (52). In situ spectroscopic measurements indicated
the formation of the metal nanoparticles was very rapid (on
the order of about 30 seconds) suggesting the microemulsion
was dynamic in nature.
By injecting an aqueous solution of Na2S into a scCO2
solution containing water-in-scCO2 microemulsions with
Cd(NO3)2 in the water core, Holmes et al. synthesized semi-
conductor nanoparticles of cadmium sulfide (53). The wa-
ter-in-scCO2 microemulsion in this study was stabilized by
an ammonium carboxylate perfluoropolyether (PFPE–NH4)
surfactant. Because an aqueous solution was introduced into
the scCO2 phase, the W value of the microemulsion was
Figure 4. Water-in-scCO2 microemulsion.
 Research: Science and Education

changing. However, CdS nanoparticles with relatively nar- supercritical N2O solutions using radio-frequency plasma in
row size distributions could be prepared by controlling the which radicals and ions from the N2O served as oxidizing
water to surfactant mole ratio. agents. YBa2Cu3O7 was prepared by post-deposition oxidiza-
Wai and coworkers also demonstrated another method tion of the metals co-deposited from supercritical pentane.
of synthesizing nanoparticles by mixing two microemulsions High-quality InP layers were obtained by rapid expansion of
containing different ions in the water core. The contents in a PPh3 and tris(o-dimethylaminomethylphenyl) indium(III)
the microemulsions can exchange rapidly, resulting in nano- mixture in supercritical CO2, C2F6, and Xe to the heated InP
meter-sized new compounds. One example of this micro- substrate in a vacuum (61).
emulsion-plus-microemulsion approach is the synthesis of
silver halide nanoparticles by mixing two microemulsions Chemical Deposition and Chemical Fluid Deposition
containing silver nitrate and sodium halide separately in the Chemical deposition processes can also be carried out
water core (54). Similarly, composite nanoparticles can be directly in a SCF medium. For non-line-of-sight application,
synthesized using this method. such as developing ultra-large-scale-integration (ULSI) inter-
connects or coating porous materials, this method of depo-
Physical SCF Deposition Processes sition is preferred. The gaslike properties and the high pressure
Physical RESS Deposition Processes of a SCF facilitate the delivery of precursors to small holes
and narrow tubing, producing thin films in small features
The physical RESS processes for preparing nanoparticles
that are difficult to accomplish by CVD, SFT–CD or SFT–
can be modified for deposition of thin solid films (19–22,
CVD. Supercritical fluid chemical deposition (SFCD) and
55). When RESS occurs, the solutes can be sprayed onto an
chemical fluid deposition (CFD) techniques have been thus
exposed substrate surface forming uniform films. Coating
developed and a typical deposition system is represented in
thin films onto solid particles can also be achieved by in situ
Figure 6.
simultaneous nucleation and deposition of dissolved materi-
Louchev et al. described a SFCD process in which a pre-
als out of a SCF solution (56). A powder modification pro-
cursor was transported to a heated substrate (700 K) in a SCF
cess was developed by RESS of a binder into a fluidized bed
where it underwent thermolysis to yield a thin copper film
to coat the surface of core particles with fine particles (57).
(62). The film produced by this method had an atomic cop-
An scCO2 solution containing the binder was expanded into
per concentration of approximately 80% (i.e., 20% impuri-
the fluidized bed of the mixtures of core particles and fine
ties).
particles through a nozzle mounted at the center of the dis-
Bocquet et al. proposed a method in which a metal
tributor. The deposition of the binder incorporated the fine
alkoxide dissolved in scCO2 was thermalized at the surface
particles into the layers around the core particles. This leads
of a substrate to form a thin homogeneous oxide layer (63–
to uniform coating granulation without the agglomeration
64). Very thin (< 1mm), very adherent films of anatase TiO2
of particles.
were formed on alumina substrates by decomposition of ti-
tanium tetraisopropoxide in a supercritical isopropanol–CO2
Chemical SCF Deposition Processes
mixture. The films consisted of particles with diameter of ap-
Various types of chemical deposition processes in SCFs proximate 100 nm. The reaction time is very short (a few
have been reported. Chemical deposition methods in SCFs minutes) and the method is adaptable to thicker films.
are distinctly different from the previously described physi- Brasseur-Tilmant et al. prepared a TiO2 particle mem-
cal processes because the deposited materials are chemically brane on macroporous alumina supports by hydrolytic de-
different from precursor compounds. composition of titanium tetraisopropoxide in sc2-propanol
Transport and Chemical Deposition
Sievers et al. described a supercritical fluid transport and
chemical deposition (SFT–CD) process, also called supercriti-
cal fluid transport and chemical vapor deposition (SFT–
CVD), for thin film production by using the system shown
in Figure 5 (58–60). A precursor dissolved in a SCF was dis-
charged through a restrictor, rapidly expanded into an evacu-
ated CVD (chemical vapor deposition) chamber, and formed
an aerosol or a vapor of the film precursor. The vaporized
precursor was then induced to a chemical reaction at or near
a heated substrate surface to form a thin film. Metal films were
formed on substrates heated to a temperature range between 500
and 800 ⬚C. Metal oxide films were deposited from a plasma
source with the substrate not significantly above 100 ⬚C.
Through SFT–CVD, metal films of Al, Ag, Cr, Cu, In,
Ni, Pd, Y, and Zr were pyrolytically deposited from metal
coordination compounds dissolved in SCFs in which organic
ligands or the solvent served as reducing agents for the metal
ions. Films of CuO, Al2O3, Cr2O3, SiO2, and SiO2 doped
with B and P were deposited on unheated substrates from Figure 5. SCF–CD apparatus.

JChemEd.chem.wisc.edu • Vol. 80 No. 2 February 2003 • Journal of Chemical Education 201

 Research: Science and Education
(65). TiO2 particles were deposited on the substrate surface
and inside the pores.
In a recent patent, a high electric-constant material, Ba-
Sr–Ti–O film was formed on a platinum thin film by reac-
tions of organometallic precursors in scCO2. An oxide or a
nitride film may also be formed by performing oxidation or
nitridation at a low temperature using supercritical or sub-
supercritical H2O (66).
A series of studies on CFD was conducted by Watkins
et al. (67–72). A precursor of the material is dissolved into a
supercritical or near-supercritical solvent and a substrate (or
porous solid) is exposed to the solution. A reaction agent is
then mixed into the solution and initiates a chemical reac-
tion involving the precursor, thereby yielding high purity
films onto the substrate surface. Metal, metal oxide, and metal
sulfide films can be deposited using this method. This method
can also be applied to deposit material particles into porous
solids. For making metal films, CFD is essentially a hybrid
technique that uniquely blends the advantages of CVD and
electroless plating. High-purity films of Cu, Pt, Pd, Au, and
Rh have been fabricated onto inorganic and polymer sub-
strates by the H2 reduction of organometallic compounds in
scCO2. Recently, they succeeded in depositing continuous
palladium films at controlled depths within porous alumina
disk (72).
In SFCD and CFD techniques, the precursors react in
the supercritical solution itself (without depressurization), and
the apparatus is essentially the same as for SFT–CD or SFT–
CVD but without the RESS stage. Subsequent cleaning of
metal surfaces can be achieved by washing with neat super-
critical fluid.
Immersion Deposition
Ye et al. recently developed a supercritical fluid immer-
sion deposition (SFID) method for producing thin films of
metals and alloys on substrates or into porous solids of sili-
con, germanium, and other “fluorine-philic” elemental semi-
conductors from supercritical or near-supercritical CO2
solutions at modest temperature (73). The deposition setup
is shown in Figure 7. The organometallic precursor was dis-
solved in a reservoir by supercritical or liquid CO2. The so-
lution was then pumped into a vessel where the loaded
polymer supported fluorinating agent released HF into CO2
Figure 6. Schematic view of a typical SCFD and CFD apparatus.
202 Journal of Chemical Education • Vol. 80 No. 2 February 2003 • JChemEd.chem.wisc.edu
solution. The solution was transported into a heated reactor
(lower than 100 ⬚C) and merged with the “fluorine-philic”
substrate mounted there, depositing a metal film onto the
substrate surface. High-purity Pd, Ag, and Cu metal films
have been thus produced on silicon or germanium substrates.
SFID involves redox reactions between an organometallic
precursor and an elemental semiconductor in scCO2 using
HF as a reagent. The reaction is probably initiated by oxida-
tion of an elemental semiconductor to a fluoride compound
with the release of electrons that cause the reduction of an
oxidized metal in a precursor to its metallic form. For SFID
deposition of copper film onto silicon substrate from scCO2
solution of Cu(hfa)2 (hfa: hexafluoroacetylacetonate), the pos-
sible deposition mechanism can be proposed as following:
Si + 4HF + 2Cu(hfa)2 → 2Cu + SiF4 + 4Hhfa
SFID is potentially useful for depositing thin films in small
features and narrow tubing owing to the gaslike properties
and the high pressure of the SCFs, combined with the mod-
est reaction temperature.
Compared to the conventional CVD approach, chemi-
cal deposition processes in SCFs have several advantages.
Supercritical media allow one to use relatively nonvolatile,
less toxic, thermally unstable, and less expensive precursors.
This extends the range of possible precursors and their com-
binations for production of thin films. Almost any precursor
that is soluble in a SCF can be used in the SCF deposition
process. Virtually all of the volatile CVD and metal–organic
chemical vapor deposition (MOCVD) reagents and many
semivolatile or nonvolatile reagents can be used (13–14,59).
Furthermore, the deposition of mixed-metal compositions by
CVD usually requires more than one precursor chamber and
the delivery rates of each of the reagents must be simulta-
neously controlled to maintain the correct stoichiometric ra-
tio. The preparation of YBa2Cu3O7−x films by MOCVD, for
example, has been shown to require separate, individual tem-
perature reservoirs and carrier-flow rate-controlled reservoirs
for the Y, Ba, and Cu precursor compounds (74–77). In a
SCF deposition process, films that require more than one re-
agent in the CVD process can be deposited using a single
supercritical fluid solution containing all of the precursor
reagent(s). The precursor mixture can be prepared by weigh-
ing the necessary species, followed by dissolution in a SCF.
This allows precise control of stoichiometry and homogene-
ity of the reagents at the substrate surface because, unlike tra-
ditional MOCVD processes, they are from a single source
Figure 7. Setup for immersion deposition process in scCO2

that is well mixed before it enters the deposition chamber.
The films obtained were usually very smooth, uniform, and
highly reflective. In addition, the deposition rate of CVD
process is low, but by using supercritical fluid deposition, the
deposition rate can be increased. Unlike sputtering or evapo-
ration deposition methods, supercritical fluid chemical depo-
sition process is not limited to line-of-sight deposition, and
complex shaped objects can be coated. SFCD, CFD, or SFID
is a promising method to coat nanotubes.
SCF Electrodeposition Processes
Electrodeposition technique can also be used in a super-
critical solution (78). Aluminum has been electrodeposited
from supercritical electrolytes consisting of toluene, ethane,
AlBr3, and Bu4NBr (or KBr) at temperatures of 75–120 ⬚C
and pressures of 1200–1600 psi. Ceramic and carbon films
have been deposited from supercritical water solution (79).
By forming microemulsions in a SCF, many SCFs can be elec-
trically conductive, thus applicable for electrodeposition.
Other Nanomaterials Processing Using SCFs
Besides the materials processing techniques discussed
above, some other methods have also been developed to make
nanoparticles or thin solid films using SCFs. For example,
carbon coating can be obtained on silicon carbide fibers by
selective etching with scH2O, which removes silicon from the
surface layer of the fiber (80). This hydrothermal-leaching
method provides a simple and inexpensive route to carbon
coatings on the surface of polymer-derived SiC fibers.
Nanoporous silica materials have been prepared using an ac-
tivated carbon as a mold and scCO2 as a solvent (81). Tetra-
ethyl orthosilicate dissolved in scCO2 was in contact with
the activated templates of various macroscopic shapes. After
the removal of activated carbon templates by calcination in
an air or oxygen plasma treatment, microporous and
mesoporous SiO2 samples, replicating not only meso-struc-
tures, but also macroscopic shapes, of activated carbon molds
were obtained.
Hazards
Silane, HF, and other hazardous materials as well as high
pressure and temperatures could be involved in the referenced
experiments. Suitable safety precautions should be taken into
consideration including the use of hoods and blast screens
to prevent possible leakage or explosion.
Conclusions
Processing materials in a SCF, especially in scCO2, is a
novel and emerging technology for preparing nanoparticles,
nanowires, and thin solid films. Supercritical CO2 is inert
and recyclable; therefore, exposure of personnel to hazard-
ous solvents and disposal of organic liquid wastes can be mini-
mized. Removing unreacted reagents, byproducts, and
contaminants from the SCF system can be easily achieved,
thus leading to production of nanoparticles, nanowires, and
thin solid films with high purity. Because of the gaslike dif-
fusivity of SCFs, diffusion-limited reactions occur more uni-
formly than in conventional solvents. Reactions involving
gases for preparing nanomaterials are more efficient in SCFs
JChemEd.chem.wisc.edu • Vol. 80 No. 2 February 2003 • Journal of Chemical Education
Research: Science and Education
because they are often miscible and homogeneously dispersed
in the fluid phase. This also contributes to high purity and
uniformity of the nanomaterials synthesized in SCFs. In SCF
deposition processes, relatively nonvolatile, less toxic, ther-
mally unstable, and less expensive precursors can be used.
Often, only a single supercritical solution reservoir is neces-
sary for depositing films that require more than one precur-
sor in the CVD process. Precise control of stoichiometry and
homogeneity thus becomes possible and higher deposition
rates can be obtained. SFCD, CFD, and SFID are promis-
ing techniques for depositing metals and oxides in small fea-
tures for preparation of smart materials needed for the future
chemical and electronic industries.
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