Chapter 14

Chemical Bath Deposition

Mark R. De Guire, Luciana Pitta Bauermann, Harshil Parikh,

and Joachim Bill

14.1 Introduction

Chemical bath deposition (CBD) is the name given to a variety of techniques that
produce films of solid inorganic, non-metallic compounds on substrates by immers-
ing the substrate (once, or repeatedly) in a precursor solution (often aqueous).
Control of the temperature (usually below 100
C), pH, and concentration of the
solution induces a solid phase to exsolve and form a film on the substrate, often
without any subsequent heat treatment. While such approaches have been used for
many years to produce sulfide, selenide, and other non-oxide films [1], relatively
little work had been done on oxide films until the early 1980s, when interest began
increasing rapidly [2].
There are several motivations for this interest. The functional properties of
oxides make them attractive in thin-film form in a variety of applications, such as
sensors, transparent conductive oxide coatings, catalysts, thermal barrier coatings,
and “superhydrophobic” layers. Producing such coatings at temperatures below
100
C allows materials that cannot tolerate high temperatures, such as polymers, to
be coated. Immersing a substrate in a liquid overcomes line-of-sight limitations of
vapor-phase deposition or spraying techniques, and allows complex surfaces such
as powders, tubes, and porous structures to be coated. Lastly, the equipment needed
for CBD is much simpler than that used for vapor-phase film deposition techniques
and readily lends itself to manufacturing scale-up and to continuous (as opposed to
batch) processing.

M.R. De Guire (*) • H. Parikh

Department of Materials Science and Engineering, Case Western Reserve University,
Cleveland, OH 44106, USA
e-mail: mark.deguire@case.edu
L.P. Bauermann • J. Bill
Institute for Materials Science, University of Stuttgart, 70569 Stuttgart, Germany
Max Planck Institute for Metals Research, 70569 Stuttgart, Germany

T. Schneller et al. (eds.), Chemical Solution Deposition of Functional Oxide Thin Films, 319
DOI 10.1007/978-3-211-99311-8_14, © Springer-Verlag Wien 2013
320 M.R. De Guire et al.

As a technique for depositing thin nonmetallic inorganic films from aqueous

solutions, chemical bath deposition is at least 140 years old: Hodes [3] cites a report
from 1869 by Puscher of sulfide layers deposited from thiosulfate solutions of
copper, lead and antimony salts. The approach was not studied extensively or
exploited commercially until the last quarter of the twentieth century, when CBD
films of sulfides and selenides began to play crucial roles in the electrodes of
photovoltaic solar cells.
During the same period, aqueous chemical routes for the synthesis of oxide
powders received considerable attention, with a focus on producing fine particles
with uniform shape and narrow size distributions. Although application of these
routes for the synthesis of oxide films is not as widespread as for oxide powders or
for sulfide and selenide films, their shared underlying chemical principles provide a
foundation for understanding oxide film deposition.
To understand chemical bath deposition processes, and thereby to be able to
exert control over aspects such as the growth rates, structures, and properties of the
deposited films, it is helpful to divide the topic into three general areas:
• Solution chemistry—controlling solution parameters such as pH, temperature,
and composition to yield desired phases and control deposition rate;
• Substrate effects—tailoring the surface energy, magnitude and sign of surface
charge density, and hydrophilicity or -phobicity of a substrate so as to localize
and promote the formation of films;
• Process control—designing a deposition process, based on an understanding of
the mode of film formation, to control the growth rate and microstructure of the
deposited film.
The next sections will address each of these topics. The chapter concludes with a
discussion of the limitations and advantages of CBD and its most attractive areas
for future research and potential applications.

14.2 Solution Chemistry

14.2.1 General Framework

To deposit a compound MXn/2 via CBD, the deposition medium will consist of one
or more salts of metal Mn+ and a source for the chalcogenide X (X ¼ O, S, Se) in
aqueous solution. Typically, these salts are chosen for their moderate to high
solubility in water, low cost, or ready availability, e.g., chlorides, nitrates, sulfates,
or acetates. (Metal-fluoride precursors are usually used for the so-called “liquid
phase deposition” approach, described in Sect. 14.2.2.)
Products containing multiple metals are relatively easily obtained when a spe-
cific cation stochiometry is not required (doped materials or solid solutions) and the
metals have similar precipitation behavior at a given temperature and pH.
14 Chemical Bath Deposition 321

A complexing agent (also called a complexant) may be added, as a means

(in addition to adjustment of concentration, temperature, and pH, as discussed
below) of controlling the rate of formation of the solid. Typically, complexants
supply ligands for the metal, and the greater their affinity for the metal relative to
that of the chalcogenide, the more the complexant helps slow down the hydrolysis
reactions that lead to formation of the solid phase. When the desired compound
contains multiple metals whose hydrolysis rates differ widely under a chosen set of
deposition conditions, a complexant can be particularly useful for slowing the
deposition kinetics of the more readily hydrolyzed species. The concentration of
the complexant is usually chosen to be a predetermined ratio of the concentration of
the metal precursor.
For non-oxide films, the chalcogenide source is present in a dilute concentration
(typically 0.01–0.1 M). This concentration constitutes an additional parameter that
permits control to be exerted over the rate of film deposition. When the desired solid
is a sulfide, thiourea ((NH2)2CS), thioacetamide (CH3CSNH2) or soluble salts
of thiosulfate (S2O32–) commonly serve as sources of S2– ions, while selenourea
(SeC(NH2)2) or selenosulfate (SSeO32–) are examples of sources for Se2– ions.
For oxide products, water provides oxygen in the form of OH– ions. For a metal
cation Mn+ complexed by i ligands Lk–, the steps to forming the oxide MOn/2 can be
formulated as the following reactions:

dissociation of water : nH2 O , nOH þ nHþ (14.1)

displacement of ligands : nOH þ MðLÞi ðnikÞþ ! MðOHÞn ðsÞ þ iLk (14.2)

deprotonation to form oxide : MðOHÞn ðsÞ ! MOn=2 ðsÞ þ n=2 H2 O (14.3)

net reaction : MðLÞi ðnikÞþ þ n=2 H2 O ! MOn=2 ðsÞ þ nHþ þ iLk (14.4)

The process depicted by reactions (14.2) and (14.3) is sometimes called “forced
hydrolysis” [4]. Note an important contrast: for non-oxides, the amount of chalco-
genide precursor added to the solution will primarily determine the concentration
[X2(aq)] of the free chalcogenide ion, one of the key parameters determining the
degree of supersaturation of the solution (and therefore its tendency to produce the
desired solid). Although pH and temperature allow some modulation of the free
chalcogenide concentration, one of the easiest ways to slow down the rate of solid
production is simply to reduce the starting concentration of the chalcogenide
source. For oxides, on the other hand, the chalcogenide source is OH, of which
its “precursor”—the water itself—provides a virtually unlimited supply. In CBD of
oxide films from aqueous solutions, the chalcogenide source is essentially never
exhausted. The remaining variables—pH and temperature—must therefore be
closely controlled, as they directly influence the thermodynamics and kinetics of
the deposition process.
Reactions (14.1), (14.2), (14.3), and (14.4) illustrate the roles that pH, tempera-
ture, and concentration play in controlling the rate of deposition:
322 M.R. De Guire et al.

Fig. 14.1 Schematic

illustration of the effect of
solution pH (horizontal
axis) and metal
concentration [M] (vertical
axis) on the tendency of a
solution to exsolve a solid
phase (adapted from [6])

• The effect of pH ( –log10[H+]) is explicit in reactions (14.1) and (14.2). Note

however that forced hydrolysis does not require addition of base; hydrolysis can
occur even in acidic solutions when the metal cation is easily hydrolyzable, as
with Al3+, Ti4+, Fe3+, Zr4+, Sn4+, and Ce4+.
• Increasing the concentration of the metal salt increases the rate of reaction by
shifting reaction (14.2) to the right, and increases the amount of material able to
be deposited from the solution according to the degree to which the solubility
limit of M(OH)n is exceeded.
• The role of temperature is less obvious: with increasing temperature, the disso-
ciation of water (reaction 14.1) shifts to the right, increasing the supply of
hydroxyl ions needed to displace the ligands from the metal (reaction 14.2).
Raising the temperature also induces deprotonation of the hydrated metal spe-
cies (reaction 14.3). Both of these effects typically accelerate the formation of
the solid. In fact, a common strategy in CBD of oxides is to use a precursor
solution that is relatively stable against precipitation at room temperature, but
which produces films in practical time frames when the temperature is raised.
The degree of supersaturation—a measure of the degree to which the
concentrations of the free ions in solution exceed their solubility limits—plays a
central role in film formation. Supersaturation is most often controlled by the
concentration, pH, and temperature of the solution. When film growth occurs by
particle attachment (see Sect. 14.3.1), the degree of supersaturation dictates the
size, population and rate of formation of the particles making up the film.
Figure 14.1 schematically illustrates the interplay between metal ion concentra-
tion [Mn+] and pH in the supersaturation of an aqueous solution. For acidic oxides
such as TiO2, ZrO2, and SnO2, the tendency for solid to precipitate increases as pH
increases from strongly acidic toward less acidic and basic values. Quantitative
versions of Fig. 14.1 for specific oxides can be found in collections such as Baes and
Mesmer [5].
If the pH and concentration place the solution deep in the field labeled “bulk
precipitation” in Fig. 14.1 (adapted from [6]), solid forms rapidly in the solution. In
the field labeled “metastable supersaturation,” solid may form on any solid surface
that lowers the thermodynamic barrier to nucleation. Ideally, the only such surface
14 Chemical Bath Deposition 323

would be the substrate, but in practice it can be difficult to avoid nucleation on other
surfaces (including container walls and adventitious particles in the solution) and to
maintain the solution conditions continuously (and with spatial uniformity) in the
metastable condition.
Because these solution parameters govern the rate of formation of solid, they
have a major influence on the film deposition process, and they will be taken up
again in the sections on substrate effects and process design. As discussed in [2] and
references cited therein, films from less heavily supersaturated solutions typically
grow more slowly but may ultimately reach higher thickness—a “tortoise and hare”
effect. Overall, the growth rate is determined by supersaturation (temperature,
concentration, and pH), while thickness is limited by the supply of reactants
(starting concentrations and avoidance of bulk precipitation).

14.2.2 Variants of CBD

Within the scope of this general description of CBD, considerable latitude exists in
the solution chemistry. Several specific approaches have been utilized for forming
oxide films:
• Liquid phase deposition (LPD) utilizes an aqueous solution of a metal-fluoro
complex (MFm)(n–m), and slowly hydrolyzes this complex by adding water, boric
acid (H3BO3) or aluminum metal. The great variety of oxides to which this
technique has been applied, notably by Deki and co-workers [7–11], and the
unique strategy of pitting fluoride complexes against fluorine scavengers to
control the rate of hydrolysis, warrant listing it as a distinct technique. Also in
contrast to CBD in general, LPD from its inception has been used predominantly
for producing oxide films: the technique was first described in a patent [12] for
producing titania films on glass in 1984.
• Successive ion layer adsorption and reaction (SILAR), uniquely among CBD
techniques, builds up a film through repeated immersions of the substrate
alternately into a metal salt solution, then a hydrolyzing solution. SILAR is
even able to promote epitaxial growth at room temperature, a fact that was
related to the high surface diffusion coefficients of the adsorbed ions and the
long surface diffusion time available to reach the lattice kinks. The sequential
character of the SILAR technique avoids some of the incompatibilities in the
deposition conditions that might exist between two components of a desired
multicomponent film. The deposits usually need heat treatment to yield the
desired crystalline phase. SILAR was first reported in the mid-1980s indepen-
dently for sulfides [13] and for Cu(I) [14] and Zn(II) [15] oxides. Tolstoy [16]
reviewed the potential applications of SILAR in gas sensing, photovoltaics,
electronics, and lighting applications.
• Electroless deposition (ED) entails a change in the oxidation state of the
dissolved metal cation to an insoluble state in the deposition medium, followed
324 M.R. De Guire et al.

by catalyzed deposition of the solid at a “sensitized” substrate without use of

externally imposed sources of electrical energy [17]. This technique is an
adaptation of electroless plating techniques that are widely used for depositing
metal films. In a recent example [17], films of β-FeOOH or Fe3O4 were depos-
ited from iron (III) nitrate solutions, and Fe from iron (III) sulfate solution, on
amine-functionalized Si that had been immersed in a Pd salt solution for
sensitization; dimethylamine borane complex (DMAB, (CH3)2NHBH3) in the
deposition medium served as the reducing agent.
Table 14.1 summarizes the oxide materials (and a few sulfides) that have been
deposited in the form of thin films via these techniques or with the use of organic
self-assembled monolayer surfaces (vide infra). Recent reviews [2, 18, 19] provide
further details about these films and give citations to the original reports.
Some variations on CBD have been extensively developed for a specific cate-
gory of materials. An example is ferrite plating [20, 21], which was developed by
Abe and co-workers to deposit films of iron-containing magnetic oxides (ferrites).
They reported depositing a wide variety of spinel ferrites (such as
(Fe3O4)1-x(γ-Fe2O3)x, MnxFe3–xO4, CoxFe3–xO4, NixFe3–xO4, NixZnyFe3–x–yO4,
Fe3-xZnxO4), Ba-Fe oxides, and Y-Fe oxides. The route includes an aspect of
electroless deposition in that it requires increasing the oxidation state of iron
from (II) in solution to (III) in the films, although unlike ED this oxidation takes
place in the bulk solution and is not believed to be catalyzed at the substrate. Many
of the variations in technique discussed below, such as the use of flowing precursor
solutions, photo-stimulated deposition, and application of electrical current to
induce deposition, have been used in ferrite plating.

14.2.3 Use of Organic Additives

The presence of organic additives in the deposition liquid plays an important role in
the control of the morphology of the formed particle and consequently the film. The
variety of the obtained morphologies is large: sponges, honeycombs, ribbons,
spheres, sheets, cubes and hexagonal platelets. The additives adsorb preferentially
on specific faces of the inorganic crystal, inhibiting the growth of those faces. The
uncoated faces then grow further, conferring unusual morphologies [22–31]. On the
other hand, crystallographically non-selective adsorption of the additives leads to
“miniaturization” of the formed crystallite by slowing the growth rate in all
directions.
Many of the additives that adsorb onto crystal surfaces have functional groups
similar to those found in effective complexants, especially carboxylic acid, alcohol,
amide, and ether groups.
In some cases the role of the organic additive is not exclusively to control the
growth rate of certain crystal faces, but also to promote formation of an intermedi-
ate amorphous phase during the crystal growth. The presence of these amorphous
14 Chemical Bath Deposition 325

Table 14.1 Listing of oxides (and three sulfides) that have been deposited as thin films via
chemical bath deposition (CBD) and related techniques: liquid phase deposition (LPD), successive
ion layer adsorption and reaction (SILAR), electroless deposition (ED), and use of organic self-
assembled monolayers (SAM)
CBD LPD SILAR ED SAM
Ag2O X
AgO X
Cd2SnO4 X
CdO X
CdS X X
CeO2 X X
(Ce,Gd)O2-x X
CoO X
Co3O4 X
Cu2O X X
CuO X
(Cu,Fe)3O4 X
Eu2O3-x X
Fe3O4 X
FeOOH/Fe2O3 X
α-Fe2O3 X X
α-FeOOH X
β-FeOOH X X
γ-FeOOH X
In2O3 X X X
In2O3:Sn X
La2O3-x X
LaCoO3 X
LaCrO3 X
LaFeO3 X
La1-xMnO3 X X
LaNbOx X
MnO2 X X X
NdCoO3 X
NdCrO3 X
NdFeO3 X
NdMnO3 X
NiO X
NiOOH X
NiFe2O4 X
α-PbO2 X
PbS X X
SiO2 X
SnO2 X X
SnO2:Sb X
Sn16(OH)xPW19Oy X
Ti2O3 X X
TiO2 X X X
(continued)
326 M.R. De Guire et al.

Table 14.1 (continued)

CBD LPD SILAR ED SAM
TiO2-dopamine X
TiO2-methylene blue X
TiO2-SiO2 X
TiO2-V2O5 X
V2O5 X X
Y2O3, Y2O3-x X X
Y2O3:Eu X
Y2O3-ZrO2 X X
ZnO X X X X X
ZnO:Al X
ZnO:Cd X
ZnO:Cu X
ZnO:Ni X
ZnO:Sn X X
ZnS X X
ZnAl2O4 X
ZrO2 X X X
ZrO2:Eu X
ZrO2:Tb X

particles can reduce the degree of supersaturation of the solution, suppressing the
rapid formation of the initial crystals. The amorphous phase then dissolves, and
nanocrystals are formed. The amorphous particles contain metal ions that are
gradually released, promoting a more controlled crystallization process.

14.3 Substrate Effects

14.3.1 Mechanisms of Film Formation

The preceding discussion does not directly address the circumstances that would
cause the forming solid phase to adhere to a substrate as a film. Expressed in broad
terms: the solution chemistry primarily dictates whether a solid can form, while the
substrate largely determines where the solid will deposit. The chemical nature of
the substrate surface and its interactions with the depositing solid and the liquid
deposition medium together influence the film’s growth rate and morphology.
Two basic mechanisms (Fig. 14.2) have to be considered:
• Dissolved ionic species may attach to the substrate according to an ion-by-ion
growth mechanism. In this case heterogeneous nucleation leads to directed
growth of nuclei of the inorganic phase on the substrate.
14 Chemical Bath Deposition 327

Fig. 14.2 Mechanisms for

the formation of inorganic
films from aqueous
inorganic solutions (after
[32])

Fig. 14.3 Scanning electron microscope images of (a) etched titanium surface (plan view);
(b) etched titanium surface with hydroxyapatite coating deposited from simulated body fluid
(plan view); (c) cross-section of hydroxyapatite coating (middle of image) on etched titanium
(bottom of image), showing coating “keyed-in” to the substrate surface. (Figure 14.3a and b
reprinted from [33], © WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Used with permis-
sion. Figure 14.3c reprinted from [34], © Carl Hanser Verlag, München. Used with permission)

• Colloidal particles may form in the solution by hydrolysis and condensation

reactions of the dissolved species and subsequently be attracted to the substrate
by electrostatic or van der Waals interactions. Here nucleation in solution is
involved, and usually results in a polycrystalline film with random crystal
orientation.
Both mechanisms can occur simultaneously, or ion-by-ion growth can be
followed by particle attachment. Transparency of the solution does not rule out
the possibility of film growth by particle attachment. Nor does the presence of
particles in the solution rule out the possibility of film formation via heterogeneous
nucleation and growth on the substrate. As discussed in Sect. 14.2.3, the ultimate
oxide phase may be preceded by one or more intermediate phases. In practice, it is
usually not possible to determine unambiguously which process dominated the
formation of a specific film from the nature of the deposition medium alone, or
by examining the film’s microstructure ex situ.
328 M.R. De Guire et al.

Fig. 14.4 Schematic illustration of the effect of the zeta potentials (ζ 1 and ζ2) of two adjacent
surfaces on the nature of the electrostatic interaction between them. When the pH of the solution
between the two surfaces is between the isoelectric points (IEP1 and IEP2) of the two surfaces, the
electrostatic interaction is expected to be attractive

When a supersaturated solution remains stable against precipitation for very

long times unless a specifically prepared substrate is present to promote film
formation, nucleation and growth is probably the dominant mechanism of deposi-
tion. One example is the deposition of hydroxyapatite coatings on titanium from
supersaturated simulated body fluid (SBF) for orthopedic implant applications
(Fig. 14.3) [33, 34]. Under deposition conditions, the supersaturated SBF remains
solid-free for months unless a substrate that has first been treated with a silicate
“nucleating layer” is placed in the solution.
In contrast, when particles are known to be present in the solution, and the
occurrence or absence of film formation correlates with the nature of the electro-
static interaction between the substrate and the depositing solid, particle attachment
is strongly implicated as a primary mechanism of film deposition. These electro-
static interactions are primarily governed by the zeta potentials of the substrate and
the solid phase, which in turn depend on the pH of the surrounding liquid phase.
When the pH of the solution is such that the zeta potentials of two solid surfaces
are opposite in sign, an electrostatic attraction is expected between the surfaces, and
repulsion when the zeta potentials have the same sign (Fig. 14.4). The condition for
electrostatic attraction is met when the pH of the solution is between the isoelectric
points, IEP1 and IEP2, of the two surfaces (Fig. 14.4). For example, films of vanadia
(which has negative zeta potential [35, 36] in moderately acidic solutions) deposit
on amine- and alkyl ammonium-treated surfaces, which are positively charged [37]
in acidic and neutral solutions, but not on sulfonate-treated surfaces (which are
negatively charged [37] at pH down to about 2) under otherwise identical
conditions. (The functionalization of surfaces is discussed in Sect. 14.3.2.)
14 Chemical Bath Deposition 329

Fig. 14.5 Schematic

illustration of an organic
self-assembled monolayer
(SAM)

Other interactions occur between solid surfaces in liquid media that can affect
their mutual attraction or repulsion. These include:
• Induced-dipole effects, such as van der Waals interactions, are shorter-range,
usually attractive,1 and smaller in magnitude than the electrostatic interactions
discussed above. Nevertheless such interactions are ubiquitous and may become
significant when electrostatic interactions diminish or are weak to start with.
When a substrate has been completely covered with electrostatically attracted
particles, the attractive van der Waals interactions between the deposited layer
and adjacent unattached particles in the solution may play a role in subsequent
growth of the film.
• Interactions between species surrounding or adsorbed onto one or both solids,
such as ionic double layers or polymer additives from the solution (Sects. 14.2.3
and 14.3.2).
• Very short-range interactions, when the separation between surfaces approaches
the size of a water molecule (so-called hydrophobic interactions) [38].

14.3.2 Functionalization of Substrates

A significant recent trend in research on low-temperature deposition of thin films

from liquid media has been the use of organic modifications of substrate surfaces to
promote the formation of films. This can be achieved for example with surfactants,
polyelectrolyte bilayers, and organic self-assembled monolayers (SAMs). The last
of these will be discussed in more detail to illustrate the options that SAMs afford
for engineering a substrate to promote film deposition.
SAMs are ultra-thin layers (typically 2.5 nm or less) formed via the spontaneous
attachment of hydrocarbon-based surfactant molecules onto a substrate, comprising
structurally ordered, two-dimensional arrays [39, 40]. One end of each surfactant
molecule bonds to the substrate. Thiol groups (-SH) bond to clean unoxidized metal
surfaces. Trichlorosilyl groups (-SiCl3), after hydrolysis to silanol (-Si(OH)3), bond
via a condensation reaction to surfaces such as glass, sapphire, and the native oxides
on Si, Ge, and Ti (Fig. 14.5).

1
This presumes that the Hamaker coefficient for the two solid surfaces and the interposing liquid
medium is positive. This is usually the case for aqueous solutions, oxide precipitates, and the
substrates discussed here and in the literature cited.
330 M.R. De Guire et al.

The functional group at the opposite end of the molecule (or a group that
replaces it in a post-deposition displacement or transformation) determines the
surface chemistry of the SAM, whether acidic or basic, hydrophilic or hydrophobic,
polar or non-polar. Thus SAMs from alkane thiols and trichlorosilanes, with
terminal methyl groups or other saturated hydrocarbon groups, are hydrophobic
surfaces. SAMs with surface sulfonic acid (-SO3H), carboxylic acid (-COOH), and
phosphonic acid groups (-PO(OH)2) deprotonate in aqueous solutions whose pH is
above that of the pKa of the SAM surface, giving hydrophilic, negatively charged
surfaces. Other surface groups are hydrophilic but tend to acquire positive surface
charge through protonation, as with amine (-NH2) groups, or are cationic in
character, such as alkyl ammonium (-NR3+) groups. (Amine- and alkyl
ammonium-terminated SAMs were used in the deposition of the vanadia films
that were cited in Sect. 14.3.1 as examples of film growth by particle attachment.)
Oxides that have been deposited as films on SAM-treated surfaces via CBD
methods are listed in Table 14.1.

14.3.3 Patterned Deposition

When the surface treatment used to promote film growth is selectively applied to
specific regions of the substrate, the subsequent film deposition can be made to
conform to that spatially predetermined arrangement, leading to what is called
patterned deposition. Patterned functionalization of a substrate can be achieved in
the way the functionalization is first applied to the surface, through microcontact
printing of a surfactant with what amounts to a “rubber stamp” [41]. Another
approach is to shine UV light through a photomask onto a uniformly functionalized
surface, either to alter the functional group photochemically or to cleave the
adsorbed species from the surface. In contrast to standard photolithography, either
approach permits patterning of the oxide to be achieved without use of photoresists
and without a subtractive step such an etching to remove oxide material that has
already been deposited. Such approaches offer the potential of creating patterned
oxide films with fewer fabrication steps and fewer processing byproducts.
The resolution that can be achieved in the functionalized pattern (i.e., prior to
deposition of the oxide film) can be well into the nanometer scale, depending on the
technique used (electron-beam etching, photolithography, etc.). In a recent example
of nanoscale patterning of an organic functional layer, Schimmel and co-workers
achieved lateral resolution of 40 nm in photodimerized thiol layers 12 nm thick by
using the tip of an atomic force microscope [42]. It remains to be seen whether this
level of resolution in the organic layer will allow higher resolutions to be achieved
in inorganic films subsequently deposited on the patterned surface.
The resolution of the deposited film itself is usually less fine than that of the
patterned functional layer. An extensive review by Gao and Koumoto [18] surveyed
this topic. Typical spatial resolutions in the range of 1–20 μm have been achieved
for various oxide films (TiO2, ZrO2, SnO2, ZnO, iron oxides, Ta2O5). With the size
14 Chemical Bath Deposition 331

Fig. 14.6 Left: Porous nickel oxide layer in the anode of a solid oxide fuel cell. Right:
Nanocrystalline cerium oxide film, ~100 nm thick, deposited via chemical bath deposition on
the porous nickel oxide layer shown at left after treatment with a sulfonate-functionalized self-
assembled monolayer. The ceria film was uniform, adherent, and conformal, and it penetrated
throughout the 40-μm depth of the porous anode [43]

of the primary deposited particles typically 15 nm or smaller in such films, and with
nanoscale resolution of the pattern itself having been demonstrated, the potential
would seem to exist for sub-micron resolutions to be achieved. This would require
overcoming at least two factors commonly observed in the deposited films. First,
when films grow via particle attachment, the primary particles are often
agglomerated into clusters 50–100 nm in size; this agglomeration may occur before
the particles deposit on the substrate, limiting the fineness of the patterned deposit.
Second, once the initial layer of particles or agglomerates is complete, subsequent
deposition is likely to be governed more by the interactions between the clusters
and the already-deposited film than by substrate-film interactions, so that the
controlling influence of the patterned substrate on film deposition in lateral
directions diminishes as the film grows thicker. This effect may be seen even if
the films form initially by heterogeneous nucleation and growth on the substrate, for
heterogeneous nucleation may later occur on the growing film. The review by Gao
and Koumoto [18] shows that the same solution parameters that control growth rate
(Sect. 14.2.1) also strongly affect the resolution of patterned films.

14.3.4 New Morphologies

An interplay of solution chemistry, film morphology, and application distinguishes

several recent advances in functional oxide film deposition from aqueous solutions.
For example, while most of the early literature on CBD of oxide films described
deposition on flat planar substrates, the ability of a liquid to permeate porous
structures and to coat fibers, particles, and other shapes with relatively concentrated
precursors for solid films is a powerful advantage of CBD approaches. Figure 14.6
illustrates this capability, showing a porous nickel oxide layer on the anode of a
solid oxide fuel cell before and after CBD of a 100-nm-thick nanocrystalline cerium
oxide film [43]. The ceria film was deposited after the porous nickel oxide was
332 M.R. De Guire et al.

treated with a sulfonate-functionalized SAM. The high degree of conformity of the

ceria film and its lack of cracks and voids are evident. The coating penetrated
throughout the 40-μm-thick porous anode.
Infiltration of surfaces with complex topographies is also of interest for photonic
crystals, data storage, and field emission devices [10]. Thus not only the chemical
nature of the substrate surface, but also its topography plays a role in the utility of
CBD as technique for depositing oxide films.
As the understanding of the deposition methods has increased, the forms of the
synthesized materials have expanded beyond thin films. For example, nanorods of
c-oriented wurzite structure ZnO [44] and nanoporous films of TiO2 [45] were
prepared by CBD routes after first depositing a dense “seed” layer of the respective
oxides.
In a unique adaption of the LPD technique, Deki and coworkers [9] formed films
of TiO2, SnO2 or β-FeOOH at a liquid-liquid interface, rather than on a solid
substrate. This approach should work on a variety of CBD systems and suggests a
way to produce free-standing films of virtually any oxides that are obtainable via
CBD (Table 16.1).
In another example of material deposition at a non-solid interface [46], micelles
of surfactants were used as “substrates” to control the morphology of TiO2-V2O5
mesoporous powders. Surface area could be controlled by the choice of surfactant
and the solution composition, illustrating how the deposition process could be
engineered to achieve a desired level of performance in a functional oxide material
synthesized via low-temperature deposition. Whereas these mesoporous materials
were formed on the outside of the surfactant micelles, another approach [47] used a
reverse micelle, synthesizing nanoparticles of monoclinic VO2, orthorhombic
Ta2O5, and Sn and Nb oxides of unidentified structures on the inside of micelles
via LPD at 30
C.
Using polymer (usually latex or polystyrene) spheres of uniform size as
substrates for deposition of oxide films takes advantage of the low temperature of
these deposition processes [22, 48]. Nanocrystalline ZnO was produced on
sulfonate-functionalized polystyrene spheres. The polymer could be dissolved or
pyrolyzed away, leaving intact hollow ZnO shells. The effects of a wide variety of
surfactant and polyelectrolyte surface treatments of such spheres were investigated
using LPD of TiO2 (anatase) [49]. While the deposition was very sensitive to the
surface functionalization of the films, electrostatic interactions between the sub-
strate and the particles did not appear to play a decisive role in the film deposition.
An LPD route yielded films of β-FeOOH on polystyrene spheres [50]. Pyrolysis of
the spheres in vacuum at 400
C for 2 h produced hollow spheres of magnetic
Fe3O4. In a variant of this approach, polystyrene spheres were assembled to form a
template for deposition of a “reverse opal” of SnO2 via LPD [51]. After burnout of
the spheres, the resulting voids in the SnO2 were then infiltrated with Eu-doped
ZrO2.
The deposition of laminated multilayer films made of alternating oxide and
organic layers was investigated. This approach aims to replicate to some extent
the remarkable strength of biominerals such as nacre, whose structure consists of
14 Chemical Bath Deposition 333

crystalline layers of CaCO3 (aragonite) between thin protein-based layers compris-

ing approximately 5 vol% of the material. Laminated composites, consisting of
alternating layers of TiO2 120 nm thick and polyelectrolyte 25 nm thick were
produced [52]. In nanoindentation measurements, films with three pairs of such
layers on silicon showed hardness values 15 % higher than a liquid-deposited TiO2
film of the same thickness.
In similar work on ZnO/polyelectrolyte laminate films [53], the laminated films
were approximately 25 % harder. These polyelectrolyte layers consisted of poly
(styrene sulfonate), poly-L-glutamic acid and poly-L-lysine hydrobromide.

14.4 Process Control

In its simplest form, a CBD process involves a single isothermal immersion of a

substrate into a non-flowing liquid precursor of the desired film. Even if no external
changes are imposed on the system—e.g. no more reagents are added to the
deposition medium, the solution is not stirred or agitated, the temperature is not
changed—the important solution parameters that affect the deposition process are
far from static. In particular, once solid has begun to form, the supersaturation of the
solution begins to decrease, and eventually reaches a level at which nucleation of
new particles stops (although growth of existing particles may continue). The pH
may significantly change from the initial value, usually in a direction that slows
particle nucleation and growth. As solid nucleates and grows (on the substrate, in
the solution, or both), solid-solid interactions become more important: e.g. adjacent
particles may agglomerate via van der Waals or other interactions, causing contin-
uous changes in the number, size, and spatial distribution of solid particles. Overall,
for a single-immersion deposition, there is usually an “incubation” period during
which no film growth occurs, followed by a period of growth (which may exhibit a
rising growth rate followed by a declining growth rate), then cessation of growth
once supersaturation has dropped below a critical level.
Niesen and De Guire reviewed the growth rates and film thicknesses achieved by
aqueous liquid deposition processes such as CBD, SILAR, LPD and their
variations [2]. Typical growth rates for such processes are 200–1,500 nm/h with
maximum film thickness up to 1,000 nm. For SILAR, typical growth rates are less
than 1 nm/cycle, and ultimate film thicknesses are often lower than for other
chemical bath processes.
Sequential deposition, a concept integral to SILAR, has also been adapted to
other CBD techniques. It provides a simple way to overcome the “exhaustion” of
the deposition process when the supersaturation of the original solution drops to a
level too low to sustain further film growth. The substrate is simply removed from
its solution and inserted in a fresh aliquot of the same precursor. In principle, this
approach can lead to thicker films than single depositions and can be repeated
indefinitely to build up thick films.
334 M.R. De Guire et al.

Another approach for avoiding the continuous change in solution concentration

and pH is to monitor and adjust these parameters periodically or continuously to
maintain desired values. Automated electronic systems for maintaining constant pH
(“pH-stats”) are readily available for small- and large-scale depositions. Sensors are
commercially available for continuous measurement of the concentrations of some
metal ions in the deposition medium. Complete systems for monitoring and
maintaining solution parameters have been developed for the commercial deposi-
tion of CdS films for the photovoltaics industry, and these approaches could
undoubtedly be adapted to the deposition of oxide films.
When a reactant is added to a solution, spatial gradients in supersaturation will
occur. This can lead to inadvertent local precipitation and other inhomogeneities at
the site of the addition until the added substance is uniformly mixed into the
solution. One way of avoiding this situation, in solutions where a rise in pH can
be used to trigger the formation of the solid, is to add urea ((NH2)2CO) to the
solution before heating. In aqueous solutions at temperatures between ~40 and
~80
C, urea will decompose to form ammonia and carbon dioxide. The net effect is
a steady rise in pH, occurring uniformly throughout the solution.
A variant of CBD known as liquid flow deposition (LFD) is designed to reduce
both spatial nonuniformities and temporal changes in supersaturation. In LFD, the
reactant solution is flowed past the substrate at a controlled rate. It was first
developed in the late 1980s [54, 55] as a variation of ferrite plating. In LFD, the
reactants are replenished continuously, allowing more constant composition of
solution and more constant degree of supersaturation to be maintained. The used
precursor may be collected, reconstituted, and reused. The rate of flow of the
deposition medium past the substrate becomes an additional and easily controlled
variable for adjusting the deposition process. With appropriate adjustment of
solution parameters, LFD can be applied to any CBD technique (except perhaps
SILAR). Ferrites [54, 55], CdS, ZnO [2], SnO2 [56] and TiO2 [57] have been
deposited using LFD at constant and high growth rates. In contrast, ZrO2 films
did not grow significantly faster or thicker via LFD than via conventional CBD
[58]. Alternatively, by varying the flow rate and solution makeup during a deposi-
tion, LFD can be designed to vary the composition, growth rate, and microstructure
within a single film, as reported by Deki et al. [59].
Using a simple LFD apparatus to deposit SnO2 films (Fig. 14.7), Supothina
et al. [56, 60] explored the interplay of solution parameters ([Sn4+] and pH) with
chamber design and flow rate. Intermediate flow rates (2–3 mL min1) gave the
thickest films, while thinner or no films were obtained at higher and lower flow
rates. Their results indicate that, when film growth occurs by particle attachment,
maximum growth rates can be obtained by coupling the residence time of the
solution in the vicinity of the substrate to the incubation time for nucleation of
particles in the solution. The maximum growth rate (85 nm h1) and the maximum
film thickness (1 μm) were obtained when the deposition chamber was configured
to decrease the distance that particles would have to travel to reach the substrate
after being nucleated in the solution.
14 Chemical Bath Deposition 335

Fig. 14.7 Schematic illustration of an apparatus used for liquid flow deposition. A pump delivers
the precursor solution (which may be preheated or which may be heated in the deposition
chamber) to the substrate. After residing in the chamber for a time that depends on the flow rate,
the volume of the chamber, and configuration of the flow field, the precursor flows out of the tube
and may be collected, reconstituted, and reused [56, 60]

Boyle et al. [61, 62] reported a closed-loop LFD process for CdS films that
filters, recirculates, and replenishes the used solution, significantly reducing the
amount of (cadmium) waste.
Other variants of CBD use different strategies for initiating solid formation and
inducing film formation. These include photochemical deposition (in which light is
used to trigger formation of the solid phase) and deposition assisted by applied
electric or magnetic fields or by ultrasonic agitation. The review by Niesen and De
Guire [2] surveyed some of these techniques.
It is not always desirable to immerse an entire substrate in a CBD medium or to
expose both sides of a substrate to a surface functionalization procedure such as
those described in Sect. 14.3.2. In the deposition of SAMs on the electrodes of solid
oxide fuel cells by Tang et al. [43, 63] it was found that one step in the sulfonate
functionalization procedure had adverse effects on the cathode side of the cell. The
problem was overcome by placing a cotton pad on the anode side of the cell, cut to
the size and shape of the anode, and then carefully saturating the pad with the
reagent in question so that none seeped out onto the rest of the cell. It is likely that a
similar strategy could be implemented in general with CBD solutions if other parts
of the substrate must be protected from contact with the deposition medium.

14.5 Conclusions and Prospects

While CBD approaches offer great versatility with regard to deposition of oxide
films as discussed above, some of the limitations of these films should be kept in
mind. For example, it remains challenging to synthesize multicomponent materials
whose individual components precipitate at widely differing pH or temperature, or
when the choice of complexants for the metals is limited. In such cases,
non-aqueous solutions, e.g. using alcohols or other polar solvents for the metal
and chalcogenide precursors, may offer more precise control over the supersatura-
tion of the solution and therefore of the deposition rate. An extensive base of
336 M.R. De Guire et al.

experience can be tapped in developing such approaches. Much of the research on

sol-gel synthesis of oxide materials over the last few decades [64] has utilized
non-aqueous solvents to produce a wide range of technologically important oxide
materials. Such approaches would increase the cost, and could increase adverse
environmental impacts, of the process; no solvent is cheaper, nor more readily
available, biocompatible, and environmentally benign than water. Nevertheless,
there are many technologically important oxide materials, such as tin-doped indium
oxide or ferroelectric oxides such as barium titanate, that do not lend themselves to
purely aqueous CBD. For such materials, non-aqueous approaches represent a
promising strategy for CBD processing.
In the as-deposited state, the films may contain residual water and other
components from the precursor solution. They are often not completely
crystallized. As a result, the films often do not exhibit the same physical properties
as fully crystalline sintered materials. For example, the as-deposited films are
mechanically much softer than fired polycrystalline ceramics, with little abrasion
resistance. Dopants added to the film may not be in solid solution in the
as-deposited host oxide, so that the as-deposited films may not show the intended
optical properties or electrical conductivity. Many of these effects can be alleviated
by a subsequent heat treatment to fully crystallize the film, to incorporate the
dopants into solid solution, to form the desired compound (if necessary), and to
develop physical properties more typical of a polycrystalline oxide. Such a heat
treatment is likely to decompose any organic components, such as SAMs (which
have been shown to pyrolyze from under the overlying oxide CBD film at
temperatures between 200 and 400
C [65]) or polymer additives in the precursor
solution. If loss of the organic component is not deleterious to the film properties,
and if the substrate can withstand somewhat elevated temperatures, such a heat
treatment would not be a severe drawback, especially in light of the control over
film formation, low costs, and other advantages associated with CBD.
In light of these limitations, the most likely first applications of CBD oxide films
will not expose them to significant mechanical loads or wear. Examples include
single or multilayer optical coatings or catalytic or sensing layers that are protected
by harder materials such as glass or some other rigid support. The cerium oxide
coatings applied to solid oxide fuel cell anodes by Tang et al. [43, 63] survived up to
hundreds of hours of operation in the absence of direct mechanical impact or
abrasion. Significantly, however, microstructural changes occurring in the anodes
during operation, and which were implicated in cell failure, led also to disruption of
the coatings.
The interactions of organic molecules with inorganic surfaces promise some of
the most exciting new prospects for CBD films and broad opportunities for further
research. These include control over film growth and morphology as discussed in
Sects. 14.2.3 and 14.3.4, but also applications involving the adsorption, sensing,
patterning, or other manipulations of biological molecules and assemblies, from
various proteins, to pharmaceuticals, to DNA and entire cells. Organic-inorganic
surface interactions lie at the heart of many potential applications in biochemical
sensing, biomimetic materials synthesis, drug delivery, and biomedical devices.
14 Chemical Bath Deposition 337

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