Journal of Sol-Gel Science and Technology 6,7-S (1996)

@ 1996 Kluwer Academic Publishers. Manufactured in The Netherlands.

Invited Review
“Sol-Gel” Preparation of High Temperature Superconducting Oxides*

MASATO KAKIHANA
Research Laboratory of Engineering Materials, Tokyo Institute of Technology, Nagatsuta 4259,
Midori-ku, Yokohama 226, Japan

Abstract. This review article focuses on the sol-gel preparation of high temperature superconducting oxides
wherein different classesof gel technologies were utilized. These involve: 1) the sol-gel route based upon hydrolysis-
condensation of metal-alkoxides, 2) the gelation route based upon concentration of aqueous solutions involving
metal-chelates, often called as “chelate gel” or “amorphous chelate” route, and 3) the organic polymeric gel route.
This paper reviews the current status of these sol-gel processes, and illustrates the underlying chemistry involved
in each sol-gel technology. It is demonstrated that the chemical homogeneity of the gel is often disturbed by the
differences in the chemistries of the cations. Prior to gelation the starting precursor solution containing various
forms of metal-complexes must be chemically modified to overcome this problem. Illustration of a variety of
strategies for success in obtaining a homogeneous multicomponent gel with no precipitation is focal point of this
review article.

Keywords: sol-gel method, high temperature superconducting oxides, multicomponent gel, chemical homogene-
ity, metal alkoxides, amorphous chelate gel, organic polymeric gel, polymerized complex method

1. Introduction superconducting oxides, as well as their technologi-

The discovery of the new class of high-temperature
copper-based superconducting oxides has stimulated
intensive scientific investigations aiming at elucidat-
ing the origin of the superconductivity at high tem-
peratures and at characterizing the new materials by
numerous physical measurements. Clearly the un-
derstanding of the unique properties of copper-based
cal application, depends crucially upon composition,
homogeneity and microstructure, and thereby upon the
progress of the synthetic method. From this viewpoint,
several review articles on the synthesis of high tem-
perature superconducting oxides have appeared [l-S].
However, the current status of the sol-gel preparation
of these oxides is not well documented. Thus I present
a review of the sol-gel processing of high temperature

*strictly speaking, sol-gel must include processing, in which asol (of- gels) and (2) a network formation route based upon destabilization of
ten defined as a suspension of small but discrete particles remaining dispersed colloidal particles in a liqurd medium (particulate gels).
dispersed in a liquid phase) undergoes a transition to a gel charac- According to the rigorous definition of gel, some solution processes,
terized by an infinite three-dimensional network structure spreading started from metal-organics (other than metal alkoxide), would not
uniformly throughout the liquid medium. Thus a gel has to be dis- be classified into a true sol-gel process. In this paper, however, the
tinguished either from a viscous liquid of one continuous phase or term “sol-gel” is broadly used to describe the preparation of inorganic
from a gelatinous precipitate in which a liquid phase is not involved materials by a variety of solutron routes. A chemical process which
in the solid network. It is generally accepted that a true gel can be can produce a solid matter or a highly viscous hquid matter wrth no
prepared in two major chemical ways: (1) a molecular route based precrpitation is treated as the so-culled “sol-gel” process, even when
upon hydrolysis and polycondensation of metal alkoxides (alkoxide rt IS likely that the system contains no infinite rigid network
8 Kakihana
superconducting oxides, and describe how chemical
homogeneity can be attained on an atomic scale in a
multi-component system using sol-gel routes. The sol-
gel synthesis of oxide materials is a multistep process
which involves conversion of a precursor solution into
a sol or a gel and subsequently transition of the gel to
an oxide compound. The chemical homogeneity with
respect to distribution of cations in the gel often de-
termines the compositional homogeneity of the final
oxide powder. It is therefore crucial to design a suit-
able precursor solution which enables the formation of
a homogeneous multicomponent gel without any phase
segregation during the sol-gel transition. For this rea-
son, a large part of this review article is devoted to the
illustration of the chemical scheme to obtain a clear gel
instead of precipitation. In addition special emphasis is
given to the discussion of advantages of the sol-gel pro-
cessover the conventional preparation methods such as
solid-state reaction and coprecipitation routes.
This review article is divided into 4 parts:
1. Characteristics for the more widely used prepa-
ration methods including the solid-state reaction
and coprecipitation routes are briefly described in
Section 2, with a view to clarifying inherent prob-
lems with these methods in production of homo-
geneous and stoichiometric materials and thereby
to stressing the importance of the sol-gel process-
ing in the field of high temperature superconducting
oxides as described in detail in Sections 3 and 4.
2. In Section 3, I try to classify the sol-gel process-
ing into several groups, those including processes
based upon destabilization of colloid disper-
sion, hydrolysis-polycondensation of organometal-
lit compounds, and formation of organic polymeric
glass. This review focuses only on the latter two
routes, and their fundamental principles and under-
lying chemistries are given in a tutorial way.
3. In each case, some relevant examples of high tem-
perature superconducting oxides for which the sol-
gel processing has been applied are discussed in
Section 4. This section is devoted to illustrate how
chemical considerations have been done so far in
obtaining a homogeneous multicomponent gel with
no precipitation during the gelation process.
4. Finally, some chemistry-related unresolved issues
are summarized as concluding remarks in Section 5.
Although it was impossible for this review to cover
all of the current works on the sol-gel preparation
of high temperature superconducting oxides, I have
included a rather extensive list of citations for the
convenience of readers. It is my hope that this review
can stimulate ceramists who focus their attention on the
compositional homogeneity of oxides with very com-
plicated compositions such as high temperature super-
conducting oxides and other technologically important
multicomponent oxides.
2. Conventional Routes
2.1. Solid-State Reaction Route
The vast majority of the powder synthesis of high
temperature superconducting oxides to date has been
carried out using the traditional “solid-state reaction
route” [8] in which appropriate metal oxides or car-
bonates (or other suitable salts) are mixed, often being
ball milled to enhance mixing and to reduce particle
sizes, and then the mixture is fired at high tempera-
ture to allow interdiffusion of the cations. As the solid-
state reaction relies on interdiffusion of the cations
characterized by the slow kinetics, the degree of mixing
and powder particle sizes are of particular importance.
Usually the starting mixture is inhomogeneous and is
comprised of coarse particles typically in the range of
l-10 pm. As schematically shown in figure 1, the
solid state reaction occurs initially at the points of con-
tact between the components A0 and BOz and contin-
ues successively by interdiffusion of the constituents
ions through the product phase ABOs. Initial reaction
is prompt because of short diffusion paths, but fur-
ther reaction goes slower as ions must diffuse longer
distances with growth of the product layer. In many
cases,a number of unwanted phases such as AzB04 and
AB20s may form through solid state reactions between
the end product ABOs and A0 or Bog. This necessi-
tates repeated cycles of grinding and firing and longer
period of heating to complete the reaction. However,
even after multiple intermittent grinding steps, pow-
ders produced through the solid-state reaction method
have still several drawbacks which may be notified by
poor sintering behavior, non-uniformity of particle size
and shape, lack of reproducibility, multiphase charac-
ter, and loss of stoichiometry due to volatilization of a
reactant at high temperatures. The last item of these
problems is particularly of problem in Pb- and Tl-based
high temperature superconducting oxides because of
the easy volatility of PbO or T120s; e.g. severe mass
loss of thallium occurs at temperatures near its melting
point of 717°C [9].
 “Sol-Gel” Preparation of High Temperature Superconducting Oxides
1Solid-State
calcination
-2-3 pm
Figure I. Schematic illustration of solid state reactions between A0 and BO2 with the average particle size of 2-3 mm:
A0 + BO2 + AB03, relies on interdiffusion of the cations, a large part of A0 and BO2 remain unreacted.
2.2. Coprecipitation Route
There have been a rapid growth in the interest in alter-
native wet chemical techniques whose goal is to obtain
a better homogeneous precursor material with well in-
terspersed elements before heat treatments at high tem-
peratures. The “coprecipitation method’ is one of the
known wet-chemical routes most commonly used in the
synthesis of high temperature superconducting oxides
[8]. The coprecipitation process involves the separa-
tion of a solid containing various ionic species from
a solution phase, and it can be conveniently classified
into three categories as schematically shown in figure 2.
Of ideal is that a quantitative and simultaneous precip-
itation of all the cations occurs without segregation of
any particular constituents in the precipitates to form a
completely mixed-metal precursor (figure 2( 1)). How-
ever, this is a very rare situation in most of solution
systems containing more than one metal ion, and ho-
mogeneous coprecipitation with respect to metal ions
at atomic level is almost impossible in solution precur-
sors for high temperature superconducting oxides with
more than two or even three metal ions. Differences
in solubility between the various precipitating phases
strongly affect the precipitation kinetics of each metal
ion component, which causes changes in stoichiometry
of the precipitate with reaction time. Thus the result-
ing precipitate should be considered as a heterogeneous
mixture of fine particles; the composition of each par-
ticle with respect to metal ions differing from one to
9
Reaction Route 1
unreacted
2
ABO,
Since the reactlon,
another (figure 2(2)). The problem mentioned above
can be reduced by introducing two or more precipitat-
ing agents that renders all the cations really insoluble
in the mother liquid . Another way to promote simul-
taneous coprecipitation of the various species is to use
multi-functional organic compounds such as oxalates,
tartarates and citrates, as they can coordinate with more
than one metal ion. The use of a well-known Ba/Ti dou-
ble oxalate coprecipitate (BaTiO(Cz0&.4HzO) in the
synthesis of BaTiOs is a case in point [ 10, 111. De-
spite the heterogeneous nature of the precipitates, the
coprecipitation process offers a solid powder precur-
sor comprising of fine particles typically in the range
between IO@-500 nm, that greatly reduces the diffu-
sion distances compared with those required for the
solid-state reaction route, resulting in shorter reaction
times or lower reaction temperatures. The third pos-
sible but highly specific route is the direct precipita-
tion of a heterometallic complex of a fixed stoichiom-
etry already formed in a mother liquid, that can min-
imize segregation of the individual component during
the precipitation (figure 2(3)). An example of this ap-
proach involves the synthesis of BaTiOs, where a het-
erometallic (Ba, Ti)-citric acid complex forming in a
weakly acidic solution at pH - 6.0 has been precipi-
tated upon decreasing the pH of the solution below 2.6.
The isolated heterometallic complex has the empiri-
cal formula of BaTi(CeH607)3.6HzO, and it was com-
pletely converted to BaTiOs upon heating at 650°C in
air [ 121. Examples of the synthesis of high temperature
 10 Kakihana

i Coprecipitation Route i
precipitants
(NH40H etc.) i

Oe_9. e_e.o 9 (1) o

9 o o^e 9 >- o
o~ ; o o
O o m o O e Oe o
%" %§ %~ %~ %, %, %"
9 o o~ o o
perfect ~5nm
coprecipitation

(2) o
9
o
o
o
r
e
o o

differential --100 nm
heterometallic I precipitation
complex

(3)
r

~lOnm
control of pH
& temperature crystallization
Figure2. Schematicillustrationofvarioustypesofprecipitations: (1) An ideal case where two different cations are simultaneously precipitated
to form a perfectly mixed coprecipitate precursor. (2) An ordinary case where two cations have different solubilities and exhibit different kinetics
to form a heterogeneously mixed precipitate. Because of the difference in the solubilities, the overall stoichiometry of the precipitate is deviated
from the initial value. (3) Crystallization of heterometallic complex with a desired stioichiometry from a solution precursor.
 “Sol-Gel” Preparation of High Temperature Superconducting Oxides
superconducting oxides by the coprecipitation method
can be found in the recent review article [8].
3. Sol-Gel Routes
The fact that the number of constituent ions is large
in high temperature superconducting oxides, 3 for
Y based superconductors, 4 for Bi- and Tl-based
superconductors, and sometimes more than 4 for their
solid solutions, amplifies the above problems with the
solid-state reaction and coprecipitation methods. As a
consequence, ceramic superconductors with the same
overall composition often exhibit somewhat different
properties, reflecting small differences in phase purity
and compositional homogeneity. Higher quality mate-
rials based on even improved control of the chemistry
and powder morphology are clearly needed to enable a
better understanding of the fundamental physics of the
new superconducting compounds. The sol-gel process
has the potential advantage over the other methods not
only for achieving homogeneous mixing of the com-
ponent cations on atomic scale, but also for forming
films or fibers from gels which are of technological
importance.
There are essentially three different kinds of sol-gel
or gel technology: a) colloidal sol-gel (3.1), b) inor-
ganic polymeric gel derived from organometallic com-
pounds (3.2), and c) gel routes involving formation of
organic polymeric glass (3.3). The primary goal in
all these sol-gel processes is the preparation of a ho-
mogeneous precursor solution from which a semi-rigid
gel can be isolated with an atomic level homogeneity.
The main purpose of this section is to illustrate the
principles and underlying chemistry involved in each
method, required for a better understanding of the sol-
gel processing.
3.1. Colloidal Sol-Gel Route
The first method involves the dispersion of colloid par-
ticles with diameters typically of l-100 nm in a liquid
medium to form a sol and then the fluid sol is converted
to a gel [ 131. The gelation in the colloidal route is con-
trolled by electrostatic or steric interactions between
the colloidal particles in the sol, and a general overview
of the colloidal processing is well documented in some
recent publications [14-191. A mixture of colloidal
particles (most frequently hydroxides or oxides) which
coprecipitate and cannot be dispersed as sols should
11
not be classified within the sol-gel route. The col-
loidal sol-gel method is sometimes called “a physical
gel route” compared with “a chemical gel route” ac-
cording to Colomban [20]. This is because interparticle
interactions in fluid sols are dominated by physical
forces on surfaces such as van der Waals forces, electro-
static forces and Brownian motion. Chemical effects
are limited generally to surface and hydrogen bonding
phenomenon. Note however that an intermediate or
hybrid process of two extremes of the “physical” and
“chemical” gel formation is possible. This review pa-
per will be restricted to the discussion of the chemical
gel routes through either inorganic or organic polymer-
ization as shown in the next two subsections.
3.2. Inorganic Polymeric Gel from Organometallic
Compounds
The second method involves the dissolution of
organometallic compounds in a suitable solvent, fol-
lowed by a series of chemical reactions of hydroly-
sis, condensation and polymerization to produce a gel
with a continuous inorganic network. Inorganic poly-
meric oxide gels are made basically in two ways either
from metal alkoxides stabilized only in water-free or-
ganic medium or from metal-chelates stabilized even
in aqueous solutions. The hydrolysis is readily initi-
ated upon adding water in the former, while in the lat-
ter the hydrolysis process, which is much slower than
those for metal alkoxides, is promoted upon the evap-
oration of the water. In this section, underlying chem-
istry involved in these two sol-gel methods is briefly
overviewed.
3.2.1. Sol-Gel Route Based upon Hydrolysis of Metal
Alkoxides. Metal alkoxides have the general formula
M(OR), where M is a metal ion and R is an alkyl group.
On addition of water, the metal alkoxides readily hy-
drolyze as represented by Eq. (1):
M(OR), + xHzO --+ M(OH),(OR),-, + xROH. (1)
Hydrolysis is followed by condensation to form
-M-O-M- bonds via either dehydration or deal-
coholation as described in Eqs. (2) and (3), respec-
tively:
(a) dehydration:
-M-OH + HO-M- + -M-O-M- + HZ0
(2)
12 Kakihana
(b) dealcoholation:
-M-OH + RO-M-
+ -M-O-M- + ROH.
(3)
In this manner, inorganic polymeric oxide networks
are built up progressively. The hydrolysis, conden-
sation and polymerization reactions are governed by
several factors, including the molar ratio of water to
alkoxides, choice of solvents, temperature and pH (or
concentration of acid or base catalysts). By suitable ad-
justment of these factors, either linear polymeric gel or
more crosslinked polymeric gel can be formed [21,22].
Partlow and Yoldas [23] have suggested that a gel can
be created in two ways. In the first case, as the concen-
tration of dispersed polymeric species increases upon
removal of the solvent, the probability of crosslinking
between the polymeric chains increases. When suf-
ficient crosslinking occurs, a sol-gel transition is ob-
served, beyond which the viscosity increases abruptly.
Aging of the solution, which allows the hydrolysis and
condensation reactions to proceed, is another way to
promote the polymerization reaction often catalyzed
by acid or base. A network is built up as the poly-
merization reaction continues. Thus polymeric gels,
which shrink within the mother liquid, are formed. The
hydrolysis, condensation and polymerization of metal
alkoxides as well as their synthesis and structural prop-
erties have been extensively reviewed in recent years
[24-371.
In the preparation of multicomponent gels compris-
ing of more than one type of metal ion, the situation be-
comes much more complicated. For clarity, I consider
a multicomponent gel containing two different metal
ions, A2+ and B4+, with the overall stoichiometry A/B
= 1. The first step of the preparation involves the mix-
ing of the two different metal alkoxides, A(OR)z and
B(OR’)4, in suitable organic solvents to make a precur-
sor solution. This is followed by the addition of water
to obtain a gel. The degree of chemical homogeneity
of the resulting gel is strongly affected not only by the
mixing level of different alkoxides in the precursor so-
lution, but also by reactivity of each alkoxide species
towards water. The former is closely connected with
the chemical reactivity between the two metal alkox-
ides, which results in formation of a number of new
chemical species in addition to the initial metal alkox-
ides. Three possible changes in microscopic compo-
sition of the precursor solution [24] are schematically
illustrated in figure 3.
In the first case (figure 3(l)), where no reaction be-
tween the two metal alkoxides occurs, chemical ho-
mogeneity of the resulting gel will strongly depend
upon the reactivity of the individual metal alkoxides
towards water. The fact that the hydrolysis and
condensation rates of different metal alkoxides are
generally different results in formation of different
sized clusters in sol, which gives rise to inhomo-
geneity of the resulting gel. Difficulties then occur
when using metal alkoxides that have very different
rates of the hydrolysis, such as those for rare-earth
alkoxides and Cu-alkoxides, where the former are
much more readily hydrolyzed than the latter even
by very small amount of water [38]. Consequently,
segregation of rare-earth elements can occur during
the hydrolysis-condensation-polymerization process,
which in turn makes it difficult to prepare homoge-
neously mixed rare-earth and Cu oxides of the re-
quired stoichiometry. This type of problem can be
overcome by using chemically modified alkoxides to
control the hydrolysis rates of the highly reactive alkox-
ides. Complexation is a popular method of mod-
ifying the original alkoxides, and carboxylic acids
or #l-diketones are most frequently used as the ad-
ditional modifying ligands. For instance, replace-
ment of two of the alkoxide ligands in Zr(OCsH7)4
and Ti(OCH(CHs)2)4 by acetic acids slows the rate
of hydrolysis, and homogeneous and transparent ZrO:!
or TiOz gels are obtained in the presence of acetic
acid [26, 31, 39, 401. Partial hydrolysis of one of
metal alkoxides that hydrolyzes at the slowest rate
prior to mixing with other alkoxides is another way to
overcome the problem of mismatched hydrolysis rates
[21,41,42].
In the second case (figure 3(2)), the two parent metal
alkoxides react with each other stoichiometrically to
form a heterometallic alkoxide with exactly the same
A/B ratio as that of the final ceramic according to the
following reaction:
A(OR)z f B(OR’)4 --+ AB(OR)z(OR’)d. (4)
The heterometallic alkoxide thus formed can then be
hydrolyzed with a controlled amount of water as if it
is a single molecule rather than the individual alkox-
ide mixture, thereby favoring the formation of mixed-
metal oxygen bonds of -A-O-B- between the
two metals. Subsequent polymerization may yield a
multicomponent gel having the same metal stoichiom-
etry as the initial heterometallic alkoxide molecule.
 “Sol-Gel” Preparation of High Temperature Superconducting Oxides 13

1 Metal-alkoxide route [

WR), wow,
000 0 0
0000
000 0
00 OOo

000
O 0 +
0
000
00 000

no reaction AB-alkoxide mixtures of A-,

B-, AB-, AB,-,
A(OR),+B(OR’), AB(OR),WW, A,B-alkoxides

1 -I- H,O
1+ H,O
1 + H,O

differential homogeneous heterogeneous

hydrolysis -A-O-B- gel gel mixtures

Figure 3. Effect of precursor characteristics on homogeneity of alkoxide-derived multicomponent gels: (1) A case where no reaction between
A(OR)z and B(OR’)4 occurs, but the rate of hydrolysis and condensation is much larger in B(OR’)d than in A(OR)2 resulting in segregation of
the B component. (2) A case where a heterometallic (double) alkoxide forms, resulting in homogeneously mixed -A-O-B- gel. (3) A
case where a variety of reactions occur to form a mixture of molecular species with different stoichiometries, causing a local heterogeneity in
the resulting gel.
14 Kakihana
However, careful search for suitable conditions of
the hydrolysis must be carried out in order to avoid
preferential precipitation of one part of alkoxides and
modification of the metal stoichiometry during the hy-
drolysis. Successful examples of this approach in-
volve the synthesis of BaTiOs [43, 441 and LiNbOs
[45-48], where the heterometallic alkoxides by the sto-
ichiometric reactions between the individual alkoxides
are hydrolyzed and polymerized to form atomistically
homogeneous multicomponent gels. This molecular
route results in powders having much higher purities
and compositional homogeneity and requiring lower
sintering temperatures than those prepared by other
wet chemical methods. A summary of available het-
erometallic alkoxides was provided by Mehrotra [49],
and more recently an extensive review on the synthe-
sis, structures and reactivity of heterometallic alkox-
ides was given by Caulton and Hubert-Pfalzgraf [34].
In the third case (figure 3(3)), where a mixture of
molecular species with different metal stoichiometries
is formed, local inhomogeneity already exists in the
precursor solution. Thus a gel created upon adding
water may exhibit heterogeneity depending upon the
degree of mixing of the different metal atoms and the
relative rates of hydrolysis of the individual molecular
species formed in the initial precursor solution. This
results in the need to process the gel at higher temper-
atures in order to attain compositional homogeneity.
Finally it should be mentioned here that it appears
to be frequently confused in the literature concerning
distinction between a polymeric gel with an infinite
network and a sol-derived precipitate. The differen-
tial precipitate solubilities and precipitation kinetics
are factors that can lead to chemical and phase hetero-
geneities in the derived precipitate. In case where any
phase separation or precipitation occurs upon adding
water in a mixed solution of metal alkoxides, the pro-
cess should be classified within the coprecipitation
route rather than the sol-gel route, although the pre-
cipitates in some instances could be genuine solid so-
lutions [8].
3.2.2. Metal-Chelute Gel (or Amorphous Metal-
Chelute) Route. Another way to trap the randomness
of the solution state is to use precursor solutions that
can be converted to an amorphous glassy state when
the solvent is removed. Note however that concen-
tration of solutions containing simple inorganic metal
salts such as nitrates without organic complexants does
not allow for attaining a good homogeneity at atomic
scale. A heterogeneous mixture of precipitates as the
original salt form or as colloidal hydroxides is gener-
ally obtained from such solution systems upon evapo-
ration of the solvent. The difficulty in constructing gel
networks from these inorganic metal salts precludes
this simple way from being classified into the sol-gel
route. The use of suitable organic acids chelating metal
ions can overcome this problem. The basic idea be-
hind the metal-chelate gel formation method is to re-
duce the concentration of free-metal ions (mostly hy-
drated in aqueous solutions) in the precursor solution
by the formation of soluble chelate complexes. From
this point of view strong chelating agents such as cit-
ric acid and ethylene-diamine-tetra-acetic acid (EDTA)
are preferably used in the synthesis of high temperature
superconducting oxides, which greatly expands a range
of experimental conditions such as pH of the solution,
temperature, and metal concentrations where gelation
can occur upon evaporation of the solvent.
In spite of the fact that this is certainly the simplest
sol-gel method and hence most commonly used, only
little is known about the basic chemistry involved in the
process. Let me briefly describe the chemistry of inor-
ganic salts in aqueous solutions before the role of the
organic complexants is discussed. The aqueous chem-
istry of inorganic salts is quite complicated owing to
the occurrence of hydrolysis and condensation reac-
tions which leads to formation of numerous molecular
species. Hydrolysis of metal ions in aqueous solutions
is well-described in a book by Baes and Meswer [50],
and more recently the so-called “partial charge model”
developed by Livage et al. [31] has been applied suc-
cessfully to describe the chemical reactions involved
in the sol-gel process and provides a useful means for
inorganic polymerization reactions. The cations of a
metal M solvated by water molecules [M(H20)n]‘+
show a strong tendency to release protons (in equiva-
lence with the hydrolysis) while preserving their coor-
dination number n, as described in the following type
of deprotonated reaction with u ( y f 2:
[M(H~O>nl”+ + Y&O
f, [MO,(OH),-~,(HzO),-,+,l~z-y~+ yH@+. (5)
An increase of the pH value favors the forward reac-
tions in Eq. (5). Noteworthy in Eq. (5) is that the cations
can be linked by three kinds of ligands depending
upon the degree of the hydrolysis. These include aquo
ligands (HzO), hydroxo ligands (OH-) and 0x0 ligands
(02-), where the latter two ligands are those generated
 “Sol-Gel” Preparation of High Temperature Superconducting Oxides 15

which occurs typically with oxo-hydroxo complexes

[MO, (OH),-,]‘“+“-“- (X < n), leads to the forma-
tion of an 0x0 bridge M-O-M. These condensation
reactions can be followed by successive associations,
leading to polymerization. In many cases, however,
the hydrolysis reactions are relatively fast compared
with the reactions forming polynuclear species. An in-
crease of the pH value may thus frequently give rise
to the formation of precipitates such as a solid hy-
droxide [M(OH),] before gelation occurs. Gels appear
to be preferentially formed when both the hydrolysis
and condensation rates are not too fast, otherwise solid
hydroxides [M(OH),], oxides [MO,,21 or gelatinous
precipitates [M0,,2(0H),-,.yH20] may be obtained
instead of stable gels. A key to successful formation
of stable gels is to slow down the rate of hydrolysis
of aquo or aquo-hydroxo complexes and to prepare a
stable precursor solution even when the pH of the so-
lution is increased. This can be achieved by introduc-
I I I I I I I ing organic complexants into the precursor solution to
J
weaken the hydrolysis of coordinated water molecules,
0 2 4 6 6 10 12 14
as described below.
PH
Replacement of coordinated water molecules in
F&m 4. Charge-pH diagram [31, 5 I, 521 illustrating the exis- an aquo metal species by organic complexants A”-
tence of three possible water related Iigands: “oxo”, “hydroxo” and (Eq. (6)) leads to a new precursor whose chemical re-
“aqua”
activity can be noticeably modified:

[M(H20),]“+ + aA”-
as the consequence of release of one and two protons,
respectively, from the mother aquo (H20) ligand. Im- t, [M(H20),(A),]cZ-Um) + (n - w)H20 (6)
portant factors determining the degree of the hydrolysis
include: 1) the formal charge z of the cation Mz+, and 2) where n > w and (n - w) = ha. h is the number of the
pH of the solution. The so-called “charge-pH” diagram coordinate bonds formed between the metal M and any
(figure 4) gives a rough formation diagram consisting atoms involved in one ligand A; i.e. ligands with h = 1,
of three domains distinguished with “Hz~“, “OH-” 2, and 3 are sometimes called monodentate, bidentate
and “02-“, in each of which “aquo (HzO)“, “hydroxo and tridentate ligands, respectively. An intention of the
(OH-)” and “0x0 (02-)” complexes are dominantly complexation of metal cations is to prevent the rapid
formed, respectively [31, 51, 521. For instance, lower hydrolysis of the coordinated water molecules in the
valent cations (z F +2) may form predominantly following deprotonated reaction:
aquo complexes below pH < 10, higher valent cations
(z 2 +7) form mostly 0x0 complexes over the whole [M(H20),(A),]‘Z-Um’ + Hz0
range of pH, and tetravalent cations (Z = +4) give rise
to a number of possible species such as aquo-hydroxo, tf [M(OH)(H20),-I(A),]cz-0m-‘) + HsO+. (7)
hydroxo, and hydroxo-oxo complexes depending upon
pH of the solution. A typical example of this concern can be seen in the
Condensation of the hydrolyzed species can occur hydrolysis of [Fe(H20)6]‘+ species and its complexed
via “olation” or “oxolation”. “Olation”, which oc- species by EDTA4- (ethylene diamine tetraacetic acid
curs typically with hydroxo-aqua complexes [M(OH), = [(OOCCH2)2N-CH2-CH2- N(CH2COO)2]4-)
(H20)n-x](z-x)+ (x < n), leads to the formation [31], where the equilibrium constant for the hydrolysis
of a hydroxo bridge M-OH-M, while “oxolation”, of the latter EDTA species is quite drastically lowered
16 Kakihana

by a factor of 1O22when compared with that of the the metal as

species before the complexation [53,54]:
a~(0H-j = (W+l + [M(OH)Z-ll + [M(oH);-2]
[Fe(H2O)d”+ + H20 + . . . + [M(oH);-“1 + ~[Mz(OH)F-~]
* [Fe(OH)(H20)d2- + H30+ + . . . + p[Mp(OH)l”“-“‘])/[M’+]. (11)
with Kh = 10-s (8)
oM(on-) can be calculated using the stability constants
[Fe(H20)2EDTA]- + Hz0 Ki and Kj,k for the following complex formation reac-
tions:
+ [Fe(OH)(H20)EDTA12- + HsO+

with Kh = 10-25. (9) Mz+ + iH20 t, [M(OH)i]‘-’ + iH+ (12)

The positive partial charge on the protons of the with

coordinated water molecules, S(H), that can be de-
duced from the “Partial Charge Model”, is decreased Kj = [M(OH)Jz-‘[H+]‘/[MZ+]
from +0.34 to +0.20 on going from [Fe(H20),#+ to
[Fe(H20)2EDTA]- [31]. The lower positive charge (i = 1,2,...,n) (13)
of 6(H) for [Fe(H20)zEDTA]- species means that the
deprotonation of the coordinated water molecules is and
less probable, and therefore is able to explain why
the hydrolysis is depressed by the EDTA complexa- jM”+ + kH20 ++ [Mj(OH),](Zj-k) + kH+ (14)
tion as is consistent with the equilibrium constant. It is
thus anticipated that the EDTA modified precursor so- with
lution does not form hydroxide precipitates even at very
high pH. Condensations between the non-hydrolyzed
Kj,k = [MI(OH)y-k)][H+]k/[MZ+]j
species and the partial hydrolysis species and the sub-
sequent cluster formation may occur upon evaporation (j = 2,3,. . . ,p and k = 2,3,. . . , q). (15)
of the solvent, although an exact description of what
is happening as the solution is concentrated is almost When i = z in Eqs.( 12) and (13), we have
impossible. From a practical point of view, any pre-
cipitation must be avoided during the concentration as Mz+ + zH20 t, M(OH), + zH+, (16)
it destroys the homogeneity maintained in the initial
solution, As shown below the so-called pM’-pH dia- with the stability constant written as
grams [55, 561 provide a useful guide for specifying
experimental conditions where no precipitation may
K, = [M(OH),][H+]Z/[MZ+]. (17)
occur during the course of the concentration.
When the stability constants for complex formation
reactions that can be involved in a given aqueous so- A precipitate is formed, when the concentration of the
lution system and the solubility products for insolu- species M(OH), in Eq. (16) is beyond a limiting con-
ble species in the solution are known, the pM’-pH centration (c-):
diagram can be constructed [55, 561, where pM’ =
- log,c[M’]/(mol . dm-s). [M’] is related to the con- C max= [M(OH),I,,,. (18)
centration of free metal ion [M”+] through Ringborn’s
side-reactions coefficient c!M(x) [57]: The solubility product K,, giving a maximum concen-
tration of Mz+, [M”+]-, below which no precipitate
[M’] = aM(x) * [M”+]. (10) occurs at a given pH, is then written using Eqs. (17)
and (18) as
When X = OH- in Eq. (lo), aM(on-) is simply defined
by taking into account all possible species containing [M”+l,,x/[H+l” = [M(OH),l,,/K, = K,,. (19)
 “Sol-Gel” Preparation of High Temperature Superconducting Oxides 17

(a) [Fe3’-H,OI
8,

’ I I I I I,, , , , , I
0 2 4 6 6 10 12
PH

6- excess EDTA
- (mol.dmJ)
B:104
g 4- c: 1 oa
D: lOa
E: 1 O-’
2-

0 1 u ’ I 1 I I , , F
1 35:/" $5'2
0 2 4 6 8 10 12
PH
Figure 5. The pFe(III)‘-pH diagram [%I. The line A in (a) IS the precipitation borderline in Fe3+-H20 systems. The borderhnes B, C, D and
E in (b) correspond to excess EDTA concentrations of 10m4, 10P3, 10m2 and IO-’ mol. dme3, respectively. For details, see text.

Substitution of [Mz+lmax in Eq. (19) by [M&J
CZ~(~~-)derived from Eq. (10) leads to a formula for
the borderline of the precipitation region:
W’l max= KS,* ($,(OH-)* D-I+]“.
An example of pM’-pH diagrams derived from Eq. (20)
is shown in figure 5(a) for a Fe’+ aqueous solution
system without organic complexants, where curve A
represents the borderline of the hydroxide precipita-
tion [55]. It is apparent that conditions for which no
precipitation occurs are limited mostly to very low pH
regions. In order to enlarge conditions for which the
solution is stable, a complexing agent such as EDTA
is usually added to the solution. pM’-pH diagrams
are also available for such aqueous solution systems
containing other complexing species besides OH-. A
number of new species having a wide range of com-
positions may form in the presence of a ligand Am-,
which can be described as a combination of Mz+, H+,
OH- and Am- depending upon the concentration of
(20) both the metal and the ligand as well as the pH of the
solution. When EDTA (= HdL) is used as a complex-
ing agent, complexes formed can be confined to 1: 1
species such as
MLZ-4, MHLZ-‘, MH2LZ-*, . . ,
ML(OH)Z-5, ML(OH)“,-6,. .. (21)
In this case, c~M(ou-,L) is used instead of ~~(ou-) in
Eq. (20) in order to give the general formula for the
borderline of hydroxide precipitation formation in the
18 Kakihana
metal-EDTA solution system:
W’l max= Ks, . aM(OH-.L) . W+l”,
where
aM(OH-.L) = aM(OH-)
+ ([ML”-4] + [MHL’-“1
+ [MH&-~] + . . . + [ML(oH)“-5]
+ [ML(oH);-(j] + . . .)/[M~+].
Turning back to the aqueous solution system contain-
ing Fe”+, pM’-pH diagrams in the presence of EDTA
are shown in figure 5(b) [55]. Curves B, C, D and E
represent the borderline of hydroxide precipitation for
excess EDTA concentrations of 10e4, lo-“, 10V2 and
10-l mol. dm-s , respectively, and have been calcu-
lated with the known stability constants [55, 601. The
precipitation region becomes narrow as the concentra-
tion of EDTA is increased. The importance of this
diagram in the sol-gel processing is that a given pre-
cursor solution can be represented by a point P and that
a locus is drawn by P as the solution is concentrated
[58]. Suppose two kinds of precursor solutions repre-
sented by points PO at (pH, p[Fe”+]) = (6, 2) and Qe
at (8, 2) in figure 5(b). When only waters are evapo-
rated during the concentration, [Fe’] and [H+] change
by the same factor. Upon evaporation of waters, points
Pa and Qa then shift along a 135” and 45” line, re-
spectively, towards lower values of p[Fe’]; points Pi
and Qi correspond to lo-fold concentrations of the PO
and Qo solutions, respectively. The 135” line of the PO
precursor solution does not penetrate the precipitation
region, while the 45” line of the Qe precursor solu-
tion crosses the borderlines of the precipitation. In the
latter case the locus of QO deeply penetrates the pre-
cipitation region when the EDTA concentration is low;
thus hydroxide precipitation being able to occur before
the solution gels. In order to prevent the unwanted
hydroxide formation, the concentration of EDTA must
therefore be as high as possible as far as the QO pre-
cursor solution is used. When ammonia is used as an
agent for adjusting pH, the locus of QO can differ from
the 45” line. During the concentration of the solu-
tion, some ammonia will evolve together with waters
which thrusts the locus of Qe towards somewhat lower
pH values as indicated by the dotted line. Under a
certain circumstance, the locus of Qa remains outside
the precipitation region, and no hydroxide precipita-
tion may be formed until the solution becomes a gel.
Specification of experimental conditions for a precur-
sor solution containing more than one kind of metal can
(22) be done with the aid of the respective pM’-pH diagrams
for different metal ions, in a way similar to what has
been explained for the Fe3+-EDTA aqueous solution
system in figure 5(b). This will be given later more
in detail in Section 4.2.4. It should finally be pointed
out that a matter of kinetics and possible precipitations
other than hydroxides are not taken into considerations
in constructing pM’-pH diagrams. This might bring
(23) about a peculiar phenomenon upon evaporation of the
solvent that cannot be predicted from the equilibrium
pM’-pH diagrams.
3.3. Gel Routes Involving Formation of Organic
Polymeric Glass
The third method is a gel route which involves for-
mation of organic polymeric network. This can be
carried out basically in two ways. The first is “in-situ”
polymerization route where the gel network is made
by polymerization of organic monomers. This is car-
ried out in the presence of metal ions, and what is ex-
pected is that all metal ions can be homogeneously
distributed into the organic polymer network. When
a combined process of metal-chelate complex forma-
tion and “in-situ” polymerization is strongly conscious,
the process can be called “polymerized complex (PC)
method” [5]. The second route involves the prepara-
tion of a viscous solution system containing metal ions,
polymers and a suitable solvent, and the process will
be simply called “polymer precursor (PP) method” in
this review article. This viscous solution can be easily
converted to a thermoplastic gel when the solution is
concentrated. Coordinating organic polymers such as
polyacrylic acid and polyethyleneimine are frequently
used in the PP method in order to stabilize metal ions
in thermoplastic gels. In this section, some important
aspects in these polymer routes are briefly described in
conjunction with their chemistry.
3.3.1. “in-situ” Polymerization Route. The basic
idea behind the “in-situ” polymerization or PC route is
to reduce individualities of different metal ions, which
can be achieved by encircling stable metal-chelate com-
plexes steadily by a growing polymer net. Immobiliza-
tion of metal-chelate complexes in such a rigid organic
polymer net can reduce segregations of particular met-
als during the decomposition process of the polymer at
high temperatures.
 “Sol-Gel” Preparation of High Temperature Superconducting Oxides 19

A representative example of this approach is the

Pechini method [59]. Although only little is known
about the chemistry involved in the Pechini route,
the basic chemistry of this process is the dehydra-
200
tion reaction of a carboxylic acid and an alcohol; i.e.
esterification. An example of the esterification reac- e
h 150
tion between a di-carboxylic acid and a di-alcohol is .Z
written as: 0”
.I:: 100
*

HO-R-OH + OH 50

-+ HO-R-O- + H20. (24)
The resulting dimeric product of the ester contains one
alcoholic hydroxyl (HO-) group in its left end and
one carboxylic acid (-COOH) group in its right end,
so that the former can react with another di-carboxylic
acid and the latter with another di-alcohol to form a
tetramer. This type of reaction occurs in sequence,
leading to a polymer molecule:
xHO-R-OH + xHO--e--R’-!-OH
+ .,0-,0-!-R’-& X OH
+ (2x - 1) H20. (25)
In fact the original patent for the Pechini process [59]
states the formation of a polymeric resin produced
through polyesterifzcation between metal chelate com-
plexes using alpha-hydroxycarboxylic acids (e.g. citric
acid and malic acid) and a polyhydroxy alcohol such as
ethylene glycol. Citric acid (CA) and ethylene glycol
(EG) is a couple most widely employed in the Pechini
process. This can be understandable when the follow-
ing three aspects are taken into account:
(1) Many of metal ions except monovalent cations
form very stable chelate complexes with CA [60].
(2) Such metal-CA complexes formed can be further
stabilized in EG as it possesses two alcoholic hy-
droxyl functional groups with strong complexation
affinities to metal ions [61-64].
0
0 5 10 15 20 25
reaction time /h
Figure 6. Viscosity of a 1 :4 molar ratio of citric acid:ethylene
glycol solution at 130°C as a function of reaction time (t): Gelation
occurs at t = 19 h, after which viscosity increases quite rapidly.
The viscosity of a purecitric acid [CA]: ethylene gfy-
co1 [EG] mixture with CA/EG = l/4 at 130°C is shown
in figure 6 as a function of reaction time. There is a slow
increase in viscosity of the solution over 19 h at 13O”C,
which I ascribe to the esterification (oligomerization)
reaction that occurs between hydroxyl groups of EG
and the carboxylic acid groups of CA. Gelation occurs
after 19 h for the pure CA/EG solutions, accompanied
with a rapid increase in viscosity. The highly viscous
gel exhibits a thermoplasticity. The occurrence of the
esterification in an early stage of the reaction is con-
firmed by 13C--NMR spectroscopy. Figure 7 shows a
“carboxyhc acid” carbon region of ‘“C-NMR spectra
for a series of CA/EG solutions reacted at 130°C. The
reaction time (t) ranges from 0 h to 2 h. Two major
resonance signals at 175.6 and 178.8 ppm in the bottom
of figure 7 are due to carbons in the two end carboxylic
acid groups (*) and a carbon in the central carboxylic
acid group (0):
HZ--* COOH
HO- 1 -*COOH [Al

(3) Successive ester reactions between CA and EG can
occur to form a polyester resin, as CA contains
three carboxylic acid groups (-COOH) in one CA
molecule and EG contains two hydroxyl groups
(-OH) in one EG molecule (see Eq. (25)).
A H2-*COOH
Weak features observed at 173.4 ppm (A) and 176.7
ppm (+) in the bottom of figure 7 can be assigned to
ester carbons resulting from the following esterifica-
tion reactions which occurred already at = 0 h (The t
20 Kakihana

Reaction
time

2h

lh

0.5 h

Oh
I I . I I I I I

184 180 176 172

chemical shift (ppm)
Figure 7, 13C-NMR spectra of citric acid (CA)/ethylene glycol(EG) solutions with CA/EG = l/4 reacted at 130°C for different durations:
Symbols marked on top of some NMR peaks are defined in the chemical formula shown in the figure.

dissolution process of CA into EG at 40°C gives rise Hz-COOH

to the reactions.):
H(& -COOH + Ha--CH2CH2--OH

%-H;?-COOH
HO -COOH + m--CH2~~2-0~

kH;?-COOH
+H + H2°.
H,-* 1 -O-CH2CH2-OH
+H20 (27)
-COOH
(26) Tbe two ester carbon peaks grow rapidly with increas-
H2-COOH ing the reaction time t. It is also noticeable that all
 “Sol-Gel” Preparation of High Temperature Superconducting Oxides
the peaks split into several components after the reac-
tion at 130°C for 0.5-2 h. These splittings indicate
that a number of ester products with similar structures
form in the solution. For instance the resonance ob-
served at the lowest value of chemical shifts (-173
ppm) in the upper three of figure 7 is due to ester
carbons (V) probably in one of the following diester
species:
WI
or
WI
HO-
Prolonged heating at 130°C promotes successive es-
terification reactions to form polyester molecules (see
Eq. (25)). As CA has three functional carboxylic acid
groups, branched polyester molecules result. Such
polyesterifications between CA and EG occurring in
the Pechini process have been proposed indirectly by
Anderson’s [65] and Messing’s [66] groups based on
rheological measurements, and more directly by Cho
et al. [67] and Uchiyama et al. [68] based on infrared
and Raman spectroscopy, respectively. Tai and Less-
ing [69] have investigated in detail foaming character-
istics of polymeric precursors by changing the organic
mass ratio of CA/EG based mainly on rheological and
thermal analyses and concluded that a highly porous
polymeric resin is formed by dehydrating an acidified
mixture of CA and EG in proper ratio. According to
the theoretical calculation by Tai and Lessing, a criti-
cal composition of a CA/EG mixture at which gelation
starts is CA/EG = 40/60 (mole ratio) on the assump-
tion that only a simplified polyesterification between
CA and EG occurs. Note that this critical compo-
sition differs considerably from the value of CA/EG
= 20/80 which has been recommended in the orig-
inal patent of the Pechini process. The excess EG
plays a role as a solvent to increase solubilities of
21
different metal salts in an early stage of processing.
Evaporation of EG should then be done to obtain a
polymeric gel.
The first step of the Pechini process is to prepare
stable metal chelate complexes such as metal CA com-
plexes. Most of metal CA complexes are soluble and
stable in a mixed solvent of EG and water. Esterifi-
cation of CA (both free CA and complexed CA) oc-
curs readily in the presence of EG at moderate tem-
peratures (lOO-15o”C), and prolonged heating of the
mixed solution with concomitant evaporation of ex-
cess EG promotes polyesterification yielding a trans-
parent polymeric resin precursor. A matter of vital
importance is to have a homogeneous polymeric pre-
cursor with exactly the same metal stoichiometry as
that of the final multi-component oxides. Because of
the high thermal stability of metal CA complexes at
operated temperatures (typically -130°C) they could
be frozen in a polymer network while preserving the
initial stoichiometric ratios of metal ions in the start-
ing solution. The principle of the Pechini route is
thus to obtain a polymeric resin precursor compris-
ing randomly branched polymer molecules through-
out which the cations are uniformly distributed, as is
schematically shown in figure 8. Heating of the poly-
meric resin at high temperatures (above 300°C) causes
a breakdown of the polymer. In spite of the thermo-
plasticity of the polymer, it is believed that less pro-
nounced segregation of various cations would occur
during the pyrolysis because of low cation mobility in
such crowded branched polymers. After Pechini, in
1980’s the Pechini method based upon the esterifica-
tion reaction has been extensively used to prepare a
variety of multi-component oxides such as lead mag-
nesium niobates [65], LaMnO [70,71], Sr-doped lan-
thanum chromite [72] and SrTiOs [67, 731. More re-
cently, it has been demonstrated in the synthesis of
copper based high temperature superconducting ox-
ides [5] that the method is quite suitable for compli-
cated systems where the compositions contain four
or more cations, which will be shown in the next
Section (4.3).
“In-situ” polymeric reactions other than the
polyesterification in the Pechini route can also be used
for the synthesis of multi-component oxides. These
include polymerizations of acrylic acid, acrylamide,
and methacrylic acid. Contrary to the Pechini route
where the polycondensation reactions (i.e., dehydra-
tion) are dominant, above-mentioned three polymer-
izations are initiated by the action of free radicals.
22 Kakihana

Concept of polymerized complex method

A rFl

A ’

AOx BOX : oxides

: residual organics : cafbon
C

stoichlometdcally homogeneous reaction

Figure 8. Concept of polymerized complex or polymer precursor method.

 “Sol-Gel” Preparation of High Temperature Superconducting Oxides 23

Azobisisobutyronitrile and benzoyl peroxide are rad- ions (M):

ical initiators most commonly used for the free-radical
polymerization, and radicals can be generated by the H H H
following respective thermal decomposition of these
compounds: - ________

OOH

.. .:
.:M:.
.. PI
+ 2(CH3)2 l + N2 .:’
(28) b
CeN \/
7 COOH COOH

-+ 2Ph* + 2C02 (29)

where a dot l represents a position where a single elec-
tron stays and Ph- means a phenyl (CbHs-) group.
Free radicals thus generated now attack monomers
to develop new radicals. An example of the radical
polymerization using acrylic acid is shown below [7 11:
H2C= H
OOH
COOH COOH
(30)
ll!I COOHj,
The polymers thus obtained are linear molecules with
flexible chains, and they are tangled together as the
polymerization proceeds. Carboxylic acid groups do
not take part in the polymerization unlike the case of
the polyesterification, but play an important role when
polymers are crosslinked by connecting some dissoci-
ated carboxylic acid groups (-COO-) through metal
Despite that a bonding between a cation and a (dis-
sociated) carboxylic acid group is generally weaker
than the chelate bonding in metal-CA complexes, the
randomness of the initial solution would retain in the
final polymeric gel. This is because the gel consists
of many chains twisted and tangled together, in which
both cations and solvents are entrapped by steric hin-
drance.
3.3.2. Polymer Precursor (PP) or Polymer Solution
Method. The PP route is a simple gel method, which
is basically similar to the above-mentioned “in-situ”
polymerization method. In most of the PP routes, the
first step is to prepare an aqueous precursor solution
containing metal salts followed by addition of a water-
soluble polymer. Water-soluble polymers most com-
monly used in the PP route involve polyvinyl alcohol
(PVA), polyacrylic acid (PAA) and polyethyleneimine
(PEI). Contrary to the “in-situ” polymerization method,
the PP method involves no active polymerization re-
actions. Noticeable is, however, that PVA, PAA and
PEI are coordinating organic polymers to cations which
strongly modify the rheological characteristics of the
mother aqueous precursor solution. Metal ions will
therefore be able to play a role as cross-linking agents
between polymers (see structure [D] for the case of
PAA). Random cross-linking across polymer chains
would entrap waters in growing three-dimensional net-
works, which can convert the system into a gel. Exam-
ples of interaction between PVA and metal ions can be
found in literature for PVA--Cu2+ [74,75] and PVA-
24 Kakihana
taitanate [76]; in the latter a titanate cross-coupling
agent (triethanol amine titanate chelate) has been used
for creating crosslinked PVA polymers as shown in [El.
Recently, Gtilgtin et al. [77] have indicated in their
study of calcium aluminate powders from the Pechini
method that the polymeric resin is able to accommo-
date a higher amount of cations than it can chelate in
the solution. Gtilgtin and Kriven [78] have then pro-
posed that chelation of the metal ions by the carboxylic
acid groups, as is the Pechini resin, is not the only
route to obtain stable polymeric precursors. In order
to evidence this proposal, they have prepared aqueous
PVA precursor solutions containing Ca and Al cations
with a positively charged valence from the cations to
negatively charged hydroxyl groups ratio of 4 : 1, and
successfully obtained a gel without forming precipita-
tion despite the large charge imbalance (They called
this simple method “solution-polymerization route”.).
Another important aspect of the PVA based method
notified by Gtilgtin and Kriven [78] is that the new gel
process has a considerably improved net yield of - 1.8
for the weight ratio of the ceramic to the organics, when
compared with 0.15 for the Pechini method.
I
RO-Ji-OR'
H20
H20
H20
H20 H20
I
RO-F-OR'
WI
4. Relevant Examples of Sol-Gel Preparation of
High Temperature Superconducting Oxides
The purpose of this section is to review the present
status of various sol-gel type processes for high tem-
perature superconducting oxides. I focus only on pro-
viding references related to three gel routes, including
the alkoxide-based route (4.1) the metal-chelate gel
route (4.2), and the organic polymeric gel route (4.3).
I present some relevant examples in each of these gel
routes, wherein main efforts have been placed on how
multicomponent gels can be prepared without forma-
tion of precipitates. However, as has been described
in the tutorial part of the Section 3.2.1, successful
gelation without precipitation should not be always
taken to imply that perfect mixing of the constituent
metal ions is achieved in the resulting gel network (see
figures 3( 1) and (3)). Such examples will be given for
calling attention of readers to this common problem in
solution-based preparation of multicomponent oxides.
The obvious difference in each individual chemistry of
the three gel routes implies that each gel technique will
be able to have its unique advantage and weakness de-
pending upon the suitability to fabricate various shaped
ceramic entities such as powders, fibers and films. For
instance, the alkoxide-based route would be more suit-
able for fiber production or film formation than in the
organic polymeric glass route as a larger amount of or-
ganics left in precursors prepared by the latter route
can deteriorate the quality of the final fiber or thin
film. On the other hand, the organic polymeric glass
routes would be favorably used for powder prepara-
tion of multicomponent oxides with very complicated
compositions.
4.1. Sol-Gel Routes Based upon Hydrolysis of Metal
Alkoxides
4.1.1. Chemical Modijication of Insoluble Metal-
Alkoxides. Alkoxides of yttrium, barium, strontium,
bismuth, thallium, calcium and copper have attracted
considerable interest as molecular precursors for the
sol-gel synthesis of high temperature superconducting
oxides, such as YBa&Jus07-d, BizSr2CaCuzOs+d or
T12Ba$ZaCuzOs+d. However, the insolubility of sim-
ple copper(I1) alkoxides in common organic solvents
casts some doubt about the versatility of the sol-gel
route using alkoxides for the synthesis of copper con-
taining superconducting oxides. The low solubility
of copper alkoxides (as well as other transition met-
als alkoxides) arises mainly from oligomeric reactions
which leads to the formation of less soluble polymeric
species 1791. In fact some early works on sol-gel syn-
theses of these compounds [SO-881 have been forced to
use a turbid precursor solution containing suspension
of insoluble copper alkoxides. In this case chemical
inhomogeneity already exists in the initial precursor
solution on a scale equivalent to the dispersed particle
size. In order to avoid this type of inhomogeneity in
the precursor solution, many previously reported sol-
gel syntheses of superconducting oxides have utilized
soluble nonalkoxide sources of copper, such as copper
acetylacetonate [89], copper nitrate [90, 911, copper
acetate [92-971 or other copper carboxylates [98,99].
 “Sol-Gel” Preparation of High Temperature Superconducting Oxides
However, since these nonalkoxide copper complexes
cannot be readily hydrolyzed even in large excess of
water in contrast to other metal alkoxides, formation
of inhomogeneous sol or gel with respect to mixing of
copper with the rest of metal elements may result. An
example of this type of inhomogeneity can be seen in
the synthesis of T12Ba2CaCu208+d using Ba- and Ca-
alkoxides and Tl- and Cu-acetates; although the precur-
sor solution can gel with no observable precipitation,
the final samples were found to be inhomogeneous and
strongly multi-phase [97]. ElKhokh et al. [92] have
then performed fast hydrolysis-polycondensation of
a precursor solution containing Y-, Ba-isopropoxides
and Cu-acetate under hypercritical conditions (235”C,
48.5 bar) to overcome the mismatched hydrolysis rates
towards water.
Search for copper alkoxides or chemically modified
copper alkoxides that can be readily dissolved in a suit-
able organic solvent and can be hydrolyzed at a sig-
nificant rate upon adding water is therefore required.
The solubility of some copper alkoxides, including
CU(OC2H5)2, CWGH40CdWz~ WOCWCH~)h
and Cu(OC4H9)2, in various organic solvents has
been thoroughly examined by Hirano et al. [3] and
Murakami et al. [91]. Table 1 lists suitable com-
bination of copper alkoxides (or their modified com-
pounds) and organic solvents, from which hydrolyz-
able copper-containing precursor solutions can be
prepared. Copper alkoxides listed in Table 1 are clas-
sified into 5 classes: Entry 1 involves simple cop-
per alkoxides such as methoxide [Cu(OCHs)2], ethox-
ide [Cu(OC2H5)2], isopropoxide [Cu(OCH(CHs)&]
and n-butoxide [CU(OC~H~)~], while Entry 2 to 4 in-
volve alkoxy-alkoxides, polyetheralkoxide and amino-
alkoxides, respectively, and finally Entry 5 involves
mixed-ligand alkoxides. The rationale behind the
utilization of these alkoxides or solvent systems is
to reduce the strong tendency for oligomerization of
copper-alkoxides [79, 11 l] and thereby to improve the
solubility [3, 241. Carboxylic acids (R-COm), /I-
diketones in the enolic form (RC(OH)CH(CO)R’) and
alcohol-amines (Rs-,N(R’m),) employed as sol-
vents or one of components in solvents in Entry 1
are thought to be of nucleophilic X-OH molecules
characterized by its hydroxyl (-OH) group, that re-
act readily with metal alkoxides M(OR), leading to the
formation of a new mixed-ligand chemical species:
M(OR), + m X-OIJ
-+ M(OR),-,(0X), + m ROH. (31)
25
Although only little is known about the structure of
copper-alkoxides modified with these molecules, it is
likely that the modifiers coordinate to the copper ion
as multidentate ligands so forming a chelate complex.
The formation of such a copper chelate complex re-
sults in an increased coordination number of the cop-
per center as compared to the parent copper alkoxide.
For instance, triethanolamine (N(&HsOH)s = TA),
which contains three hydroxyl oxygens and one ni-
trogen, can act as a tetradentate ligand to metals, as
has been shown in some metal-TA complexes such as
Sn(TA)2 [112, 1131 and Ba(TA)2 [114]. Replacement
of one of the monodentate alkoxide ligands in M(OR),
by one tetradentate triethanol amine thus increases the
coordination number of the metal center from 1 to 4,
which, in the case of copper-alkoxides, prevents or re-
duces their oligomerization and consequently improves
the solubility. Alkylamines such as ethylenediamine
(NH2CH2CH2NH2 = en) in Entry 1 can also be used
for reducing the oligomerization of copper alkoxides,
as they can coordinate to copper ions as a bidentate lig-
and causing an effect similar to what is observed in the
triethanol amine-modified copper alkoxide. The fol-
lowing addition reaction rather than a ligand exchange
reaction was suggested by Katayama et al. [103, 1151
in the case of a mixture of Cu(OCHs)2 and ethylenedi-
amine (en):
Cu(OCH3)2 + 2en + Cu(OCHs)2(en);!, (32)
where the en-modified alkoxide is soluble in ethanol.
The same authors [103, 1151 have investigated the
structures of Cu(OCHs)2 and its en-modified alkoxide
by an extended X-ray absorption fine structure
spectroscopy (EXAFS) and concluded that the
en-modified alkoxide possesses a monomeric form of
Cu(OCHs)2(en)2 dissolved in alcohols in sharp contrast
to the insoluble parent Cu(OCHs)2 which exhibited a
highly polymeric structure [ 1161.
Alkoxy (ether)-alkoxide [3, 101, 1021, polyether-
alkoxide [ 1171 and amino-alkoxide [ 1021 in Entry 2
to 4 are potentially multidentate chelating ligands,
since in addition to the alkoxo oxygens the ether oxy-
gens involved in the first two type of ligands and
the amino nitrogens involved in the third type of lig-
ands can also participate in the coordination. Experi-
mental evidence for the multidentate character of the
amino-alkoxide ligand has been given in a compound
CU(OCH(CH~)CH~N(CH~)~)~, where both the amino
group and the alkoxo group coordinate to the Cu center
26 Kakihana

Tuble 1. Suitable combination of copper alkoxides and solvents for non-precipitated precursor

Entry Classification Cu-alkoxides Solvents Ref.

1 Non-chelating alkoxides Cu(OCHs)z(methoxide) ethanol or 2-methoxyethanol + ethylenediamine uo31

2-methoxyethanol + 2-dimethylaminoethanol [104. 1151
methanol + triethanolamine [107,109]
methanol + diethanolamine UlOl
Cu(OC2Hs)z (ethoxide) acetic acid or formamide t911
ethanol + diethauolamine or triethanolamine
ethanol + 2-dimethylaminoethanol
acetylacetone L3.911
diethylamine or 2-aminoethanol 131
ethanol + diaminoalcohol 11’361
Cu(OCH(CHs)z)z (iso-propoxide) acetic acid or propionic acid or formamide [911
ethanol + diethanolamine or triethanolamine
ethanol + 2-dimethylaminoethanol
acetylacetone
iso-propanol + 2-ethylhexanoic acid [to81
Cu(OC4Hy)z (n-butoxide) acetic acid or propionic acid or formamide [911
ethanol + diethanolamine or triethanolamine
ethanol + 2-dimethylaminoethanol
acetylacetone
2 Alkoxy(ether)-alkoxide Cu(OC2H40C2Hs)z (ethoxy-ethoxtde) diethylamine or tetrahydrofuran or [31
2-ethoxyethanol
toluene [loll
CU(OCZH&GHY)~ tetrahydrofuran uw
(n-butoxy-ethoxide)
3 Polyether-alkoxide CU(OC~H~OC~H~OCH~)~ benzene t1171
4 Amino-alkoxide CWZH4WGW2)2 tetrahydrofuran [lo21
5 Mixed-ligand alkoxide (acachCu.dOWbh polar solvents (most of alcohols) u191
(acetylacetone-modified
n-butoxide)
(acac)zCu2(OC3HnOCH3)2
(acetylacetone-modified
methoxy n-propoxide)
(acac)&&(OCzH40CHs)z WOI
(acetylacetone-modified
methoxy ethoxide)

to form a Smembered chelate ring per one amino- from 2 for non-chelating (i.e. monodentate) copper
alkoxide [ 1181: alkoxides such as ethoxide up to 4 in structure [fl,
which results in the decrease in oligomerization com-
,KH3)2 pared to the non-chelating alkoxides.
The last approach (Entry 5) for improving the
solubility of copper alkoxides can be found in the
work by Payne’s group [119] and Sauer et al.
[ 1201, who developed alcohol-soluble copper species
having formula (acac)zCuz(OCH2CH2CHzOCHs)z,
(acac)&u4(0C4Hs.)4 and (acac)Cu(OCH2CH20CHs),
where acac is a deprotonated acetylacetone of com-
/ position CHs(CO)CH(CO)CHs. All these molecules
(CH3 )2
are acetylacetone-modified alkoxides and can be pre-
The coordination number of the copper center increases pared by reacting the parent copper alkoxides with
 “Sol-Gel” Preparation of High Temperature Superconducting Oxides
acetylacetone according to Eq. (31). A single crystal
X-ray diffraction study of the acetylacetone-modified
copper n-butoxide with a unit of (acac)&u4(0-
CdHs)a has revealed that each copper ion is coordinated
to one bidentate acac and three monodentate butoxides
resulting in a coordination number of 5. The perspec-
tive view of this acac-modified alkoxide indicates a
tetramer structure with respect to copper ions consist-
ing of two symmetric dimer units weakly bonded each
other, but importantly indicates no polymeric struc-
ture. This is consistent with the significant improve-
ment of the solubility of this compound in alcohols
when compared with the solubility of the parent cop-
per n-butoxide which is soluble only up to 36 mmol/l
in butanol [ 1051.
Finding an appropriate bismuth precursors for Bi-
based superconductors such as Bi#r2CaCu20s+d is
also troublesome, as, for instance, the solubility of
Bi(OCHs)s in a common solvent such as ethanol
is greatly limited [81, 851. Non-alkoxide Bi com-
pounds of Bi-naphthenate [85] and triphenyl Bi [99],
which are soluble in toluene, have been used as a
source of Bi in the synthesis of Bi(Pb)-Sr-Ca-
Cu-0 thin films and powders, respectively. The
above-mentioned arguments concerning the solubil-
ity and stability of copper alkoxides may hold for
Bi-precursors. Matsumura et al. [85] have found
in their sol-gel synthesis of c-axis oriented Bi(Pb)-
Sr-Ca-Cu-0 film with zero resistance at 100
K that precipitation or colloidalization owing to the
rapid hydrolysis of some of alkoxides or triphenyl
Bi can be avoided by adding diethanolamine. Hi-
rano et al. [loll developed a solution route to su-
perconducting Bi-Sr-Ca-Cu-0 films compris-
ing of the high-T, and low-T, phases with (001)
preferred orientation on a MgO(100) single crystal
substrate using partially hydrolyzed metal-alkoxide
solutions with 2-dimethylaminoethanol. The metal
alkoxides used in their study were Bi(OCH(CH&)s,
Sr(OCdHs)2, Ca(OC4H9)2 and CU(OC~H~OC~H~)~.
The role of 2-dimethylaminoethanol is probably to in-
crease the solubility of both CU(OC~H~OC~H~)~ and
Bi(OCH(CHs)& and to retard the rapid hydrolysis of
alkoxides.
4.1.2. Synthesis of YBa#u307--d Using Metal-
Alkoxides at Temperatures Below 800°C. Most of
previously reported sol-gel processes which use metal
alkoxides for the synthesis of YBa$us07-d lead to the
formation of BaCOs, CuO and Y2Os as intermediate
27
phases at temperatures below 800°C giving only few
advantages over the conventional solid-state reaction
process [ 1211. In particular BaCOs is a principal obsta-
cle to the low-temperature synthesis of YBa2Cus07-d,
as temperatures higher than 800°C are required for the
complete reaction of this BaCOs with the other phases
even with fine particle precursors. The formation
of BaCOs may occur as far as the carbon-containing
alkoxides/organic solvents systems are employed. This
is enhanced when all the organic components (solvents
and ligands) cannot be completely eliminated from
the gel prior to pyrolysis. BaCOs forms through the
prompt reaction between the active BaO or BaOH par-
ticles produced upon the pyrolysis of the gel and the
evolved CO2 gas upon decomposition of the organics in
the gel. Note that the active BaO or BaOH can be read-
ily carbonated by atmospheric CO:! to form BaCOs.
This means that BaCOs can still form even when all
the organic components can be successfully eliminated
from the gel. The formation of the above-mentioned
intermediate phases may also arise from a low degree of
homogeneity with respect to mixing of cations in mul-
ticomponent gels. A possible source for the chemical
inhomogeneity in the resulting gel is the mismatched
hydrolysis and condensation rates of the metal alkox-
ides upon adding water. Because of this chemical inho-
mogeneity some islands of particular metals may form
in the gel leading to the formation of unreacted interme-
diate phases upon pyrolysis of the gel at low temper-
atures. Low-temperature synthesis of YBa2Cus07-d
at temperatures below 800°C may therefore be
achieved, when the following matters are taken into
account:
I> Precursor solutions containing metal alkoxides or
chemically modified metal alkoxides should be de-
signed such that the ligands and solvents undergo
facile elimination upon drying or pyrolysis of the
gel. To avoid the conversion of the active BaO or
BaOH formed at low temperatures to BaCOs, heat
treatments should be carefully done under C02-free
atmosphere (e.g., inert gas atmosphere).
2) Success in obtaining multi-component gels of high
homogeneity depends mainly upon the control of
hydrolysis and condensation of metal alkoxides.
Matching of hydrolysis rates can generally be at-
tained by the chemical modification of metal alkox-
ides using hydroxylated ligand additives such as
polyols [122], organic acids [123, 1241 and B-
diketones [ 1251. The ultimate end should be thought
28 Kakihana
to design precursor solutions for YBa2CusO,-d,
which, upon hydrolysis and condensation, can pro-
duce atomistically mixed-metal oxygen bonds of -
Y-O-(Ba-O)~-(Cu-O)s-Y-O- between
the three metals with the cation stoichiometry
Y:Ba:Cu= 1:2:3.
Attempts to synthesize YBa#@-d powders,
films or fibers at temperatures below 800°C have been
made by different techniques, which include: 1) con-
trolled hydrolysis of chemically modified alkoxides, 2)
pyrolysis of alkoxide-derived precursors under flowing
ozone/oxygen mixture, 3) decomposition of solution-
derived, carbonless precursors in CO*-free inert atmo-
sphere, and 4) utilization of Y-Ba-Cu heterometallic
complexes, as described below:
1) The enormous potential of the alkoxide-based route
has been shown already in the early work by Zheng
and Mackenzie [108], who prepared a rigid dark
blue amorphous gel without precipitation by a con-
trolled hydrolysis of the iso-propanol precursor so-
lution containing Y-, Ba-, Cu-isopropoxides modi-
fied with 2-ethylhexanoic acid and obtained a nearly
phase-pure YBazCus07-d after firing the gel at
780°C in air for 1 h. 2-ethylhexanoic acid plays
an important role not only in increasing the sol-
ubility of the Cu-isopropoxide in isopropanol but
also in decreasing the extremely fast hydrolysis of
the Y-isopropoxide [38], and as a result the overall
chemical homogeneity of the resulting gel is greatly
improved when compared with the case of a simple
mixture of Y-, Ba-, Cu-isopropoxides in the absence
of 2-ethylhexanoic acid where precipitation can eas-
ily occur upon hydrolysis [ 1261.
Acetic acid exerts an effect similar to 2-ethyl-
hexanoic acid, as has been demonstrated by Ad-
maiai et al. [ 1271. It has been found that the
gel derived from the isopropanol precursor solution
containing Y-, Ba-isopropoxides and Cu-ethoxide
modified with acetic acid gives YBazCus07-J as
a major product with less formation of BaCOs,
YzOs and CuO at 750°C for 6 h, while the gel
prepared with Y-, Ba-, Cu-acetates and ethylene-
diamine gives a mixed-product of BaCOs, CuO and
Y203 with less formation of YBa2Cus07-d at the
same processing temperature. The essential role of
acetic acid is to reduce the large gap of hydrolysis
and condensation rates between the different alkox-
ides. Acetic acid reacts easily with metal alkoxides
(see Eq. (31)), leading to the formation of mixed-
ligand alkoxides of type M(OR),-,(CHsCOO),
(M = Y, Ba, or Cu). Despite that the reactiv-
ity of each mixed-ligand M(OR),-,(CH&OO), to-
wards water is not identical, the dramatic reduction
of hydrolysis and condensation rates relative to
the parent alkoxides avoids the precipitation and
makes segregations of particular metal hydroxides
or oxides less pronounced, thus leading to the for-
mation of the greater number of -Y-O-(Ba-
0)2-(Cu--O)s-Y-O- bonds during the con-
densation of the acetic acid modified alkoxides.
Formation of more -Y-0-(Ba-Oh-(Cu-
O)s-Y-O- bonds reduces the synthesis tem-
perature of YBazCus07-d more remarkably com-
pared to the solid state reaction. On the other
hand, the bond formation of -Y-0-(Ba-0)2-
(Cu-O)s-Y-O- is less probable in the acetate-
ethylenediamine route, as the gel derived can con-
tain many stable metal-nitrogen bonds such as -
M-NH2-CzI&-NH2-M- (M = Y, Ba, or Cu)
which inhibits further hydrolysis to form -M-
O-M- networks, This requires a higher synthesis
temperature to obtain phase-pure YBa2Cus07-d.
2) Hirano et al. [loo] have found that the use of
ozone gas during the pyrolysis of precursors de-
rived from a controlled hydrolysis of Y-, Ba-
isopropoxides and Cu-2-ethoxyethoxide is effec-
tive to suppress BaCOs formation. Processing
temperatures of 650°C and 750°C were reported
in the powder preparation of YBa2Cus07-d with
and without ozone, respectively. Non-oriented
films of YBa$&07-d have been made on yttria-
stabilized ZrO2 polycrystalline substrates also at
65o”C, when ozone gas was utilized for pyrolysis
of the precursor thin films prepared with a partially
hydrolyzed 2-methoxyethanol solution containing
Ba metal, Y-acetylacetone and Cu-ethoxyethoxide
[ 1281. YBazCus07-d thin films with c-axis orien-
tation perpendicular to a SrTiOs( 100) single-crystal
substrate were successfully prepared at 800°C in a
flowing ozone/oxygen mixture, which completely
suppressed the formation of BaCOs.
3) Horowitz et al. [102] have produced organo-
metallic-derived precursors by complete hydro-
lysis of tetrahydrofuran (THF) solutions containing
Y-, Ba-isopropoxides and a hydrolyzable cop-
per compound such as Cu(N(CqHs)& Cu(OC2
H4N(GHs)2)2 or Cu(OGH40GH9)2)2. The pre-
cursor dried at 100°C in vacuuo contained only
 “Sol-Gel” Preparation of High Temperature Superconducting Oxides
0.2-0.3 wt% of carbons. However, the carbon con-
tent was increased to 0.8 wt% and 3.56 wt% after 2
hours and 24 hours exposure to ambient air, respec-
tively, which implies that the precursor (most prob-
ably hydrated oxides) reacts readily with ambient
CO2 to form carbonates. Some precautions for pro-
tecting the reaction from ambient CO2 gas are there-
fore needed in handling alkoxide-derived precursors
for YBaaCusOT-d. The precursor freshly prepared
was then fired in CO2 free argon at 650-700°C for
2-12 h to yield tetragonal YBa$us07-d which on
oxidation at 400°C in oxygen for 2-12 h resulted
in submicron particles of the orthorhombic (super-
conducting) YBa2Cus07-d. The ability to produce
essentially phase-pure YBa$us07-d was due to the
lack of BaCOs. It has been concluded that forma-
tion of YBa2Cus07-d with the complete avoidance
of BaCOs can be achieved even at 650°C when the
carbonless precursor, which is derived from the hy-
drolysis of organometallic solutions under argon, is
fired in flowing (COZ-free) inert gas.
4) The most challenging approach to ensure chemi-
cal mixing at the molecular level is to employ the
synthesis of heterometallic complexes with exactly
the same metal stoichiometry as that of the desired
oxide product. In particular, heterometallic alkox-
ides, which contain two or more different metals
linked via ,LL-or ps-bridging alkoxo (-OR) groups
or via 0x0 (-0-) ligands of various bridging
modes [34], are claimed to provide the most promis-
ing molecular precursors in the sol-gel synthesis of
multicomponent oxides at lower processing temper-
atures.
Kordas et al. [81, 86, 129-1311 have recognized
in their sol-gel synthesis of YBa2Cug07-d and
Tl-Ba--Ca-Cu-0 superconductors that hetero-
metallic alkoxides may form between Ba- (or
Y-) methoxyethoxide and Cu-ethoxide.
has been shown based upon the quasielas-
tic laser light scattering experiments [81, 861
that the insoluble Cu-ethoxide suspended in
methoxyethanol/methylethylketone react with Ba-
methoxyethoxide, which caused a reduction in the
particle size of Cu-ethoxide down to 1100 nm. Ex-
posure of the solution containing Cu-ethoxide and
Ba-methoxyethoxide to ambient moisture followed
by the addition of Y-methoxyethoxide produced sta-
ble 3 component sols with an average particle size
of 60 nm [86], which were converted to gel upon
evaporation of solvents. Processing temperatures
29
of 700°C were reported for the crystallization of
bulk superconducting YBa2Cu307-$ phase with
T, = 75 K.
It is known that heterometallic oxoalkoxides can
be obtained through condensation reactions be-
tween alkoxo (-OR) and hydroxyl (-OH) ligands
according to the following general equation:
M(OR), + M’(OR’),-,(OH),
+ (OR),-lM-O-M’(OR’),-,(OH),-,
+ ROH. (33)
Katayamaetal. [103, 104,115,132,133] havethen
designed a heterometallic oxoalkoxide precursor so-
lution for Y-Ba-Cu-0 superconducting pow-
der, fibers and films based upon Eq. (33). First, an
ethylenediamine (en)-modified copper methoxide,
Cu(OCH&(en)2, was partially hydrolyzed with
equimolar water to form Cu(OCHs)(en)2(OH):
CWCHMenh + H20
+ Cu(OCHs)(en)2(OH) + CHsOH. (34)
Second, the product Cu(OCHs)(en)2(OH) was re-
acted with either Y-isopropoxide modified with
ethyl acetoacetate (EAA) or Ba ethoxide according
to the following presumed reactions:
Cu(OCHd(eMOH) + WOGH&
--+ (CHsO)(en)2--Cu-O-Ba(OC2Hs)
+ C2HsOI-I (35)
Cu(OCHd(enh(OH) + Y(OCHKHdd@W
+ (CHsO)(en)z-Cu-0-Y(OCH(CHs)2)
x (EAA) + (CH3)2CHOH. (36)
It
In gel films prepared from the presumed het-
erometallic alkoxide solution, calcination at 600°C
under an Ar atmosphere produced a tetrago-
nal YBa2Cus07-d with no X-ray evidence for
the presence of BaCOs, which was subsequently
converted to an orthorhombic (superconducting)
YBa2Cus07-d by annealing in oxygen at 400°C for
24 h.
Rupich et al. [ 134-1371 have reported the syn-
thesis of the heterometallic YBazCus-oxo alkoxides
with the general formula YBa2Cus(px-0)s(px-
OR)-,, from which superconducting YBa2Cus07-d
30 Kakihana
powders [134, 1361, filaments [137] and thin films
[135, 1361 were directly prepared at temperatures
below 800°C without the intermediate formation of
individual metal oxides or carbonates. A precursor
with the composition of YBa2Cus(pX-0)s(p,-
OC2H40CHs)7 was prepared by reaction of a pyri-
dine solution of ~-0x0 copper (II) polymer with
2-methoxyethanol solutions of Ba(OC2H40CH&
and Y(OC2H40CHs)s according to the following
reactions:
2n Ba(OC2H40CHs)2 + 3(~-OCu),
+ n Badh(p,--0h (~~-0GH40CHd4
(37)
Y(OWWCHd3 + Ba2Cw (P~--O)~
x ~L---OC~WCH~)~
+= YBa2CudpCLx--0h (/-b--OC2&0CH3)7.
(38)
The product of the reaction (38) was isolated as
amorphous brown solids by removal of the sol-
vent under vacuum, and the proposed composi-
tion was confirmed by gravimetric, inductively cou-
pled plasma (ICP) and molecular weight exclu-
sion chromatographic analyses. The heterometal-
lit 0x0 alkoxides were found to be soluble in the
parent alcohol or other nonaqueous solvents such
as pyridine. The potential advantage of these 0x0
metal alkoxides has been demonstrated in the low-
temperature preparation of superconducting films,
where c-axis oriented YBa2Cus07-d thin films per-
pendicular to a (100) yttria-stabilized ZrO;! substrate
were successfully prepared at 730°C with zero re-
sistances at 89.5 K and critical current densities of
2 x lo5 A/cm2 at 77 K.
4.2. Sol-Gel Routes Based upon Water-Soluble
Metal Chelates
The sol-gel route described in this section is char-
acterized in that the precursor solution is mostly an
aqueous solution of inorganic salts or metal organic
compounds. Most of the previously reported aqueous
sol-gel synthesis of high temperature superconduct-
ing oxides employ potentially chelating agents, which
involve acetates [ 138-1621, tartarates/acetates [ 154,
163-1721, citrates [58, 173-2091, oxalates [210-2121,
lactates [213], trifluoroacetates [214-2171, propionates
[218], EDTA (ethylenediamine-tetraacetic acid) [58,
219-2281, polyol[185,229-2351 and urea [236]. The
basic idea behind the use of such chelating agents is to
reduce the fraction of free-metal ions in aqueous so-
lution by the formation of soluble chelate complexes.
Most of the constituent metal ions of high tempera-
ture superconducting oxides can undergo hydrolysis in
aqueous medium in the absence of chelating agents,
which can be promoted at higher pH or upon evapo-
ration of water, leading to the formation of insoluble
species before gelatin occurs. For this reason, the con-
centration of the precursor solution must be carried
out in the presence of strong chelating agents to avoid
unwanted precipitation. Alternatively, metal-chelates
in a non-aqueous medium have also widely been used
for the synthesis of high temperature superconducting
oxides especially for thin film fabrication [237-2501.
A detailed description for this approach is beyond the
scope of this review, and those who are interested in this
area can find some illustrations related to such tech-
niques in recent publications [251,252].
4.2.1. Synthesis of YBa2CuqOg Under 1 atm of
Oxygen. In general materials fabricated by the sol-
gel routes have shown a better compositional homo-
geneity in comparison with a conventional material
produced by a solid-state reaction. This has been im-
mediately demonstrated in the low temperature syn-
thesis of YBa2Cu40s under 1 atm of oxygen. Unlike
the synthesis of YBa$us07-d, the temperature for the
synthesis of YBa$&Os must be below 830°C as far
as under 1 atmospheric oxygen pressure is used. This
is because YBa2Cu40s phase is partially or completely
decomposed into YBa2Cus07-d, Y2B%Cu7014+d and
CuO between 830°C and 950°C under 1 atm of oxy-
gen. Time needed for the formation of YBa2Cu40s
depends upon the reaction temperature and more cru-
cially upon the compositional homogeneity of the start-
ing precursor used. YBa$&Os can therefore be
regarded as a system suitable for judging the composi-
tional homogeneity of precursors fabricated by differ-
ent routes, when the synthesis is carried out under 1 atm
of oxygen at low temperatures (typically 760-800°C).
For instance, in the conventional solid-state reaction
route using a mixture of Y203, BaCOs and CuO, pure
YBa2Cu40s can never been prepared under 1 atm of
oxygen below 800°C because of the nonuniformity
of the starting powder mixture. Feng et al. [253]
have claimed the synthesis of YBazCu40s under 1 atm
of oxygen starting from a powder mixture of Y203,
 “Sol-Gel” Preparation of High Temperature Superconducting Oxides 31

Tub/e 2. Synthetic conditions and some physical properties of YBazCu4Os prepared under 1 atm of oxygen by various sol-gel routes.

Temp. TCIK AT!‘4’

Methods Precursor solutions “C Firing time(“) onset(*2) zero(‘3) 1; Impuritiest*5) Ref.

M-complex M-nitrates + citrate 800-815 3-5 days 83 CR) 66 --1WL-01 cue-20% [1931
gel route + ethylene diamine 80 G) - cue-10% uw
+ H20, pH = 5.5
Y(N03)3, Ba-, Cu-acetates 800 50 h (c) + 20 h (s) 85 (RI 80 ~5 (RIO-YO) none 12571
in 25 ~01% aq. acetic
acid + tartaric acid,
pH = 5.8
Y-, Ba-, Cu-acetates 780 30 h (c) + 30 h (s) 85 CR) 75 -5 6-L-o) none 11631
+ tartaric acid + Hz0 75 (Ml - ~(M~o-Yo)
Y(NOs)s, Ba-, Cu-acetates 810-814 60 h (c) + 30 h (s) 82-84 (R) 72 -6 (Rm-01 cue-5% [I671
+ acetic acid + tar&c none(*“)
acid + H20, pH = 6.2
Y2O3, Ba-, Cu-acetates 780 10 h (c) + 30 h (s) 78 h (S) - - cue-2% [I651
in 0.2 moUl aq. acetic acid BaCuOz-7%
+ tartaric acid, pH = 5.6
Y-, Ba-, Cu-acetates 790 48 h 89 CR) 74 -8 (Rm-o) none [I44
+ 5.5 wt%PVA + 6 wt%PA
+ 1.5 wt%2-HIA + HzO(*~)
Hydrolysis of Y(n-OC4Hy)3 + Ba(OCzH5)2 800 5h(c) + 10 h(s) 80-83 (R) 76 -4 &n-o) cue-2% 1901
M-alkoxide + Cu(NOs)z m ethanol u.k.(*‘)-6%
and xylene
780 5 h(c) + 10 h(s) 80 CM) - cue-10% 1911
u.k.(*“) -12%
Y-, Ba-, Cu(n-OC4Hy), in 760 20h -84 (R) 78 -3 (K-o) cue-3% [IO51
buthanol and xylene u.k.(*‘)-12%
Organic Y-, Ba-, Cu-nitrates in 780-790 24 h(c) + 60 h (s) 82.6 (M) - 4.5 (MN-YO) cue< 1% [2581
polymeric HlO/ethylene glycol
glass + citric acid
Y-, Ba-, Cu-nitrates 800-820 24 h(c) + 30 h (s) 82 W 79 2 none I2591
m polyvinyl alcohol/H20 80 04
(’ I) “c” and “s” in parentheses stand for “calcination” and “sintering”, respectively.
(‘2) “R”, “ S” and ‘Xl” in parentheses stand for determinations of T, (onset) by “resistivity ” , “SQUID” and “complex magenetic susceptibility
(real part)” measurements, respectively.
(*s) Temperatures at zero resistance.
('4) “R,-(,", “Rl+ao” and “Mt+~tr” in parentheses stand for “resistivity transitions between midpoint and zero point”, “resistivity transitions
between 10% and 90%” and “complex magnetic susceptibility (real part) transitions between 10% and go%“, respectively.
(*j) Impurity levels relative to the strongest I1 1 reflection from YBazCu4Os.
(*WA longer heat treatment depressed completely CuO.
(*7) Abbreviations: PVA = polyvinyl alcohol, PA = propionic acid, HIA = 2-hydroxy isobutyric acid.
(*U “u.k.” stands for “unknown phase”.

BaC03 and CuO. However, substantial amounts of
unreacted CuO were detected in their X-ray diffrac-
tograms even after extending the heat-treatment at 830-
850°C to 216 h. Alternatively, Cava et al. [254] have
found in the synthesis of YBa$&Os that catalysts
(fluxes) such as KzCOs or Na$Os can promote dra-
matically the solid-state reaction of the respective ni-
trates even under 1 atm of oxygen. It may, however,
be claimed that a finite amount of the catalyst possibly
enters the lattice. The synthesis of YBazCudOs based
upon a solid-state reaction route is therefore usually
carried out using high oxygen pressure (typically 400
atm) under which YBazCuaOs can be stable even at
higher temperatures around 1000°C [255,256].
The sol-gel method is of potential advantage over
these solid-state reaction methods as it affords a con-
venient means for synthesizing YBazCu40s using nei-
ther high oxygen pressures nor additive catalysts.
Table 2 gives some representative examples of the
synthesis of YBa$u40s under 1 atm of oxygen by
32 Kakihana
aqueous sol-gel techniques from various kinds of
metal complexes which include citrates [ 193, 1941,
acetate/tartarates [ 163, 165, 167, 2571 and acetates/
propionates/PVA/2-hydroxy isobutyric acid [ 1441. Ex-
amples of YBa2Cu40s prepared under 1 atm of oxy-
gen by other sol-gel routes using metal alkoxides [90,
91, 1051 and organic polymeric glasses [258,259] are
also included in Table 2 for comparison. The immedi-
ate conclusion drawn from Table 2 is that gels derived
from a mixture of acetate and tartarate have produced
eventually single-phase YBa.$udOs at temperatures
below 800°C for relatively short reaction times, typ-
ically 30 to 70 h. The role of tartarate will be dis-
cussed in the next section. Gels derived from metal-
alkoxides seem to have the advantages of shortening the
reaction time (15-20 h) and of lowering the synthetic
temperature even down to 7OO”C, but X-ray diffrac-
tograms of the final samples have indicated the pres-
ence of unidentified impurities with 10% level as well
as CuO with 2% level relative to the strongest 111 re-
flection from YBa,$ZudOs. This phenomenon could
be attributed to the possible heterogeneity of the gels,
arising from the mismatched hydrolysis and conden-
sation rates of the Y-, Ba- and Cu-alkoxides. Nev-
ertheless, this alkoxide route should be regarded as a
promising method for the low temperature synthesis
of YBa+&Os, since the reactivities of the respective
metal alkoxides towards water could be controlled as
described in the preceding section. It should be fi-
nally pointed out that gels derived from organic poly-
meric glasses have also produced eventually single-
phase YBa2Cu40s at temperatures below 820°C for
54-84 h. In particular, the YBa2Cu40s sample pre-
pared by a water-PVA route [259] has shown proba-
bly the best superconducting properties among others
as is evident for a sharp superconducting transition,
AT,(lO-90%) < 2 K.
4.2.2. Acetate Gel (Amorphous Acetate) Processes.
The (aqueous) acetate gel (or amorphous acetate)
method has been widely used for the synthesis of
YBa2Cus07-d powders [127, 139-143, 148, 2601,
fibers [153,154,157-1621 or films [ 1461 and of Biz-
Sr$Za@-tsO, [151, 152, 155, 1561 powders. The
homogeneity of the acetate gel can be ascertained only
in a narrow pH region. The importance of the pH value
of the initial solution has first been pointed out in the
synthesis of YBa2CusO,-d fibers via acetate gels by
Sakka and his coworkers [154, 157-1621, who indi-
cated that the solution should be adjusted to pH =
6.0-6.1 in order to achieve homogeneous gels with-
out phase separation. It has subsequently been re-
ported that the homogeneity of the acetate gel is of-
ten disturbed during the gelation process either by the
crystallization of Cu(CHsCOO)z.HzO in solutions ad-
justed to pH < 5.6 or by the flocculation of copper
hydroxide in solutions adjusted to pH > 6.1 [141]. A
study by Rama Rao et al. [260] has indeed shown
that gels derived from a mixed aqueous solution of Y-,
Ba-, and Cu-acetates adjusted to pH = 7.0 have pro-
duced a strongly multiphase sample with an impurity of
YzBaCuOs phase after the heat-treatment at 900°C for
24 h in air. This was attributed to the presence of indi-
vidual metal acetates in the acetate gel, which brought
about an inhomogeneous distribution of metal ions in
the gel. The same authors have shown in their subse-
quent publication [261] that it was possible to improve
the homogeneity of the acetate gel, thereby to avoid
the formation of YzBaCuOs phase when the pH of the
initial solution was adjusted to 6.0. Similarly, it has
been reported in the synthesis of (Bi, Pb)2SrzCa$usO,
powders that the pH of the starting solution has to be
adjusted precisely to 5.5 in order to avoid the formation
of precipitation [152, 155, 1561.
Alternatively, McHale et al. [262] have reported a
simplified preparation of REBa2Cus07-d (RE = Y, Eu,
Gd, Nd, La) powders using metal-acetates as the start-
ing reagents and practically water-free glacial acetic
acid as a solvent. Glassy gels were obtained by boil-
ing away the acetic acid solution until1 the volume of
the solution decreased to about half of the initial value.
Despite that the solution has been left strongly acidic,
neither crystallization nor precipitation occurred dur-
ing the gelation process. It has been presumed that in
the water-less acetic acid precursor solution dehydrated
metal acetates are slow to crystallize when compared
with the corresponding hydrated metal acetates. As
expected, addition of water into this acetic-acid pre-
cursor solution, after the boiling and drying, resulted
in a crystalline precursor. A heat-treatment of the ac-
etate gel at 900°C for 2 h in air produced a single-phase
YBa&us07-d with a T, onset at 93 K and zero resis-
tance at 9 1 K.
Another way to stabilize the acetic acid precursor so-
lution during the concentration (gelation) process is to
use chelating agents that interact with metal ions more
strongly than the acetic acids do. Chelating agents most
commonly used for this purpose include tartaric acid
[154, 166, 168-1721, citric acid [260], ethanolamine
[147] and triethanolamine [150, 263, 2641. Studies
 “Sol-Gel” Preparation of High Temperature Superconducting Oxides
by Sakka and Zhuang et al. [154, 170-1721 have
shown that transparent acetate gels for the synthesis
of (Bi, Pb)&CazCusOy superconducting powders,
fibers and films have been successfully achieved even
at low pH (3.2-3.3) when the molar ratio of tartaric acid
to copper (C4H40&u) is kept at values between 0.39
and 0.43. Cu(CHsC00)2.H20 is crystallized when
(C4H40&u) is less than 0.26, while X-ray amorphous
white precipitate is formed when (C4H4G&u) is larger
than 0.52.
4.2.3. Citrate Gel (Amorphous Citrate) Processes.
The citrate gel process is thought to be highly promis-
ing and was originally used to obtain highly dispersed
mixed oxides or oxide solid solutions of perovskites,
spinels and garnets [265-2701. The technique was later
on developed for high temperature superconducting ox-
ides by many research groups [58,173-209,260,271].
The first example of the citrate gel process for the
synthesis of YBa$us07-d can be found in works by
Chu et al. [ 1761 and Dunn et al. [ 1811, who prepared
an amorphous citrate gel, starting from an aqueous so-
lution of metal (M)-nitrates and citric acid (CA) with a
CA : M ratio of 1 : 1. Both the CA : M ratio and the pH
value of the initial solution are of utmost importance to
obtain a clear gel with no precipitation. The molar ratio
of CA to total metal cations is usually fixed at 1, which
is the minimum amount of CA needed to bind all metals
assuming that only 1: 1 metal-citrate complexes form in
the solution. Survey of literature describing the syn-
thesis of YBasCus07-d by the citrate gel process has
revealed that the optimum pH lies in values between 5.0
and 7.0 [173, 175, 176, 178, 188, 189, 191, 197, 199,
203, 2081, which is a less limited window of pH when
compared with that (5.6 < pH < 6.1) required for the
acetate gel process. Both the theoretical consideration
[ 1751 and titrimetric data [ 1781 have shown that com-
plexation reaction occurs at pH M 6.0 when citric acid
is added into the aqueous solution containing Y, Ba and
Cu ions, leading to a process of gelation instead of pre-
cipitation. Studies by Chu et al. [176] and Sale et al.
[201] have shown that in solutions that are too acidic
(pH < 2), a precipitate identified as barium nitrate by
X-ray diffraction analysis was formed during evapora-
tion of water. Precipitation of barium nitrate has also
been observed in spray-dried powders derived from
strongly acidic aqueous solutions of metal-nitrates and
citric acid [ 1861. This phenomenon can be interpreted
in terms of the weak interaction between barium ions
and citrate ions under acidic conditions [ 1761. Citric
33
acid (=HgCit) is a tribasic acid that can be dissociated
in aqueous solution to give H2Cit-, HCit2- and Cit”-
ions depending upon the pH of the solution. At low
pH, HzCit- (or even non-dissociated HsCit) is the pre-
dominant species, which interacts weakly with barium
ions owing to the low value of the stability constant
for BaHzCit+; i.e. log,, K (BaHzCit+)/(mol-‘dm’)
= 0.6 [272]. This low value indicates that a non-
negligible amount of free barium ions is left in the solu-
tion. Because of the relatively low solubility of barium
nitrate, it can crystallize as the citrate-&-are solution is
concentrated or spray-dried. The crystallization of bar-
ium nitrate can be avoided when the pH of the initial
citrate-nitrate solution is increased up to a value close to
6.0 by addition of ammonia. At this pH, Cit”- ions are
the predominant species, that interact more strongly
with barium ions to form a stable BaCit- complex
(log,,, K (BaCit-)/(mol-‘dm’) = 2.95) than HzCit-
ions do. The high stabilization of barium ions with
Cit”- ions reduces the concentration of free barium ions
in the solution, thus being able to lead to the formation
of a clear gel with no precipitates upon the evaporation.
Note, however, that further increase in pH exceeding
7 can bring about the formation of precipitates (most
probably hydroxides and their reacted carbonates) as
has been pointed out by Blank et al. [ 1731.
Karen et al. [273] have proposed a simple modified
citrate gel method for the synthesis of YBa$u307-d,
which eliminates the step of pH control in producing
the citrate gel. The procedure involves a liquid-mixing
technique in concentrated citrate solutions (melts) with
a minimum amount of water, starting from non-nitrate
sources of Y, Ba and Cu such as Y203, BaCOs and
CU(OH)~CUCO~.O.~H~O. Highly viscous gels with no
precipitation have been directly obtained by boiling the
concentrated citrate solutions, in spite of no adjustment
of pH. It has been presumed that complexation with the
bridging polydentate citrate ligand is of importance for
the high viscosity.
From a processing point of view, the technique based
upon the concentration of a citrate-nitrate solution has
a unique aspect characterized not only by the forma-
tion of a clear gel but also by “autoignition” (or spon-
taneous combustion). For this reason, the technique
is sometimes referred to as “autoignited citrate gel
process” [ 179,180,200] or merely classified into one of
“combustion” methods [274-2801 rather than “sol-gel”
methods. The autoignition of the gel occurs by a ther-
mally induced oxidation-reduction reaction between
the citrate and nitrate ions, which can be written
34 Kakihana
according to Pederson’s reaction model [278-2801:
9 M(NOs), + 2.5x C6Hs07+ 15x CO2
+ (9/2)x N2+ 10x Hz0 + 9 M0,/2. (39)
Roy et al. [200] have synthesized YBa2Cu307-d pow-
ders using various compositions of gels with differ-
ent citrate-nitrate ratios ranging from 0.13 to 1.OO,and
found that the visible autoignition is restricted to gels
with citrate-nitrate ratios between 0.16 and 0.50. An
important conclusion is that the exothermic nature of
the reaction can be controlled by changing the citrate-
nitrate ratio in the gel, and the best result with regard
to the particle size distribution of the powder has been
obtained for a ratio of 0.3, a value close to the stoi-
chiometric ratio (0.28 derived from Eq. (39)) needed
for the complete combustion of each nitrate ion. It
is thus natural that the use of metal-acetates [208] or
carbonates [197] instead of metal-nitrates as starting
reagents induces no autoignition. YBa2Cus07-d sam-
ples prepared by the (autoignited) citrate gel process us-
ing citrate-nitrate gels with the optimum citrate-nitrate
ratio of x0.3 have shown improved properties com-
pared to those prepared by solid-state reaction tech-
niques [188, 189, 2061; e.g., a sharper superconduct-
ing transition (A.C. susceptibility, AT,( lO-90%) =
0.39 K), larger Meissner effect (56%, field cooling at
H = 17 Oe) and a well-defined specific heat jump at T,
(57 mJ/(K2.mol)).
The citrate gel process has also been successfully
used for the synthesis of high-purity Bi-based [179,
180, 183, 195, 196, 204, 2051, Tl-based [192] and
Pb-based [271] high temperature superconducting ox-
ides. With a few exceptions [204, 2711, the optimum
pH of the initial solution seems to lie between 5 and
7, in a range of values often selected to synthesize
YBa2Cus07-d materials by the citrate gel route as de-
scribed before. A study by Ma and Pierre [195] has
shown that in Bi-Pb-Sr-Ca-Cu-0 systems a so-
lution with the molar ratio of citric acid to cations equal
to 1 gave precipitation near pH = 6 at 60°C. It has then
turned out that clear gels instead of precipitation can be
obtained when a molar ratio of citric acid to cations is
equal to 2 and the pH of the initial solution is adjusted to
7.0. Similarly, precursor solutions for Bi-Pb-Sr-
Ca-Cu-0 superconductors with the molar ratio of
citric acid to metal ions equal to 1 can be stabilized
when an appropriate amount of ethylenediamine [ 179,
1801 or a mixture of ethylenediamine and tartaric acid
[204] have been added to the solutions. The citrate
gel process offers much saving in processing time over
the conventional solid-state reaction method, particu-
larly in the synthesis of (Bi, Pb)$Sr2Ca2CusO, (Bi,
Pb-2223) with a superconducting transition tempera-
ture T, = 110 K. Tampieri et al. [205] have demon-
strated that the high-pure 2223 phase (98% in volume
fraction) can be prepared by the citrate gel process in
a greatly reduced total time (24 h) when compared to
the 150 h or more usually required for the solid-state
reaction method.
4.2.4. EDTA Gel (Amorphous EDTA) Processes.
The main advantage of the EDTA gel method stems
from the fact that under a certain condition EDTA can
bind with most metallic elements in the periodic ta-
ble, making the technique a versatile means in the
synthesis of high temperature superconducting oxides.
The technique has been successfully applied to the
synthesis of YBa2Cus07-d [58, 182, 219, 220, 223,
224,227], BizSr$aCu20s+d [ 182,220-2221 and (Bi,
Pb)$r2Ca2CusOrc+d [219,221-226,228] powders. A
representative example of this approach can be found
in a work by Fransaer et al. [220], who have shown
a general scheme for the preparation of YBazCus07-d
(Y123) and Bi&CaCu20s+d (Bi2212) using EDTA
as a chelating agent. Both the materials made by the
EDTA gel technique have shown a better compositional
homogeneity in comparison with a conventional mate-
rial prepared by a solid-state reaction method. The
precursor for the Y 123 was prepared from Cu powder,
Y203 and BaCOs dissolved in warm nitric acid. Af-
ter mixing the solution, 1 mol of EDTA was added for
every equivalent mole of cations, followed by the ad-
dition of enough ammonia to bring the solution to pH
= 5. The role of ammonia is to dissociate the weak
EDTA acid into one of its complexing subunits (at pH
= 5, EDTA2- is the predominant species; see figure 9).
The solution has first yielded a viscous solution upon
evaporation of water that subsequently vitrified into
a transparent glassy resin upon further concentration.
The precursor for the Bi2212 was also prepared in a
way similar to what has been done in the Y123. Of
particular importance is that no signs of precipitation
are observed until the solution is converted to a gel.
Key parameters that have to be precisely adjusted for
avoiding any segregation or precipitation of the ele-
ments upon concentration involve the pH of the start-
ing solution and the molar ratio of EDTA to total metal
ions. An important publication by Van der Biest et al.
 “Sol-Gel” Preparation of High Temperature Superconducting Oxides 35

The values of stability constants for metal-EDTA com-

plexes are usually large for most of metals that are asso-
ciated with high temperature superconducting oxides
[60], which implies that the concentration of free metal
0.8 ions, [M”+], is lowered (see values of K in Table 3).
This must be considered as a desirable situation in
that the formation of insoluble species derived from
free-metal ions can be avoided upon evaporation of the
solvent. The fully dissociated EDTA, L4-, which is
predominantly formed at pH > 12 (see figure 9), can
strongly interact with a metal ion, M”+, to form a very
stable 1 : 1 complex:

L!u!A
M”+ + L4- tf ML-(4-n) (44)
0.2
with a stability constant K defined as

K = [ML-(~-~)]/([M”+][L~-]). (45)
0.0
0 2 4 6 8 10 12 However, like in the case of citric acid, as the pH of
PH the solution is decreased, other EDTA species such
as HL”-, H2L2-, HsL- and H4L become more and
Figure 9. Mole fraction of ethylene-diamine-tetra-acetic acid
more important (see figure 9) which requires to con-
(EDTA c H4L) and its dissociated species (H3L-, HzL*-, HL3-
and L4-) as a function of pH [281].
sider many side-reactions between the metal ion and
these EDTA species. In order to know how strongly
metal ions are stabilized by EDTA in a given precursor
[58] has shown that pM’-pH diagrams can be used to solution with different values of pH, a sort of condi-
design precursor solutions that bring about no precipi- tional constant, K', instead of the stability constant, K,
tation upon evaporation of the solvent. In what follows, is of much more practical importance. When [L’] is de-
some important chemistries, which should be consid- fined as a total concentration of any free EDTA species
ered in the EDTA gel method, are described in terms of that are not combined with metal ions (Eq. (46)), K'
the so-called conditional constants of M-EDTA com- can be related to [L’] or more practically to Ringbom’s
plexes and related pM’-pH diagrams. side-reactions coefficient QL [57] as written in Eq. (47):
EDTA (=HJL) is a weak tetrabasic acid that can
be dissociated into complexing subunits such as HsL-,
[L’] = [L4-] + [HL’-] + [H2L2-]
HzL2-, HL”- and L4-. Distribution of each species can
be calculated using the known dissociation constants of + W&-l + CH4Ll. (46)
EDTA (Eqs. (40)-(43)) and is shown in figure 9 as a
K' = [ML-‘4-“‘]/([M”+][L’]) = K/aL. (47)
function of pH [281]:
Substituting Eq. (45) for K in Eq. (47) yields:
&I = W+IW&-l/W&l
= 1.02 x 10e2 mol dm-’ (40)
[L’] = [L4-] x CYL. (48)
Ku2 = W+1D-12L2-1/W~L-l
= 2.14 x 10-s mol. dm-’ (41) Introduction of Eqs. (40)-(43) into Eq. (46) leads to
7 2
Ku3= W +IWL--l/F-bL -1
= 6.92 x 10e7 mol. dm-’ (42)
&‘I = L4-I( I+ W+l/%4 + W+12/W~4Kd
Ku4 = [H+][L4-]/[HLs-] + W+l’IU?,4Ku~K,2>
= 5.50 x IO-” mol. dm-‘. (43) $-[H+14/(K,4Ka3K02Ku,)} (49)
36 Kakihana

Table 3. Selected stability constants (K) of various metal-EDTA complexes and their conditional
stability constants (K’) at various pH (Ionic strength is kept at 0.1 mol dme3) [60,281].

pK’ = log,,,[K’/(mol-‘dm3)]
Metal ions pK = log,,,[K/(mol-‘dm3)] pH=4 pH=5 pH=6 pH=7 pH=8

Y3+ 18.1 9.66 11.7 13.5 14.8 15.8

Ba2+ 7.8 -0.64 1.35 3.15 4.48 5.53
cu*+ 18.7 10.3 12.3 14.1 15.4 16.4
La3+ 15.5 7.06 9.05 10.9 12.2 13.2
Bi3+ 27.8 19.9 21.4 23.2 24.5 25.5
Pb2+ 17.9 9.46 11.5 13.3 14.6 15.6
sr2+ 8.7 0.26 2.25 4.05 5.38 6.43
Ca2+ 10.6 2.16 4.15 5.95 7.28 8.33

which can be compared with Eq. (48) to give I I I I I

a~ = { 1+ [H+l/&4 + [H+12/WdGd
+ [H+l’/Wa&dGd 20
+ [H+14/(Ko4Ku3K02K~1)}. (50)

oL is a function of [H+], and logaL is plotted against pH

in figure 10. K’ (Eq. (47)) at a given pH is thus easily 15
calculated using (zr~.derived from figure 10 together
with known values of K. Values of K and K’ with dif- 6c
ferent pH’s are shown in Table 3 for some metal-EDTA
chelate complexes [60] that are important in the EDTA z la
gel synthesis of high temperature superconducting ox-
ides. An immediate conclusion drawn from Table 3 is
that in solutions adjusted to pH 2 6.0 the listed metal
ions except barium, strontium and calcium ions can 5
form sufficiently stable EDTA chelate complexes as is
evident for the high values of K’. The intermediate val-
ues of conditional constants for Ba2+, S?+ and Ca2+
at pH = 6.0 still indicate that these alkaline-earth metal
ions can react nearly quantitatively with EDTA, drop- 4 6 2
ping the concentration of free metal ions down to a level w
at which a sol-gel processing is feasible. At high pH,
M-EDTA complexes must be further stabilized as val- Figure IO. Relationship between Ringbom’s side reactions coeffi-
cient (YL (L = EDTA) and pH [57,281].
ues of their conditional constants are further increased.
However, an upper limit of pH, beyond which precip-
itates form, exists, since OH- or CO:- ions compete
more remarkably with EDTA with increasing pH. EDTA to the total metal ions = 1 or slightly higher
The upper limit of pH can be determined from pM’- than 1, the particular borderlines corresponding to the
pH diagrams. Figures 11 and 12 display such dia- excess EDTA concentration of 10m4 mol. dm-” (i.e.
grams which represent the borderlines of the precip- [EDTA] = [M] + 10m4 mol. dmm3) were chosen from
itation region for various M-EDTA systems divided those calculated by Kragten [55] for the various values
into two groups, {Y3+, Ba2+, Cu2+} and {Bi3+, Sr’+, of the excess EDTA. The lines for Ba2+ in figure 11
Ca2+, Cu2+}, respectively. As the EDTA gel pro- and those for Sr2+ and Ca2+ in figure 12 represent the
cessing is usually carried out with the molar ratio of borderlines for carbonate precipitation in air-saturated
 "Sol-Gel" Preparation of High Temperature Superconducting Oxides 37

8 /
/
7- I (Y,Ba,Cu) "EDTA ] /

6-
/
i |
5- ~',

/
i
I
f %-,t,
4- / !
I
Q. / o
/ I
3- I

Qo P o / / "
2 /
t

1 I
I
I
I
0 I I I ' '~sY' I I I I ! ,
1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
Figure 11. The pM' (M r = y3+, Ba2+ or Cu 2+ )-pH diagram [55]. The precipitation borderlines correspond to excess EDTA concentrations
of 10-4 mol, dm-3: i.e. [EDTA] = [M] + 10-4 mol, dm -3. For details, see text.

8 r

7 I(Bi,Sr,Ca,Cu)-EDTA I
9 !

6 /
/ /
s

5
~ 4 // /
Q.
3
2
Oo
~/.."/,/
/;:iiIIi@
1
I //
0 I I I t r I
1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
Figure 12. The pM' (M' = Bi 3+, Sr2+, Ca 2+ and Cu 2+ )-pH diagram [55]. The precipitation borderlines correspond to excess EDTA
concentrations of 10 -4 mol. dm -3 : i.e. [EDTA] = [M] + 10-4 mol. dm -3, For details, see text.

aqueous solutions, while the remainders correspond to
those for hydroxide precipitation. From figure I 1 we
can design a suitable EDTA precursor solution for the
synthesis of YBa2Cu3OT-a. For instance, the precipi-
tation region of BaCO3 is penetrated by the line I for
concentration, starting from Po which corresponds to
a solution obtained by dissolving each metal salts in a
slightly alkaline-EDTA medium adjusted to pH = 7.5
by ammonia. When the EDTA gel process is planed in
alkaline solutions, all the operations including the con-
centration procedure should be carried out under CO2-
free atmosphere to avoid the formation of insoluble
BaCO3. In this case, concentration wilt not cause pre-
cipitation: the concentration locus of Po does not pene-
trate the precipitation regions of Y(OH)3 and Cu(OH)2,
being able to lead to the formation of a gel. Ba(OH)2 is
38 Kakihana
not needed to consider because of its high solubility in
COz-free aqueous solutions. The point Qs at pH = 6.5
shifts along the line II towards lower pH upon evapo-
ration of water and will not penetrate the precipitation
regions (Evaporation of ammonia which reduces pH of
the solution is not taken into consideration.). However,
as the pH is decreased, the Ba-EDTA complex becomes
unstable which could induce the precipitation of barium
salts upon concentration. This unwanted phenomenon
can be avoided by adding ammonia continuously to
the solution during the concentration, which prevents
a rapid decrease in pH. The concentration locus of Qo
along the line III is a case in point; even a hundred-
fold concentration shifts the experimental condition
to agree with the point Qr at pH = 6.0. In a simi-
lar way, an EDTA precursor solution for the synthesis
of Bi&$aCu20s+d can be designed with the aid of
figure 12. A tenfold concentration of a precursor solu-
tion represented by a point POgives a penetration of the
SrCOs precipitation region (PO+ PI along the line I);
the formation of SrCOs can be avoided by removing
dissolved CO2 gas from the solution. Another ten-
fold concentration shifts the point PI to a new point P2
across the borderline of the bismuth-hydroxide precip-
itation, thus making it difficult to convert the solution
into a clean gel. On the other hand, the locus of Qo
along the line II remains outside the precipitation re-
gion and neither hydroxide nor carbonate precipitate is
formed. The same argument as what has been given
for the line III in figure 11 is true for the concentration
locus of Qo along the line III in figure 12. It should
be borne in mind that the argument described above
is valid provided that neither mixed-ligand (other than
EDTA-OH) nor heterometallic complexes are formed.
Such mixed-ligand complexes are indeed possible in
solutions containing ammonia (e.g. Cu-EDTA-NHs).
However, their influence on the borderlines for the hy-
droxide or carbonate precipitation in the pM’-pH dia-
grams is usually not very significant because of higher
values of K’ in M-EDTA complexes than those in M-
(NH&, complexes [28 11.
4.3. Gel Routes Derivedfrom Organic Polymeric
GhS
The gel route described in this section involves the
formation of organic polymeric glass and may pos-
sess the advantage over other solution routes in that
less tendency for cation segregation can occur during
the process of gelation and pyrolysis of the result-
ing gel. Note, however, that the technique generally
suffers from its own unique problems such as effec-
tive removal of carbon-containing organic polymers
and large shrinkage during heat treatment. The lat-
ter disadvantage renders fabrication of fibers or films
by this technique rather difficult. This explains why
most of previously reported works employing organic
polymeric glass routes have been confined to pow-
der synthesis only with a few exceptions [66, 282,
2831. Nevertheless, because of the potential advan-
tage mentioned above, the technique has to be con-
sidered as one of preferable means in preparing sam-
ples of solid solutions, that are subsequently used to
study doping effects for which a uniform distribution
of the dopant through the lattice is strictly required
[284]. In what follows, several organic polymeric glass
routes to the synthesis of high temperature supercon-
ducting oxides are reviewed. Methods introduced in
this section involve those based upon: a) Pechini-type
polyester reactions (4.3.1), b) radical reactions (4.3.2)
and c) gelation of aqueous polymer precursor solutions
(4.3.3).
4.3.1. Polymerized Complex Routes Based upon
Pechini-7jpe Polyester Reactions. The polymerized
complex process based upon the Pechini route involves
the ability of a-hydroxy carboxylic acids to form metal
chelate complexes, which can undergo polyesterifi-
cation when heated in polyhydroxyl alcohol to form
an organic polymeric glass. Polyesterification be-
tween citric acid (CA) and ethylene glycol (EG) is
most widely used to obtain the Pechini-type polymeric
glass, and it has been applied to the synthesis of vari-
ous high temperature superconducting oxides such as
Lai,ssSra.&u404-d [282, 285, 2861, YBazCus07-d
[66, 282, 283, 285, 287-2951, YBa$&Os [258],
Y2Ba@t70is-d [296], BizSr$aCu20s+d [297-3011,
(Bi, Pb)#zCa2Cus0iu+d [297, 302-3101, Pb$!&,
Ba,Lni-,Ca,CusOs [311] and Pbt-,Cu,Sr2-,Ba,
Yt-,Ca,CuzO~ [311]. Shieh and Thomson [293] have
claimed that it is possible to decompose BaCOs be-
low 690°C and to form YBa2Cus07-d in an helium at-
mosphere using a polymeric precursor derived from a
mixture of metal-acetates, CA and EG. This result sug-
gests a potential of the Pechini-type CARG polyester
route for low-temperature synthesis of YBa2Cus07-d
despite the utilization of carbon-rich polymeric precur-
sors. Unfortunately, there is no concrete description
about the most critical parameters such as the molar
 “Sol-Gel” Preparation of High Temperature Superconducting Oxides 39

Table 4. Factors affecting the homogeneity of gels derived from Pechini-type polyesterilication between citric acid (CA) and ethylene
glycol (EG) mixtures

Entry Oxides cA/Er-$* 1) cm(‘Z) Raw materials HNOs NH40H pH(*“) Precipitation Ref.
la Y-123 112 2.311 M-acetates none none 2.5 none [283]
lb M-nitrates none none n.m. BaNAh
IC none 0 l-9 none
2 111 0.711 M-nitrates none 0 5 none(*4) 12881
3 l/5.3 2.5/l Y-nitrates, BaCOs, none none n.m. none [‘W
CuCO3 Cu(OH)z
4 l/4 2.8/l Y-carbonate, BaCO3, none none nm. none WI
CUCO~CU(OH)~
5 l/5 5/l Y-carbonate, BaC03, none none l-2 none ~2911
CuC03Cu(OH)z
6 Bi-2212 1IO.45 0.711 Bi202, SrCOs, 0 none n.m. Sr(N03h 12911
CaC03, CuO
7 l/2.6 l/O 9 M-nitrates none 0 6.65 none(*5) [301]
8 115 5.311 Bi(NOs)s.5H20, SrCO3, none none l-2 none [352]
CaCOs, CuCO3 Cu(OH)2
9 Bi, Pb-2223 l/15.6 1.14/l M-nitrates none none n.m. Colloidal [3041
precipitate
10 l/5 5.86/l Bi(N0&,5H20, SrCO3, none none l-2 none [352]
Pb(CHsCOO)z, CaCOs
CuCO3 CUE

(*I) “CA/J%” stands for mole ratios of (citric acid)/(ethylene glycol)

(*2) “CAAW stands for mole ratios of (citric acid)/(total metals).
(*3) “n.m.” stands for “not measured”.
(*4) After storage for several days, Ba(NOs)z crystallizes.
(*5) Not described in detail about the appearance of the gel.

ratio of CA to total metals and the CA/EG ratio, the
importance of which will be shown below.
The homogeneity of the resulting gel derived from
the CAiEG mixture is closely related to the distribu-
tion of different elements within the gel. In order to
achieve maximum homogeneity, any precipitation or
crystallization should be avoided during concentration
and polymerization. Success in obtaining clear poly-
meric gels depends mainly upon solubility of metal-
chelate complexes and their stability in a polymeric
medium. Several parameters must then be considered
to ensure the homogeneity of the gels. Among these,
the molar ratio of CA to total metals, choice of raw
materials and the pH of the solution are of major im-
portance as summarized in Table 4. When no pH is
controlled, addition of a large excess of CA relative
to metal ions seems to be indispensable for avoiding
precipitation (see, for example, entries 4, 5, 8 and 10
in Table 4). CA plays an important role in forming sol-
uble M-CA complexes, which are generally stabilized
in excess of CA. The fact that some M-CA complexes
have limited solubility in EG-based medium would lead
to their crystallization during concentration. However,
this can be avoided by freezing each M-CA complex
species in a polyester network derived from the reac-
tion between EG and CA (or even CA in M-CA com-
plexes) before M-CA or M-salts are precipitated. From
this view point, apart from the problem of increasing
the amount of carbon, a large excess of CA with EG
counterbalanced is favorable for obtaining more homo-
geneous multicomponent polymeric gels. Care must be
taken when metal-nitrates are chosen as raw materials
or nitric acid is used to dissolve metal oxides or carbon-
ates. Entries 1b and 6 (and probably 9) in Table 4 show
that Ba(NOs)z or Sr(NO& can be crystallized when
there is a large concentration of NO, ion in solution. To
avoid such crystallization the free NO;concentration
should be kept as low as possible. Supposing that 1
mol of YBa2Cus07-d is prepared, the relative amount
of NOs- is decreased from 13 mol in Entry lb to 3 mol
in Entry 3; no precipitation occurs only in Entry 3 in
spite of nearly equal values of CA/M(total) between
40 Kakihana

the two cases. Increasing pH by addition of ammo- Characterization of Phase Purity

nia, which is another way to avoid the crystallization
of barium nitrate, stabilizes barium-citrate complexes
(Entries lc and 2). Excess nitric acid can react with
ethylene glycol as a strong oxidant to produce glycolic
acid (HOCH2COOH), which is subsequently converted
to unwanted oxalic acid (HOOC-COOH) as it often I
forms insoluble metal-oxalates. Finally, utilization of crystal
acetates (Entry la) or carbonates (Entries 4 and 5) in-
t )
stead of nitrates has produced transparent polymeric
gels with no precipitation.
Typical examples of the synthesis of high tempera-
ture superconducting oxides by the polymerized com-
plex method using CA and EG can be found in a se-
ries of works by Kakihana and his coworkers [5, 258,
289-291, 296, 298, 307, 3101. A matter of concern,
which is worthwhile to mention here, is that a term
“single-phase” often used without much thought would
be highly doubtful. Kakihana et al. [5,290,298] have
then proposed that the phase purity of superconducting
Tb[suue r conduct in&
oxides has to be carefully examined by three indepen-
dent techniques; i.e. X-ray diffraction (XRD), Raman
scattering and complex magnetic susceptibility. The piiizzq
general scheme for impurity detection in oxide super-
Figure 13. A scheme for detectmg impurities in high temperature
conductors by the three techniques is summarized in
superconducting oxides by means of different analytical techniques.
figure 13, where emphasis is placed to the importance According to types of impurity phases (i.e. crystal vs amorphous
of using an appropriate analytical technique in ensur- or superconducting vs semi-conducting/insulating), an appropriate
ing the phase purity according to types of impurity technique must be chosen.
phases (i.e., crystal vs amorphous or superconducting
vs non-superconducting). First, the powerful aspect
of Raman spectroscopy is demonstrated with regard to other hand, in conventional XRD the analysis volume
detection of traces of impurities as compared with the cannot be localized and consequently volume fractions
XRD technique. Figure 14 shows Raman spectra of of impurity phases below several % are sometimes dif-
Y 123-related compounds with a nominal composition ficult to detect. Moreover, very small crystalline re-
of Y1-0,75xBa0.*-0.25xCaxCu307-d. Both theXRD and gions and thin layers of dimensions less than about
Raman scattering measurements have shown that the 10008, (i.e. 0.1 pm) give rise to line broadening of
sample x = 0.1 is virtually of single phase. In con- XRD, which deteriorates the ability of the XRD tech-
trast, the Raman scattering measurement for the sam- nique to detect such impurities. Some precaution is
ple x = 0.3 has shown a spectrum contaminated with a therefore necessary when the phase characterization
very small amount of impurities not readily detectable of superconducting oxides is carried out solely by the
by XRD. Scatterings from traces of impurities such as powder XRD technique. Problems may arise in case
BaCu02 and YzBaCuOs are indicated by shaded parts, where a sample tested contains different superconduct-
and the rest corresponds to scattering from the Y123 ing phases with very similar crystal structures. In such
superconducting phase. It should be stressed here that a case the complex magnetic susceptibility technique
the insulating impurities that could not be detected by can be a very sensitive method to detect unwanted su-
XRD can be readily identified by Raman scattering in perconducting impurity phases in a given supercon-
spite of very small fractions of the impurities [5,290]. ducting sample, even when the corresponding XRD
This is because, on the one hand, the insulating or semi- and Raman patterns indicate a single-phase character.
conducting compounds have much larger Raman cross- A typical example how to apply the complex magnetic
section than the metallic superconductor, and on the susceptibility technique for detecting superconducting
 “Sol-Gel” Preparation of High Temperature Superconducting Oxides
X-ray diffraction
I I I I
28.0 29.0 30.0 31 .o
28
Figure 14. X-ray diffraction (left) and Raman scattering patterns (right) of Y I-u.75xBa2-o.25x CaJIu#-d superconductors. Some insulating
impurities such as YzBaCuOs and BaCuO2 were clearly detected in the sample x = 0.3 by Raman scattering, but hard to be detected by X-ray
diffraction.
impurity phases is shown for a sample with a nominal
composition Ye,sCaa 2Ba$Zus07-d in figure 15, where
the x” peak is composed of at least three components,
implying that the sample contains different supercon-
ducting phases with similar superconducting transition
temperatures.
Keeping this in mind, the purity of one of
YBa2Cus07-d (Y123) samples has been checked by
the three techniques mentioned above. The sam-
ple tested was prepared by the polymerized complex
method according to the flow chart of figure 16 [291].
Stoichiometric amounts of Y2(COs)s . 3Hz0, BaCOs
and CuCOsCu(OH)2 were dissolved in a solution con-
taining CA and EG in the proportions of 5 moles and
25 moles, respectively, for each mole of metal cation. A
clear blue solution was then heated at 130°C to make
a polymeric gel. No precipitation occurs during the
polymerization. The viscous polymeric mass was de-
composed at 350°C and the resulting powder precursor
was calcined at 940°C twice first for 6 h and second for
12 h in 02. The powder was then sintered in pellet form
at 950°C for 15 h and the temperature was decreased
to 400°C at a rate of l”C/min where the sample was
annealed for 12 h. All sintering and annealing were
done in an atmosphere of flowing oxygen. The pos-
sible non-superconducting impurity phases BaCuOz,
41
1Raman scattering
I I I I 1
300 400 500 800 700
Raman shift (cm-‘)
Y2BaCuOS and Y$J.120s, which are most frequently
formed as by-products during the synthesis of Y123,
were not detected by both XRD and Raman scatter-
ing as shown in figure 17. The feature of the Raman
spectrum of the Y123 sample can be fully interpreted
in terms of superposition of various Raman spectra
of single-crystals with different orientations, which in
turn indicates the “single-phase” character of the sam-
ple. Note that the Raman scattering has the advantage
over the XRD technique with regard to detection of in-
sulating impurities. The high-pure nature of the Y 123
sample with regard to superconducting impurities was
confirmed based on results from a complex magnetic
susceptibility measurement in the temperature region
80-100 K as shown in figure 18. The profile of x is
typical of that of a conventional disk sample of ox-
ide superconductors [312]. The real part, x’, exhibits
a typical two-step transition representing the bulk su-
perconductivity and inter-granular weak coupling of
superconducting grains at their boundaries. The on-
set temperature, T&onset), of x’ is 91.5 K (shown by
an arrow in the figure) followed by a sharp transition
corresponding to the weak-link coupling between the
bulk superconducting grains. A blowup of the real
part of the susceptibility near the superconducting tran-
sition determines precisely the onset temperature, as
42 Kakihana
I I I I
0 20 40 60 60
TIK
I I I I I I
0 20 40 60 60
77K
Figure 15. Real (x’ ) and imaginary (x” ) components of x vs tem-
perature for a Ca-substituted superconductor with a nominal com-
position YosCao2Ba#.Iu307-d. The sample tested contains super-
conducting impurity phases as is evident by plural peaks (J-) in x”.
it corresponds to the off-balance temperature in the
carefully zero-balanced bridge. The diamagnetic sig-
nal is almost completely saturated at a temperature
lower than T,(onset) by approximately 2 K; the tran-
sition width (lO-90%) of the full diamagnetism being
0.45 K. Importantly, a single loss peak with a maxi-
mum at about 90.8 K is observed in the x” part of the
susceptibility, which strongly indicates that the sam-
ple is a monophase superconductor within the resolu-
tion of the susceptibility measurement. It is generally
acceptable that the broadening of the superconduct-
ing transition usually reflects the presence of extra-
neous phases such as bulk secondary phases or some
grain boundary phases and inhomogeneities of the ma-
terial. The narrow superconducting transition and a
single x” peak demonstrated in figure 18 should be
attributed to the high purity and compositional unifor-
mity of the sample obtained by the polymerized com-
plex technique. This is consistent with the conclusion
drawn from the X-ray diffraction and Raman scattering
measurements.
It is also possible to utilize couples other than CA/EG
for obtaining polyester-type glassy gels, those involv-
ing oxalic acid/EG [313-3161, EDTA/EG [226, 3171,
EDTA/glycerol [226], tartaric acid/glycol [169] and
salicylic acid/EG [318]. Among these, the couple
EDTA/EG (or glycerol) is of great promise in view of
I I facts that EDTA has the greatest ability to form stable
100
and soluble chelate complexes and that EDTA having
four carboxylic acid groups can react with glycol to
form a more branched polyester, thus greatly inhibit-
ing cation segregation and a more homogeneous pre-
cursor. Chen et al. [3 171have exploited a modified type
of Pechini method to prepare Pb-doped Bi-Sr-Ca-
Cu-0 high-T, superconductors using EDTA to form
stable EDTA metal chelate complexes, which are sub-
sequently polymerized by EG to form a polyester gel.
Although desirable Bi-based materials have been syn-
thesized by this EDTA/EG route with a high percentage
of the 110 K phase and zero resistance at 108 K, there
appears to be still great room for improvement par-
100 ticularly in preparing more homogeneous polymeric
gels. The pH value of 3.0 that they used was prob-
ably too low to keep the solution stable; a colloidal
suspension instead of a clear solution formed. The
formation of such a colloid should be considered as
a factor to introduce chemical inhomogeneity in the
solution system, despite that the as-formed colloidal
suspension was converted to a gel-form precursor af-
ter aging at 40-90°C for 3 h followed by heating at
150°C for 1 day. This problem can be avoided by
increasing pH up to 6.0 which ensures the forma-
tion of EDTA complexes without any precipitation or
colloidalization as pointed out by Gholinia and Sale
[226].
4.3.2. “in-situ” Polymerization Routes Based upon
Radical Reactions. “In-situ” polymerization routes
based upon radical reactions using acrylamide [260,
319-3221, acrylic acid [323] and methacrylic acid
[324-3261 as a monomer can be the alternative to the
Pechini-type polyesterification routes. A representa-
tive example of this approach can be found in a work
by Douy and Odier [319], who have described a new
concept for the preparation of inorganic oxide powders
based upon an “in-situ” polymerization route where the
 “Sol-Gel” Preparation of High Temperature Superconducting Oxides 43

I Y,(CO,), = 3H,O + 4BaC0, + 3CuC0, Cu(OH),

in citric acid/ethyleneglycol I
n

1evolution of CO, gas\

1Metal-Citrate Complexes)
I
condenseat 110430 “c
I
polyesterification
I
1gelation 1
1Polymerized Complex1

r Powder Precursor)

rl calcination at 940 “c for 6 h (1 st time)

and for 12 h (2 nd time) in 0,
I 1pulverization
I
1pelletization under a pressure of 3000 kg/cm” 1
I
1sintering at 950 IZ for 15 h in 0, 1

Figure 16. Flow chart for the polymerized complex procedure used to prepare a YB&u307-d superconducting oxide.
44 Kakihana

1Raman Scattering 1

I I I I I

200 300 400 500 600

Raman shift (cm -’ )

1X-ray Diffraction 1

“s 3
In
s
\ AJ
20 30 40 50
28
Figu~ 17. Raman spectrum (upper) and X-my diffraction (down) of a pure polycrystalline sample of YBa2Cu307--d prepared by the poly
merized complex technique. Symbols “o” in the Raman spectrum correspond to scatterings from pure YBazCu307-d.
 “Sol-Gel” Preparation of High Temperature Superconducting Oxides 45

I I I 1

~6

80 84 88 92 96 IO
T(K)
Figure 18. Complex magnetic susceptibility of YBazCu307-d prepared by the polymerized complex technique. The amplitude of the applied
field is 10 mOe and the frequency is 132 Hz. T,(onset) = 91.5 K and AT,(lO-90%) = 0.45 K.

gel network is made by an organic polymer presumably
independent of the metal ions in solution. Prior to
polymerization an aqueous solution containing all the
desired elements in their stoichiometric ratios was pre-
pared. Complexing the cations by citric acid greatly
improved the stability of the initial solution against
hydrolysis or precipitation. Monomers used were
acrylamide and N,N’-methylene-his-acrylamide. The
gelation of the solution was then initiated by free radi-
cals afforded by hydrogen peroxide and was promoted
by radical transfer agents like N,N,N’,N’-tetramethyl-
ethylenediamine (TEMED). It has been stressed that
the gelation of the solution is achieved by “in-situ” cre-
ating a polyamide network, which is apriori chemically
independent of other species previously in solution. Of
particular importance in this process is that the gel con-
stituted by the polyacrylamide polymer network immo-
bilizes the liquid solution precursors; i.e., the chemi-
cal homogeneity with respect to cation distribution be-
ing maintained almost at a molecular level even in the
gel. Another great and practically important advan-
tage of this process over other solution methods is its
great simplicity. Almost phase-pure tetragonal Y 123
can be obtained by heat treating the gel at 800°C in
air for 5 h. The powder was transformed to its or-
thorhombic form after annealing at 860°C in air for
a few hours followed by a slow cooling. A pellet
specimen obtained after sintering at 950°C in oxygen
followed by a slow cooling exhibited a good super-
conducting property with a T, at 93 K. The same re-
search group has reported in their later publications
[321, 3221 that an intermediate oxycarbonate phase
with a stoichiometry close to YBa2Cu2.95(C03)o.s506.6
forms when apolyacrylamide-citrate gel is heat-treated
between 800 and 850°C in flowing oxygen, which im-
pedes obtaining the pure YBa$us07-d phase at low
temperature. A pure superconducting YBa2Cus07-d
has been easily obtained when the polyacrylamide-
citrate gel is annealed at 925°C in 02 or at 800°C
in Ar and then cooled in 02. The powder ob-
tained using the latter heat-schedule is composed of
much finer and more uniform particles (x0.3 pm),
46 Kakihana
when compared with those of a commercially
available sample.
Rama Rao et al. [260] have synthesized supercon-
ducting YBa2Cus07-d through various sol-gel pro-
cesses using acetate, nitrate-citrate, acetate-citrate and
polyacrylamide-citrate gel routes, and the quality of
the individual gels with regard to chemical homogene-
ity was compared. pH of the mixture solution was
adjusted to 7.0 for all the different processes, and ex-
cept the nitrate-citrate route raw materials used were
confined to metal-acetates. IR, electronic and ESR
spectral studies suggest that copper(I1) acetate aggre-
gates in gels derived from acetate and acetate-citrate
routes, whereas homogeneous distribution of the Cu(I1)
ions is achieved in gels derived from nitrate-citrate
and polyacrylamide-citrate routes. A series of heat-
treatments of these gels under the same condition have
produced YBa$Zus07-d with impurities in different
amounts depending upon the degree of chemical ho-
mogeneity of each gel. The samples derived from
the polyacrylamide-citrate gel route have been found
to yield the purest superconducting YBazCus07-d
with zero resistance at 90 K and AT,( lO-90%)
= 1.2 K.
4.3.3. Water-Soluble Polymer Precursor Routes.
The basic idea behind the water-soluble polymer pre-
cursor route is to lower the mobility of free metal ions
in a polymer solution by increasing interaction be-
tween metals and polymers. Removal of the excess
water forces the polymer species into closer prox-
imity, which increases the probability of crosslink-
ing between them leading to a sudden increase in
the viscosity. Metal ions often behave as cross-
linking centers between polymers when the polymer
possesses the ability to form metal-polymer com-
plexes. Immobilization of such cations in highly
cross-linked polymers is thought to imply inhibition
of segregation of metal ions throughout the result-
ing gel. Polymers most frequently used for the
synthesis of high temperature superconducting ox-
ides involve polyacrylic acid (PAA) [327-3291, poly-
metacrylic acid (PMA) [330-3333, polyamic acid [333,
3341, polyvinyl alcohol (PVA) [335-3381, polyethylen-
imine (PEI) [339-3411, polyethylene glycol (PEG)
[340], EDTA-ethylenediamine (ED)-polyamide [342]
and high molecular weight primary amine [343,
3441.
Chien et al. [330-3331 have developed a poly-
mer-metal-complex (PMC) technique to produce
superconducting YBazCus07-d in the form of pow-
ders, fibers or films. A key principle of the PMC
method proposed by Chien et al. [330, 3331 in-
volves the preparation of a polymeric precursor in
which the various metal ions in the desired stoichio-
metric ratio are homogeneously and uniformly com-
plexed to the polymer. The success or failure of this
type of process depends upon the choice of a poly-
mer possessing functional groups with comparative
complexation affinities for all the metal ions involved.
Polymers chosen involve PMA, poly(viny1 acetate-co-
methacrylic acid), poly(itaconic acid-co-methacrylic
acid) and polyamic acid; all possess carboxylic acid
groups as complexing units for metal ions. As the
maximum homogeneity of the polymer gel would be
achieved by complexing metal ions with equal affinity
to a functional polymer chain, the presence of other
complexing ligands such as an acetate could influ-
ence negatively on the chemical homogeneity of the
final gel. For this reason, utilization of nitrates rather
than acetates has been recommended as raw materi-
als [333]. This type of heterogeneity arising from
different complexing affinities of metal-salts to a func-
tional polymer can be seen in a system of PEI/metal-
acetates. Dela Fuente et al. [339-3411 have syn-
thesized superconducting (Bi, Pb)2SrzCazCu30ie+d,
based upon the use of PEI aqueous solutions containing
the respective metal acetates in stoichiometric amounts.
Ultraviolet-visible and infrared spectroscopic measure-
ments [341] of the initial polymer-containing precursor
mixture have shown the presence of Cu-PEI-acetate
complex resulting from the strong coordinating abil-
ity of N-donor ligands towards Cu, but no evidence
for the formation of polymer-metal complexes have
been found for the rest metals, i.e. metal acetates
can be the form more preferentially present in the
solution.
Heterogeneity of the final gel brought about by the
differences in the complexation affinities of the individ-
ual cations to a polymer can be avoided to a great extent
by utilizing a polymer possessing functional groups
with a much stronger complexation ability than those of
the carboxylic acid group in PMA and the imine group
in PEI. This has been achieved by Maeda et al. [342],
who used water-soluble EDTA-ethylene diamine (ED)
polyamide for a polymer-metal-chelate-complex pre-
cursor for preparing superconducting YBazCus07-d.
The EDTA-ED polyamide prepared by reacting EDTA
dianhydride with ED in equimolecular amount has a
great ability to form a stable polymer-metal-chelate-
 “Sol-Gel” Preparation of High Temperature Superconducting Oxides
complex in water according to a scheme (Eq. (51))
proposed by Maeda et al. [342]:
NH-COCHpN-CH2-CH2-N-CH2CO-NH-(CH2)2
+M
t CH2COOH CH2COOH I- "
NH-COCH2-NrCH2-CH:!,N-CH2CO-NH-(CH2)2
/ ',.., :., \
I y~d,;,y /CH2 7 n
b-C
/ since sequential precipitation rather than simultaneous
0 A
(51)
where M=Y’+, Ba2+ and Cu2+. Maeda et al. [342]
have obtained a clear transparent film upon removal of
the excess water under reduced pressure at 60°C for
5 h. Of particular interest is that neither crystallization
nor precipitation of any of the constituents has occurred
during the gelation process even when pH of the initial
precursor solution has not been adjusted. Pyrolysis of
the gel at 900°C for 10 h in air and sintering at 950°C for
2 h in 02 has resulted in a nearly single-phase supercon-
ducting YBa2Cus07-d with T,(onset) = 90.0 K and
zero resistance at 88.6 K. The temperature dependence
of complex magnetic susceptibility of the same sample
has shown a sharp superconducting transition AT,( lo-
90%) x 0.6 K and a single x” peak similar to that in
figure 18, indicating that the sample is monophase with
respect to superconductivity.
Finally, a unique approach using natural gelling
compounds reported by Macho et al. [345] is worth-
while to be mentioned here. A gel precursor containing
Y, Ba and Cu salts for the synthesis of YBa$us07-d
was prepared using a variety of natural gelling agents
such as gelatin, agar, pectin, alginates, polysaccha-
rides, etc. A typical scheme for obtaining a gel in-
volves the preparation of a hot aqueous solution con-
taining gelatin with l-5 wt% of the solution and the
stoichiometric amount of Y-, Ba- and Cu-acetates fol-
lowed by cooling down to room temperature. A dried
precursor gel (refereed to as “xerogel”) can be easily
obtained by placing the as-prepared gel in a drying
chamber evacuated down to a pressure below 30 Torr
at 45°C or below. One of the characteristic features of
this simple process pointed out by Macho et al. [345]
is that a rigid gel can be obtained even at quite low
concentrations of gelling agents, which practically un-
alters the vapor pressure of the solvent water. This is of
practical importance, as the gel allows the rapid evapo-
ration of the water suitable for scaling-up. XRD phase-
pure (99% or better) YBa2Cus07-d has been prepared
47
by calcining the xerogel precursor at 900°C in air for
16 h followed by annealing at 550°C in O2 for 6 h.
A pressed pellet of the xerogel derived YBa2Cus07-d
powder sintered at 900°C in air for 6 h and annealed
at 550°C in 02 for 24 h has exhibited a sharp resistiv-
ity drop at T,(onset) = 91 K with a AT,(lO-90%) of
the order of 2 K and a linear behavior of the resistivity
vs temperature before the drop at T,, extrapolating to
zero resistance at ~0 K. The above-mentioned advan-
tage of this process can, however, be a disadvantage,
precipitation of all the metal components might occur
during evaporation of the excess water owing to the dif-
ferences of the metal acetate solubilities. Despite no
XRD evidence for crystallization of any compounds
in the xerogel, this does not necessarily ensure a ran-
dom atomic mixture of the cations, as XRD is almost
powerless for identification of amorphous or extremely
small crystalline materials. A possible phase segrega-
tion not detectable by XRD might be at least partly a
reason why lowering the heat-treatment temperatures
significantly below 900°C was not achieved in spite
of the utilization of a relatively carbon-poor xerogel
precursor.
5. Concluding Remarks
The preceding sections (3 and 4) have dealt with some
principles of the chemistry necessary for a better under-
standing of the varied chemical behavior of the three
major sol-gel routes including the alkoxide, chelate gel
and organic polymeric gel routes. They offer many po-
tential advantages over the conventional solid-state re-
action route, including lower processing temperatures,
shorter processing times, higher homogeneity and pu-
rity, and the ability to fabricate thin films or fibers as
well as submicron-size powders. However, in order for
these sol-gel technologies to be used as areally versatile
means in the field of high temperature superconduct-
ing oxides, a number of unresolved chemistry-related
issues must be overcome. One of the serious problems,
that hinders a further progress of the sol-gel synthesis
of high temperature superconducting oxides, is that one
is forced to rely heavily on experience or scanty knowl-
edge of chemistry in designing a molecular precursor
suitable for the subsequent sol-gel processing. The
fact that high temperature superconducting oxides are
highly complicated multicomponent materials having
three or more types of cations in the lattice blocks the
understanding of the overall chemistry involved in a
48 Kakihana
given sol-gel processing due to an increased number of
interactions between different chemical components in
solution. Chemistry that has to be thoroughly studied
differs depending upon the type of the sol-gel method
employed, because of the difference of the principal
attribute of each sol-gel technology. The major issue
that must be considered over the future is summarized
for each individual sol-gel route as follows:
1. The chemistry of the sol-gel route using alkoxides
is primarily based upon hydrolysis and condensa-
tion of the alkoxides in the presence of water. What
is a problem is that almost nothing is known about
the chemistry and behavior of complicated multi-
component alkoxide precursors for high tempera-
ture superconducting oxides when compared with
the tremendous progress of understanding the chem-
istry involved in the gelation of silica sol. The cur-
rent goal is to get rid of mismatch of the hydrolysis
and condensation rates of different alkoxide compo-
nents by chemically modifying a given multicom-
ponent alkoxide precursor solution. Thus the rel-
ative rates of hydrolysis and condensation of the
individual alkoxides upon adding water should be
fully characterized, and their variation induced by
changing in various solution parameters should be
systematically studied. In particular, chemical mod-
ification of the parent alkoxide by adding an appro-
priate organic compound is an important means to
control the hydrolysis and condensation rates. An-
other important subject that has to be studied is to
know if a given precursor solution containing differ-
ent alkoxides has the ability to produce heterometal-
lit alkoxides. It is of vital importance to design such
a precursor solution that forms a heterometallic com-
plex in which the different metal atoms are mixed
in the appropriate ratio in each molecule. Precise
determination of the coordination behavior of the
functional group towards metal ions and the geom-
etry around the metal ion is essential for the further
development of the sol-gel processing. Some spec-
troscopic techniques such as EXAFS and NMR will
be used for investigating such heterometallic com-
plexes in solution.
2. The metal-chelate gel route is basically concerned
with the chemistry of inorganic salts or metal com-
plexes in aqueous solution. A multicomponent
metal-chelate precursor solution is usually designed
on the basis of known thermodynamic data such as
stability constants of various metal complexes. A
serious problem is that thermodynamic data avail-
able have been confined to those valid only for di-
lute aqueous solutions. Detailed evaluation of the
chemical behavior of the precursor solution upon
concentration would need stability constant data on
the metal-complexes in highly concentrated solution
systems, which unfortunately is lacking. Besides
this problem, the fundamental questions related to
the mechanism of sol-gel transition still remain
unanswered: (1) Is there conservation of a metal-
chelate bonding or complete expulsion of the organic
groups from the metal-chelate during the concen-
tration process? (2) Does continued polymerization
leading to oxide network formation occur? (3) Does
the organic group contribute to the formation of gel
network? (4) How does hydrogen bonding play a
role in network formation?
3. Compared with the other two sol-gel routes, the
understanding of the chemistry involved in the or-
ganic polymeric gel route is quite premature. This
is partly due to the fact that the precursor solu-
tion is highly complex chemical mixture of poly-
mer, solvent, cations and anions involving various
kinds of interactions among them. Particularly,
the “in-situ”polymerization route based upon the
Pechini type polyesterification involves a number of
chemistry-related unresolved issues. These include
the uncertainties with respect to (1) the chemical
behavior of metal-chelates during the esterification,
(2) the degree of degradation of free chelating com-
pound (most notably in citric acid [346,347]) during
the polymerization at elevated temperatures, (3) the
degree of crosslinking of polymers which may af-
fect the homogeneity of the cation distribution in
the resulting gel, and (4) the coordination structure
of metal-complexes or polymer-metal-complexes in
solution. The last item is of special importance, as
some ligands such as citric acid, EDTA and ethylene
glycol are known to form heterometallic complexes
when certain pairs of metals are present in solution.
[291,348-3511.
Role of the sol-gel techniques in development of
various substituted or doped high temperature super-
conducting oxides is another important area, which
has not been addressed in this review article. Prin-
ciples and ideas described in the preceding sections
may be adaptable to such more complex doping sys-
tems. Apart from current issues related to techno-
logical applications, the sol-gel technique can lead to
 “Sol-Gel” Preparation of High Temperature Superconducting Oxides 49

high-pure and homogeneously doped superconducting 3. S. Hirano and T. Hayashi, Thermochimica Acta 174, 169
oxides that can be used for various physical property (1991).
4. J.M. Gonzalez-Calbet, Vallet-Regi, and X. Obradors in Srudies
measurements. Careful and systematic studies on the
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