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Research News
Engineering Oxide - Oxide
and Metal- Oxide Microstructures
in Directionally Solidified Eutectics
By Alexandre Revcolevschi* and Guy Dhalenne
1. Introduction
Unidirectional solidification of eutectics from the melt is
an elegant method of fabricating very regularly aligned com-
posite structures made of the two phases of a eutectic. It can
be easily shown that depending on the value of the volume
fraction of one phase with respect to the total volume, the
resulting microstructure consists ideally of either single crys-
talline rods of one phase regularly distributed in a matrix
made of the second phase or of alternating lamellar single
crystalline plates of the two phases. Such aligned structures
have been grown in the last three decades in many metallic
systems, leading to applications mostly related to the good
mechanical properties of these “composite” materials. More
recently unidirectional solidification has been applied to ce-
ramic systems and quite a large number of oxide-oxide eu-
tectics have been studied.“
In the case of systems in which a lamellar structure is
expected, the crystalline symmetry of each phase of the eu-
tectic is an important consideration in the choice of binary
oxide-oxide systems. It was indeed interesting to examine
how the matching of two lattices of similar or different sym-
metry would take place at the interface. As a result it was
generally observed for these lamellar microstructures that
the interfaces separating the two phases are generally sharp
and flat and that they correspond to low Miller index crystal-
lographic planes with rather simple crystallographic relations
between the two phases. Another interesting consideration
guiding the choice of a eutectic system to be grown into a
lamellar microstructure is the tentative engineering of new
microstructural features by inducing a chemical reaction be-
tween the two alternating phases of the eutectic structure.
The first point can be illustrated by discussing several
examples of oxide-oxide lamellar eutectics, namely those
grownin the binary systems NiO-CaO, NiO-Y,O,, NiO-
ZrO,(CaO) and NiO-Gd,O, in which there are no interme-
diate compounds and where the eutectic structures are made
of simple oxides. Nickel oxide has a cubic NaC1-type struc-
I*] Prof. A. Revcolevschi, Dr. G. Dhalenne
Laboratoire de Chimie des Solides, Universite de Paris-Sud
Bit. 414, F-91405 Orsay Cedex (France)
Adv. Muter. 1993, 5, No. 9 0 VCH VL.rlugsgrsdlsrhuftftmbH, 0-69469 Weinheinz, f993
ture and is associated at the eutectic interfaces of these sys-
tems with calcium oxide CaO, which also has an NaC1-type
structure, yttrium oxide Y,O, , which has a cubic bixbyite-
type structure and will be discussed later, calcium-stabilized
zirconium oxide ZrO,(CaO), which has the cubic fluorite
(CaF,) type structure, and gadolinium oxide, which has the
monoclinic B-type structure of the rare earth oxides.
To illustrate the possibility of engineering new microstruc-
tures by chemical reaction at the eutectic interface we show
here that when one has oxide-oxide structures in which one
of the two phases of the eutectic is an oxygen ionic conduc-
tor, one can selectively modify the composition of the second
phase by oxygen addition or removal, thus getting new regu-
larly aligned metal- oxide or oxide-oxide microstructures,
structures impossible to grow directly from the melt.
After briefly examining the growth methods of aligned
oxide-oxide eutectics we shall analyze some general struc-
tural features of such composite materials. In a third section
we shall concentrate on chemical reactions taking place at
the eutectic interface which yield new aligned composite ma-
terials.
2. Growth of Oxide-Oxide Lamellar Eutectic
Structures
Growth from the melt of very regularly aligned eutectic
structures requires a dendrite-free planar liquid- solid
growth interface. Such an interface is obtained when the
constitutional supercooling associated with the presence of
impurities in the liquid is avoided by using growth tech-
niques which allow high C/ R ratios, where C is the tempera-
ture gradient at the solid-liquid interface and R is the growth
rate.C4J
Several crystal growth methods providing such favorable
G / R values can be used,[’. 21 in particular floating zone tech-
n i q u e ~ [’] ~in, which a molten zone is established between two
cylindrical rods of eutectic composition, prepared by powder
compression and sintering, and is slowly moved through the
upper rod.
0935-9648/93/0909-0657 $5.00+ ,2510 651
 Research News

With oxides, growth experiments can be carried out in air,
grow rates being generally of the order of 1 c m h - l ; at this
rate the intermellar spacing /1 of the eutectic structures is
about 1 pm. A relationship between iand the solidification
rate R has been established and is of the form i 2 R = a con-
stant.['] This relationship has been experimentally verified
for most of the systems studied to date and allows, through
proper choice of the growth rate, an easy control of the
microstructure.
Figure 1 represents a typical microstructure of a longitudi-
nal section of an aligned eutectic made of parallel single
crystalline laniellae of the two phases of a NiO-.ZrO,(CaO)
eutectic.
tion of the Miher indices of the interface plane for each phase
are achieved by combining Weissenberg and Buerger preces-
sion diffraction techniques with optical or scanning electron
microscopic observations.l'] Table 1 summarizes the eutectic
compositions and crystallographic data for the four eutectic
structures studied here.
Several interesting features should be noted. The growth
axis is [I 101for the NiO i n all four systems, even though [OOl]
is the preferred growth direction for nickel oxide and more
generally for crystals with the rock salt structure, Also, one
observes that the interface planes have low Miller indices.
Generally these planes correspond to dense arrangements of
atoms as is the case, for example, in the ( 1 1 1) plane of NiO
or (201) plane of Gd,O, . In most samples the growth direc-
tions and crystallographic orientations are unique.
High-resolution electron microscopy (HREM), which
makes lattice imaging possible, confirms these well defined
and simple crystallographic orientations, and indicates that
transition from one phase to the other actually occurs over
a few atomic distances (Fig. 2).[338-101

Fig. 1. Longitudinal section or the NiO ZrO, (CaO) eutectic directionally

solidified a t 1.5 ctnh-'

3. Crystallography of the Eutectic Interfaces

The crystallographic characteristics of the aligned lamellar

eutectics (growth directions and relative orientation of the
two phases and indexation of the interface plane) can be
determined by X-ray and electron diffraction.
The growth directions of the two phases of a eutectic are
determined by carrying out diffractometry experiments on
transverse sections of solidified rods: the preferred growth
direction for each phase is indicated by the enhancement of
Fig. 2. Transverse section of an NiO-calcia stabilized ZrO, lamellar eutectic.
the corresponding X-ray line. The relative crystallographic High-resolution image of a (1 1 I)NiO//(I0O)ZrO2 interface, with a unit step
orientations of the lattices of the two phases and determina- height S.

TJhle I . Cliaracter~sticsand crystallographic rclationships of examples of lamellar eutectic systems.

NiO -CaO NiO- Y,O, NiO- ZrO,(CaO) NiO-Gd,O,

~ ~

Eutectic Composition 40 inolL"4 CaO 31 niol-% Y,O, 70 mol-% NiO

Eutectic P h u e s NiO CaO NiO YD3 N10 ZrO,
Structure Type NaCl N'iCI NaCl pseudo NaCl CdF,
CdF,

Lattice Parsmeter of 4-20 4.7s 4.38 10.60 4.18 5 12

the Eutectic Ph:iaec [A]

Growth Direction

Orientation Relations

Interpace PImc
Research News
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Another interesting feature common to the oxide-oxide
eutectics considered here is a similar atomic stacking on both
sides of the interface: in each phase the sequence of planes
parallel to the eutectic interface corresponds generally to an
alternate stacking of cationic and anionic planes with com- Gd, Gd2 Gdg 0

parable atom density. This is obvious for the three systems

NiO-CaO, NiO-Y,O, and NiO-ZrO,(CaO) as seen in
Figure 3. In the case of Y,O,, which has a bixbyite-type

Fig. 4. Projection (dong the b axis) of the 8-type rare-earth sesquioxidc struc-
ture adopted by Gd,O,.“” The layered character of the structure eiiiphasizcd
ClllS ClllS c100>
in the literature[i8Jis evidenced by broken lines dividing the structure into
(LnO):O and oxygen sheets, indicated by B and A, respechvely.

Ca.~i 4. Engineering of New Microstructures by

Chemical Reaction at the Eutectic Interfaces

Among the lamellar structures discussed above let us con-

I &y2 Ni Zr sider now the NiO-ZrO,(CaO) eutectic. If we heat such a
composite at a temperature of about 1100°C under a low
Fig. 3. Schematic representation of the NiO--CaO interface and of the atomic partial pressure of oxygen of about lo-’’ atm (which is re-
layers of Y 2 0 p ,NiO and ZrO, (cubic), viewed perpendicularly to growth direc-
tions (i.e. parallel to interfaces). In the case of the NiO-CaO system, the small
ducing for NiO) we note that a rapid formation of Ni occurs
amounts of Ni in the Ca planes and Ca in the Ni planes which are indicated in the longitudinal direction between the ZrO, plates, where-
correspond to the existence of extended terminal solid solutions in the NiO- as these plates maintain a constant dimension, but may expe-
CaO phase diagram. In the bixbyite structure (YzO,), along a (001) direction
the atoms are not strictly coplanar and define either planes which contain both
rience some plastic deformation (Fig. 5). If we now take a
Y, and Y, ions or “sheets” composed of Y, ions only.

structure (a structure which can be described as a defective

cubic fluorite structure in which one out of the four fluorine
atoms of the (100) type planes is removed from the lattice cell
with relaxation of the three remaining ones in the (100)
plane), the oxygen planes and one type of the yttrium planes
(Y,) are represented as thick layers because of the puckered
distribution of atoms in these planes;[”] the crystallographic
relations at the interface found for these three systems
(Table 1) show that, parallel to the interface, the plane se-
quence from one phase to the other is of the type metal-oxy-
gen-metal-oxygen-(metal)’-oxygen-(metal)’, indicating
that the transition from one phase to the other takes place
through an oxygen plane.
This is not immediately obvious for the NiO-Gd,O, eu-
tectic where at the interface we have (lll)NiO//
(201)Gd,0,.[121 (207) does not seem at first sight to be a
simple plane of the monoclinic B structure of the rare earth
oxides adopted by Gd,O,. However, if one projects the
structure of Gd,O, along its b axis one can observe a lamel-
lar structure made of mixed layers (LuO);@ of 201 orienta-
tion separated by parallel oxygen ions (Fig. 4). Therefore
here again, the transition from NiO to Gd,O, seems to take Fig. 5. Optical observation of the reduction front in the longitudinal direction
of an NiO-ZrO, (CaO) lamellar cutcctic showing in the upper part of the
place through a succession of oxygen-nickel-oxygen- picture the oxide-oxide eutectic and below, the Ni-ZrO, (CaO) composite (Ni
(LnO): -oxygen - (LnO): planes.[’ ’1
@
is the white phase and ZrO, the darker phase).

Adv Muter 1993, 5, No. 9 0 VCH VerlaggeJellschuft mbH, 0-69469 Wernherm,1993 0935-964Rl93109OU-0659 $ 5 OO+ Z i / O 659
 ADVANCED
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large NiO single crystal and expose it to the same experimen-
tal conditions, the rate of reduction is about two orders of
magnitude slower than for the reduction of the composite in
the longitudinal direction.
Another interesting feature of the reduction of this oxide-
oxide lamellar structure to a metal-oxide lamellar structure
is that the crystallographic relationships outlined above for
the starting oxide-oxide material are maintained in the re-
sulting metal-oxide aligned structure.
Both the rapid reduction and the topotaxy which is ob-
served can be interpreted using an electrochemical local cell
model, which takes into account the high electrical conduc-
tivity of oxygen ions in stabilized zirconia at high tempera-
ture as well as the electronic conductivity of metallic nick-
e1.[13~
Figure 6 is a schematic drawing of an aligned NiO-
ZrO,(CaO) composite at steady state, after longitudinal re-
duction has been initiated. Initially some direct reduction of
GAS PHASE
I
I I
I
It
Id
I
L-I
I
I I
NiO
Fig. 6. Schematic diagram of a cross-section ofthe Ni/NiO interpace in a lamel-
lar eutectic NiO-ZrO,(CaO) partially reduced at high temperature under a
CO/CO, mixture.
NiO by the CO,/CO gas at the surface (y = 0) occurs quite
quickly to form a dense surface layer of Ni which insulates
the NiO plate from the gas phase. Further reduction would
require the slow diffusion of atomic oxygen through this
layer of Ni at the surface. In this case, one would expect that
faster reduction kinetics are achieved if oxygen is transport-
ed to the external surface as oxygen ions in the zirconia,
while the electrons reach the reduction site in the interior
through the nickel phase. The following three interfacial re-
actions would comprise the reduction sequence :
at the composite interface
CO(g) + OZ0(ZrO,) -
CO,(g) + 2e'(Ni) + V,(ZrO,)
660 m h H , 0-69469 Weinhein?, 1993
Q VCH ~,rlu~.s~csrllschrrft
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at the internal Ni/ZrO, interface
O(Ni) + V,(ZrO,) + 2ee(Ni) - 020(Zr0,)
NiO -
at the internal Ni0,"i
Ni + 0
interface
(3)
As shown in Figure 6, because the oxygen is removed at
the advancing reaction front by conduction through the zir-
conia, the Ni/NiO interface must maintain a sloping geome-
try (fork shape). The lateral diffusion of atomic oxygen (in
the x direction) to reach the Ni/ZrO, interface would con-
tribute to rate control at very short times, but at steady state,
the conduction of oxygen ions through the ZrO, plate to the
surface would limit the kinetics. In comparison, the electrical
resistance in the nickel phase is considered to be negligible.
Comparison between theory and experimental kinetic
data relative to the variation of the penetration depth of Ni
in the longitudinal direction of a eutectic structure shows a
very good agreement and also the forks of nickel predicted
by the model are observed experimentally at the Ni/NiO
interface (Fig. 7).Li3]
Fig. 7. SEM micrograph of an Ni/NiO interface showing long forks of Ni in an
oriented NiO-ZrO,(CaO) eutectic after exposure to a gaseous CO;CO, mix-
ture (PO, =1.6x lo-'' alm) at 1075'C for 3 hours.
Let us consider now, in addition to the systems discussed
above, the Coo-ZrO,(CaO) system, which is a parent sys-
tem of Ni0--ZrO,(CaO): NiO and COOboth have a sodium
chloride type structure, and aligned lamellar eutectic struc-
tures made of C o o and ZrO,(CaO) plates can also be grown
in this system by directional solidification at a composition
of 73.5 mol0/0 COO, 22.5 % ZrO, and 4 mol YOCaO.
When selective reduction experiments similar to those
mentioned earlier are carried out on this system, with the
oxygen partial pressure and temperature being such that
COO should be selectively reduced to metal cobalt, once
again well-aligned metal-oxide Co--ZrO,(CaO) structures
(1)
are ~ b t a i n e d . " ~ ]
However, there is an additional feature of interest associ-
ated with the Coo-ZrO,(CaO) system with respect to the
0935-9648/93/0909-0660$5.00+ .Z5,!0 Adv. Mntcr. 1993. 5 , N o 9
Research News
nickel oxide-zirconia system; it is the existence of cobalt in
both the oxidation states I1 and 111. This has led us to oxida-
tion experiments on C o o - ZrO,(CaO) lamellar eutectic
samples, in conditions where COO should be oxidized to
Co,O,: by heating samples of aligned composite structures
at 880°C under 1 atm pure oxygen, aligned samples of
Co,O, and ZrO,(CaO) phases were obtained as shown by
X-ray diffraction experiment~.['~]
Upon oxidation, samples get slightly fractured but retain
the very regular aligned lamellar structure of the starting
material. In order to understand the oxidation mechanism, it
is interesting to partially oxidize the samples and examine
their microstructures (Fig. 8) A striking feature made of up-
ward pointing forks appears in the cobalt oxide phase. These
forks mark the phase boundary between the upper part of
the lamellae made of Co,O,, and the lower part made of
unreacted COO.
Fig. 8. SEM micrograph showing a cross-section of a eutectic COO-
ZrO,(CaO) compositc partially oxidized aftcr an exposure of 0.33 hours under
1 atm 0,.
The analogy between this fork-type morphology and that
observed upon reduction of ZrO,(CaO)-NiO lamellar com-
posites into lamellar ZrO,(CaO)-Ni structures[13]suggests
the existence of an electrochemical local cell process whereby
the rapid oxidation of COO into Co,O, would occur by
oxygen transport through the cubic zirconia phase. To con-
firm such a mechanism, the depth of oxidation in the longi-
tudinal direction of the composite structure was compared to
that observed for single crystalline samples of COO submit-
ted to an identical oxidation treatment, and indeed for the
aligned composite structure the oxidation depth was about
three times greater after four hours heating at 880 "C.
To interpret the fast oxidation process, it i s important to
consider that the oxidation of COOto Co,O, takes place by
outward diffusion of Co ions over cation vacancies leading
to formation of Co,O, at the Co,O,/O, interface. Simulta-
neously, an inward conversion of COOinto Co,O, occurs at
Adv Muler 1993. 5,N o 9 $) VCH Verlugcgr,elh<huftmDH D-69469 Wernherm. 1993
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a flat interfacial boundary.['61 The fork-shaped microstruc-
ture resulting from the partial oxidation of ZrO,(CaO)-
COOcan hence be explained here again by considering that
the faster oxidation kinetics can be achieved by oxygen-ion
transport through zirconia but this time from the external
surface to the internal oxidation front. Co,O, forms at the
cobalt monoxide/zirconia interface and the sloping geometry
(fork shape) for the interior Co,O,/CoO interface can be
explained by lateral diffusion of Co ions from the advancing
reaction front towards the zirconia phase.
The comparison between the Weissenberg and precession
patterns of non-oxidized as-grown samples and partially
and/or totally oxidized samples indicates that the crystallo-
graphic orientation of Co,O, with respect to the zirconia
phase is identical to that of the initial COO with zirconia
(Fig. 9). The crystallographic relationships between
Co,O, and ZrO,(CaO) are therefore: [I 1O]Co,O4//[O011-
ZrO,(CaO) and (1 1 1 ) Co30,//(l0O) ZrO,(CaO).
021 20?
0 coo
10 I01 2r02
rTTz1cojo4
I I
/!%2+3
021 020 012
Fig. 9. Precession zero-level patterns and schematic indexing of CoO-
ZrO,(CaO) eutectic (top) and Co,O, . ZrOl(CaO) composite (bottom) ob-
tained by oxidation of CoO-ZrO,(CaO) eutectic: Top) normal to [lUO] of
ZrO,(CaO) and [ l l l ]ofCoO [(Mo-K, radiation)]. Bottom) Normal to [loo] or
ZrO,(CaO) and [ l l l ] of Co,O, (Cu radiation, Ni filter).
Such a topotactic reaction can be easily explained when
considering that the spinel-type structure of Co,O, is made
of a close-packed cubic arrangement of oxygen ions with
one-half the octahedral holes and one-eighth of the tetrahe-
dral holes filled with cations. We have seen above that oxida-
tion into Co,O, of sodium chloride-type COO, which has a
structure made of two interprenetrating fcc sublattices of Co
0938-9648/93/0909-06613 5 00 + 2510 661
 ADVANCED
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and oxygen ions, takes place through an outward diffusion
of Co ions, leaving intact the fcc oxygen sublattice of COO.
This anionic sublattice, which has become that of Co,O,,
keeps its original crystallographic relationship with respect
to the zirconia phase and imposes the orientation which is
observed between ZrO,(CaO) and Co,O,.
5. Conclusion
It is shown here for a few typical examples that directional
solidification of oxide-oxide eutectics can provide interest-
ing lamellar microstructures made of very regularly spaced
alternating oxide phases. The crystallographic relationships
between the phases are simple and the interfaces are general-
ly flat, transition from one phase to the other taking place
over a few atomic distances.
The engineering of new microstructures can be achieved
by selective chemical reduction or oxidation of one of the
two phases, leading, through topotactical reactions, to novel
regularly spaced metal-oxide or oxide-oxide microstruc-
tures impossible to fabricate directly from the melt.
Research News
Charge Transport in Random
Organic Photoconductors
By Heinz Bassler*
1. Introduction
To date, electrophotography is the only area in which the
photoelectronic properties of organic materials are exploited
on a large-scale industrial basis. The current technology of
xerography requires that the photoconductor be manufac-
turable in the form of a homogeneous large area film, typi-
cally 20 pm thick, be suitable for corona charging and able
to discharge completely in no less than, say, 1 ms upon expo-
sure to flash irradiation. It is obvious that neither crystalline
[*] ProT. H. Biissler
FB Physikalische Chemie und Zentrum fur Materialwissenschaften
Philtpps-UniversitHt Marburg
Hans-Meerwein-Strasse, D-35043 Marburg (FRG)
662 I( VCH K ~ / a g ~ ~ e ~ e l lmhH
r ~ / ~0-65465
aft
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[I] R.L. Ashbrook. J. Am. Ceram. Soc. 1977, 60, 428.
[2] V.S. Stubican, R.C. Bradt, Ann. Rev. Muter. Sci. 1981, 11, 267.
[3] A. Revcolevschi, G. Dhalenne, D. Michel, Muter. Sci. Forum 1988, 2Y,
173.
[4] F.R. Mollard, M.C. Flemings, Trans. A I M E 1967, 239, 1526.
[S] L. Trouilleux, G. Dhalenne, A. Revcolevschi, J. Crysr. Growth 1988, 51,
268.
[6] W.A. Tiller, Liquid Metals und Soli&fication. ASM, Cleveland, OH, 1958,
p. 276.
[7] M. Fragneau, A. Revcolevschi, J. Am. Cerum. Suc. 1983,66, C-162.
[XI V.P. Dravid, C.E. Lyman, M.R. Notis, A. Revcolevschi, Ulfrumicroscop!:
1989, 29, 60.
[9] V.P. Drdvid, C.E. Lyman, M.R. Notis, A. Revcolevschi, Meral. Trans.
1990,2i, 2315.
[lo] J. Echigoya, G. Dhalenne. A. Revcolevschi, Proc. lnl. Conf Science of
Ceramics f4 (Ed: D. Taylor) The Institute of Ceramics, London 1988,
p.437.
[Ill M. Fragneau, A. Revcolevschi, D. Michel, Advances in Cerumics, 1983, 6,
110.
[12] B. Dubois, G. Dhalenne, F. D'Yvoire, A. Revcolevschi, J. Am. Ceram. Soc.
1986, 69, C-6.
1131 B. Bonvalot-Dubois, G. Dhalenne, J. Berthon, A. Rcvcolcvschi, R. Rapp,
J. A m . Ceram. Soc. 1988, 7 t , 296.
[I41 B. Bonvalot-Dubois, G. Dhalenne, A. Revcolevschi, Proc. Chararterira-
tion o f t h e Structure und Chemistry of Defects in Materials, Vol. 138. (Eds:
B.C. Larson M. Ruhle D.N. Seidman) MRS, Pittsburgh 1989, p. 587.
1151 G. Dhalenne, P. Berthet, F. D'Yvoire, A. Revcolevschi, Solid State Ionics
1993, in press.
[16] K. Przybylski, W.W Smeltzer, J. Elec!rochem. Soc. 1981, (28, 897.
1171 D.T. Cromer, J. Phys. Chem. 1957, 61, 753.
1181 P.E. Caro, J. Less-Common Me!. 1968, 16, 367.
nor polycrystalline materials fulfill these requirements. Ob-
vious candidates are polymers and, notably, molecularly
doped polymers in which the dopant is responsible for the
photoelectronic properties while the polymer binder deter-
mines the morphology and, concomitantly, the mechanical
properties. On the other hand it was, at the beginning of
modern organic photoconductor technology, anything but
obvious whether or not polymeric materials can ever meet
the purity requirements for trap-free transport. In fact, trap-
ping, supposedly by inadvertant incipient carbazole sand-
wich pairs, turned out to be the main disadvantage of
polyvinylcarbazole,['] the first known polymeric photocon-
ductor. It reduced the charge-carrier mobility 1.1 to values
incompatible with the above limit of the transit time that
Weinhefm i953 0935-5648/93/0505-0662$ 5 00+ 2510 A h M m e t 1993, 5 , No 9