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D. Hesse, S. Senz: Interfacial reaction mechanisms and the structure of moving heterophase boundaries
Dietrich Hesse, Stephan Senz
Max-Planck-Institut für Mikrostrukturphysik, Halle (Saale), Germany
Interfacial reaction mechanisms and the
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structure of moving heterophase boundaries
during pyrochlore- and spinel-forming solid state
reactions
If bulk or thin-film ceramics consisting of more than one
component are subjected to a high temperature during pro-
cessing or use, interfacial solid – solid reactions occur be-
tween the components. To understand this type of reactions,
the atomic structure of various reactive oxide/pyrochlore
and oxide/spinel model interfaces is studied by high-resolu-
tion transmission electron microscopy. Kinetics of the pyro-
chlore- and spinel-forming reactions at these interfaces are
shown to depend on the atomic structure of the interface,
in particular on that of the interfacial dislocations. During
the reaction, these dislocations have to move together with
the advancing interface. Accordingly, reaction kinetics are
determined by the mode of dislocation movement and, thus,
by the Burgers vector geometry of the interfacial disloca-
tions. The type of interfacial dislocations is, in turn, influ-
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enced by the stress conditions during the initial stage of
the solid state reaction.
Keywords: Solid state reactions; Reactive interfaces; Spi-
nels; Pyrochlores; Electron microscopy
1. Introduction
© 2004 Carl Hanser Verlag, Munich, Germany
Solid state reactions in ceramic materials have been investi-
gated for many years and are still the subject of intensive re-
search [1 – 8]. Studying such reactions, one can learn about
the influence of thermodynamic potentials, crystal defects,
interfaces, and their interactions, on phase formation pro-
cesses during solid state reactions. If bulk or thin-film ceram-
ics consisting of more than one component are subjected to
high temperature during processing or in use, interfacial
solid – solid reactions may occur between the components.
Even if these reactions extend only a few nanometers into
the adjacent phases, they may affect the desired properties
of the ceramics. Investigating the interfacial reaction mech-
anisms and the structure of the moving heterophase bound-
aries will improve the understanding of such solid state re-
actions. Spinel- and pyrochlore-forming topotaxial solid
state reactions as
AO + B2O3 ! AB2O4 (1)
2 AO + BO2 ! A2BO4 (2)
2 AO2 + B2O3 ! A2B2O7 (3)
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are prototypes of chemical reactions in complex oxides, cf.
[1, 3]. As will be shown, interfacial dislocations may play
an important role in these reactions. This role has been
investigated experimentally, using (high-resolution) trans-
mission electron microscopy (TEM), scanning force
microscopy (AFM), and X-ray diffraction.
2. Experimental
Reactive MgO/spinel and ZrO2/pyrochlore interfaces
were prepared in a high-vacuum environment or in air,
using commercial MgO(100) and Y2O3-stabilized cubic
ZrO2(100) (YSZ) single-crystal surfaces of different micro-
topography. The MgO or YSZ substrates were heated to a
high temperature (1100 to 1300 °C) and then subjected to
the vapour of a binary oxide (TiO2, Cr2O3, SnO2, In2O3,
La2O3, etc.). The vapour was generated by electron-beam
evaporation (5 kV; 100 mA) of a pressed or sintered powder
target, or – in case of SnO2 and In2O3 – by thermal evapora-
tion of an oxide powder. The evaporation/deposition rate of
about 0.2 nm/s was controlled by a quartz microbalance. In
this way, crystallographically well-defined reactive inter-
faces between the initial substrate and a certain product
phase – a spinel or a pyrochlore in the form of a thin
film, or of thin islands – were prepared, in particular
MgO/Mg2TiO4, MgO/MgCr2O4, MgO/MgIn2O4, MgO/
Mg2SnO4, and ZrO2/La2Zr2O7 reactive interfaces.
The initial MgO and YSZ surfaces, the spinel and pyro-
chlore phases, and the reactive interfaces were investigated
by scanning force microscopy (AFM), X-ray diffractometry
(XRD), and particularly by high-resolution transmission
electron microscopy (HRTEM) of cross sections. The elec-
tron microscope investigations were performed in the trans-
mission electron microscopes Philips CM20T (at 200 kV),
and JEM 4000 EX (at 400 kV). The samples were thinned
by standard grinding, gluing and ion-beam methods. Details
of the experiments are described, e. g., in Refs. [9 – 14].
Table 1. Lattice parameters (in Å) of the involved phases.
MgO ZrO2 MgAl2O4 Mg2GeO4 MgCr2O4
4.213 5.1 8.08 8.246 8.33
MgFe2O4 Mg2TiO4 Mg2SnO4 MgIn2O4 La2Zr2O7
8.39 8.44 8.64 8.83 10.8
 Carl Hanser Verlag, München Z. Metallkd. 95 (2004) 4
Not for use in internet or intranet sites. Not for electronic distribution.
D. Hesse, S. Senz: Interfacial reaction mechanisms and the structure of moving heterophase boundaries
3. Results
3.1. Lattice misfit and orientation relationship
The structure of reactive interfaces depends on the crystal-
lography and on the mutual orientation of the phases sepa-
rated by the interface. Depending on the lattice parameters,
a, of these phases, a lattice misfit, f (in %), is present along
the BO/PS reactive interface (PS – pyrochlore or spinel;
BO – binary oxide, i. e., MgO or ZrO2)
f = 200 · (aPS/2 – aBO)/(aPS/2 + aBO)
Sign and amount of the lattice misfit, in turn, determine the
geometry of the misfit dislocation network forming. All the
phases investigated (MgO, ZrO2, spinels, pyrochlores) have
a cubic crystal structure. Table 1 gives an overview of the
lattice parameters of the phases involved in our experi-
ments. In a first approximation, the prepared BO/PS reac-
tive interfaces turned out to be characterized by cube-on-
cube orientation relationships between the binary oxide
and the spinel or pyrochlore, respectively:
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(001)BO || (001)PS; [100]BO || [100]PS
© 2004 Carl Hanser Verlag, Munich, Germany
Fig. 2. Plan-view diffraction contrast analysis of the Burgers vectors of the misfit dislocations at the MgO/MgCr2O4 reactive heterophase bound-
ary. (a) Bright field (BF) image. (b) – (e) Dark field (DF) images. g is the diffracting vector.
Z. Metallkd. 95 (2004) 4
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Fig. 1. Cross-sectional TEM
micrographs of the MgO/
Mg2TiO4 reactive hetero-
phase boundary.
This was established by XRD, electron diffraction, and
high-resolution electron microscopy [9 – 14]. As an exam-
ple, Fig. 1 shows the TEM overview (a) and a high-resolu-
tion micrograph (b) of a cross section of the MgO/Mg2TiO4
reactive interface formed due to a reaction of type Eq. (2),
with A = Mg and B = Ti. The cube-on-cube orientation re-
lationship between MgO and Mg2TiO4 is clearly revealed
by the HRTEM image.
3.2. The network of misfit dislocations
(4) Depending on sign and amount of the lattice misfit, misfit
dislocation networks of different Burgers geometries were
found at the reactive interfaces. The network spacing, and
the Burgers geometry (Burgers vector b and line vector <)
of the dislocations constituting the network were analysed
in detail applying diffraction contrast methods to plan-view
samples and also Burgers circuit analyses of HRTEM cross
section images. As an example, Fig. 2 shows the plan-view
diffraction contrast analysis of the misfit dislocation net-
work at the MgO/MgCr2O4 interface, and Fig. 3 shows a
corresponding cross-sectional HRTEM image of this inter-
(5) face. The analysis yields a spacing of (25  5) nm, and a
Burgers geometry characterized by the Burgers vectors
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D. Hesse, S. Senz: Interfacial reaction mechanisms and the structure of moving heterophase boundaries
Not for use in internet or intranet sites. Not for electronic distribution.
Fig. 3. HRTEM image of a cross section of the MgO/MgCr2O4 reac-
tive heterophase boundary, seen along the [110] direction of MgO and
spinel. ‘B’ marks a coherent region of the boundary, whereas ‘C’ marks
a misfit dislocation with an in-plane Burgers vector b = 1/2 aMgO [110].
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© 2004 Carl Hanser Verlag, Munich, Germany
Fig. 4. Part of an X-ray pole figure of a sample containing a MgO/
Mg2SnO4 reactive heterophase boundary. The (008) spinel peak is split
into four sub-peaks. The polar angle ranges from 0 (centre) to 3° (rim).
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b1 = 1/2 aMgO [110] and b2 = 1/2 aMgO [110] for the two sets
of dislocations, and by the corresponding line vectors
<1 = [110] and <2 = [110]. This shows that the dislocations
are of pure edge type, and that the Burgers vector lies in
the plane of the interface. The MgO/MgCr2O4 orientation
relationship was shown to exactly correspond to Eq. (5).
In other cases, however, well-defined small deviations
from this orientation relationship occur, with the crystal lat-
tice of the spinel or pyrochlore phase, respectively, being
tilted away from Eq. (5) by a few degrees. This tilt may oc-
cur into four directions, in correspondence with the fourfold
crystal symmetry of the BO (001) crystal surface, resulting
in a split-up of the (00<) spinel and pyrochlore reflections
in XRD pole figures into four sub-reflections (Fig. 4). Ac-
cordingly, tilt domains of four types appear in the spinel
and pyrochlore phase, which can be visualized by AFM
and TEM in the initial reaction stages, when individual spi-
nel or pyrochlore islands are formed (see Figs. 8 and 9 be-
low). Moreover, in the cases of deviations from Eq. (5),
out-of-plane Burgers vectors of the misfit dislocations were
found (Fig. 5) instead of in-plane vectors. Sense and
amount of the tilt of the spinel (or pyrochlore) lattice are
correlated to the Burgers vector geometry of the disloca-
tions of the corresponding misfit dislocation network. Ta-
ble 2 presents a summary of the experimental findings at
the different reactive interfaces investigated, viz. the mor-
phology (p – plane; r – rough), the amount of the deviation
from Eq. (5) in terms of tilt angle, the absence ( – ) or pres-
ence (+) of a dislocation network, and the Burgers vector
geometry (b; <) of the dislocations constituting this net-
work. Also shown are sign (+; – ) and amount (in %) of the
lattice misfit, f, involved.
From Table 2, the following phenomenological summary
can be deduced. In cases of very low misfit (MgO/
Mg2TiO4; MgO/MgFe2O4) no dislocation network and no
tilt occur. The reactive interface is coherent (cf. Fig. 1b),
which can be explained by the inert f.c.c. oxygen sublattice
of MgO simply being taken over by the spinel due to
Wagner’s cation counterdiffusion reaction mechanism [15]
(cf. Ref. [16] for thin-film reactions). At negative misfit
(e. g., MgO/MgCr2O4), a network of misfit edge disloca-
tions with in-plane Burgers vectors is present at the reactive
interface, while at positive misfit (e. g., MgO/MgIn2O4 and
ZrO2/La2Zr2O7), a network of misfit edge dislocations with
Fig. 5. HRTEM image of a MgO/MgIn2O4 re-
active heterophase boundary. (a) Unfiltered,
(b) (200) Fourier-filtered, and (c) (002) Four-
ier-filtered images, indicating two sets of extra
half-planes, and accordingly two Burgers vec-
tor components b|| and b?, respectively.
Z. Metallkd. 95 (2004) 4
 D. Hesse, S. Senz: Interfacial reaction mechanisms and the structure of moving heterophase boundaries
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Table 2. Determined characteristics of the reactive interfaces prepared on flat MgO and YSZ (001) substrate surfaces, respectively, by
reactions with binary oxide vapours.

Interface Misfit f (%) Morphology Tilt angle Disloc. network Burgers vector Line vector
1
MgO/MgAl2O4 – 4.2 p 0 + /2 aMgO [110] [110]
1
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MgO/Mg2GeO4 – 2.0 r 0 + /2 aMgO [110] [110]

1
MgO/MgCr2O4 – 1.1 r 0 + /2 aMgO [110] [110]
MgO/MgFe2O4 – 0.4 p 0 – – –
MgO/Mg2TiO4 + 0.2 p 0 – – –
1
MgO/Mg2SnO4 + 2.5 p 0.8° + /2 aMgO [101] [010]
1
MgO/MgIn2O4 + 4.7 p 3.5° + /2 aMgO [101] [010]
1
ZrO2/La2Zr2O7 + 5.5 p 2.5° + /2 aZrO2 [101] [010]

out-of-plane Burgers vectors occurs, the perpendicular
component b? = 1/2 aBO [001] of which is the reason for
the observed small tilt of the spinel and pyrochlore lattice
off the orientation Eq. (5). No correlations of these observa-
tions with the morphology of the interface were found.
3.3. Burgers geometry, mode of misfit dislocation
movement, and reactivity
As a consequence of these findings, two principal Burgers
geometries are found: One with in-plane Burgers vectors
(at negative misfit), the other with out-of-plane ones (at
positive misfit). These two principal geometries result in
two different modes of the unidirectional misfit dislocation
movement into the [001] direction. The latter occurs be-
cause the misfit dislocation network has to move together
with the advancing interface due to the interfacial solid
state reaction proceeding into the [001] direction, i. e., into
an overall direction perpendicular to the interface plane.
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cally unfavourable process, because it requires the diffusion
of lattice molecules (in particular oxygen ions) to the misfit
dislocations in order to add them to the extra spinel lattice
planes at the interface [9, 10]. Since oxygen ions are rather
slowly diffusing in a dense-packed oxide lattice, the reac-
tivity of those interfaces where out-of-plane Burgers vec-
tors are present should be higher than that of those where
in-plane Burgers vectors constitute the network of misfit
dislocations. The zero-misfit interfaces should be even
more reactive than the former two, because the conservative
glide process suffers from an additional resistance due to
the Peierls stress experienced by gliding dislocations. These
predictions were qualitatively confirmed by our observa-
tions. The three different principal structures of the reactive
interfaces – without dislocations, with dislocations of in-
plane Burgers vector, and with dislocations of out-of-plane
Burgers vector – thus result in three different values of in-
terface mobility, or reactivity.

The two modes are
(i) diffusional climb in the case of in-plane Burgers vec-
tors (Fig. 6), and
(ii) conservative glide in the case of out-of-plane Burgers
vectors (Fig. 7).
While the glide mechanism (Fig. 7) can proceed easily and
quickly, the climb mechanism (Fig. 6) is a slow and energeti-
© 2004 Carl Hanser Verlag, Munich, Germany
3.4. Initial microtopography, stresses, and the Burgers
geometry
In view of the above findings, the questions arise, when and
by which processes the misfit dislocations form, whether
their Burgers vector is univocally determined by the sign
of the lattice misfit or not, and if not, which other factors de-

Fig. 6. Scheme of the diffusive climb mechanism of the misfit disloca- Fig. 7. Scheme of the conservative glide mechanism of the misfit dis-
tion movement at the MgO/MgCr2O4 boundary. Open circles designate location movement at the MgO/MgIn2O4 boundary. For the meaning
oxygen ions, black arrows Burgers vectors. Open arrows indicate the of the arrows, see Fig. 6.
direction of movement of the reactive heterophase boundary.

Z. Metallkd. 95 (2004) 4 255

B
Not for use in internet or intranet sites. Not for electronic distribution. Basic
D. Hesse, S. Senz: Interfacial reaction mechanisms and the structure of moving heterophase boundaries
termine the Burgers vector. To study these questions, the in-
itial reaction stages were investigated by AFM and TEM,
using BO (001) crystal surfaces of different microtopogra-
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phies [12 – 14]. Fig. 8 shows an AFM image and a TEM
plan-view image of La2Zr2O7 islands that have grown on a
flat YSZ(001) substrate during the initial stage of reaction
Eq. (3), with A = Zr and B = La. Each island consists of
© 2004 Carl Hanser Verlag, Munich, Germany
Fig. 10. Plan-view TEM image of a La2Zr2O7 island grown around a
surface pit on a YSZ (001) substrate. Four <110>-tilted domains
(Nos. 1 to 4) and two <100>-tilted stripe domains (Nos. 5 and 6) are
visible.
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Fig. 8. (a) AFM and (b) TEM plan-view
images of La2Zr2O7 islands on a flat YSZ
(001) surface. Inset: Greyscale indicating the
vertical coordinate (height).
Fig. 9. (a) Part of an X-ray pole figure and (b)
TEM plan-view image of La2Zr2O7 islands
grown on a flat YSZ (001) surface. In the pole
figure shown, the polar angle ranges from 0
(centre) to 5° (rim). The TEM image shows
four tilt domains, and dislocation networks.
four tilt domains, as demonstrated by the XRD pole figure
(Fig. 9a). Fig. 9b shows the internal structure of an island
together with the network of misfit dislocations at the
ZrO2/La2Zr2O7 interface. These dislocations, running along
<100> directions at a spacing of about 8 nm, were analysed
by TEM [13,14]. They turned out to be edge dislocations
with Burgers vectors b1 = 1/2 aZrO2 [101] and b2 = 1/2 aZrO2
[011], i. e., out-of-plane Burgers vectors. The interface-par-
allel component of the Burgers vector accommodates the
lattice mismatch, while the perpendicular component
causes a tilt of the La2Zr2O7 lattice around the <110> axes
by about 2.5° (cf. Fig. 9a). A different picture occurs when
the reaction is performed on YSZ (001) surfaces containing
a large number of pits of about 20 to 30 nm in diameter.
(The origin of the pits is not clear. They might be due to
small precipitates of tetragonal ZrO2 that were removed
from the surface during surface polish.) On these surfaces,
the islands grow around the pits, leaving a central hole,
and, in addition to four tilted domains of trapezoidal shape,
they always contain between one and four stripe domains
tilted around <100> (Fig. 10). The latter have misfit dislo-
cations with an in-plane Burgers vector of type b =1/2 aZrO2
[100], as was revealed by Fourier-filtered HRTEM images
[12].
The observed structural and morphological differences
between the case of a flat YSZ surface and the one with pits
can be explained considering the generation mechanisms of
misfit dislocations (Fig. 11). On flat surface areas, misfit
dislocations of a Burgers vector b =1/2 aZrO2 ½101] are gen-
erated at the corners of the growing islands, where the epi-
taxial stress has a maximum. They subsequently move to
the ZrO2/La2Zr2O7 interface by glide on {101} planes, thus
Z. Metallkd. 95 (2004) 4
 D. Hesse, S. Senz: Interfacial reaction mechanisms and the structure of moving heterophase boundaries
Not for use in internet or intranet sites. Not for electronic distribution.
forming the <110>-tilted domains (Fig. 11a). Near a pit
rim, however, part of the stresses arising in the growing is-
land can certainly relax by deformation of the pit rim. (De-
tails of the mechanism still remain open.) The remaining
stress components result in the generation of dislocations
with Burgers vector b =1/2 aZrO2 [100] at the pit rim on the
level of the ZrO2/La2Zr2O7 interface. The dislocations sub-
sequently move under the island by glide on the (001) plane
forming the <100>-tilted stripe domains (Fig. 11b). For de-
tailed models, see Refs. [12 – 14].
Considering the previously established relation between
reactivity and the mode of movement of misfit dislocations
– given by the Burgers geometry – it is suggested that the
reactivity of a plane ZrO2/La2O3 interface is higher than
that of an interface providing many sites of stress relaxa-
tion, like pit rims of a high density. This is a somewhat sur-
prising result, because usually plane interfaces are believed
to be less reactive than rough interfaces.
4. Conclusions
Crystallography and atomic-scale structure of a reactive in-
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terface play an important role in determining the reactivity
of this interface. The reactivity (or reaction kinetics) de-
pends on the mobility of the interfacial dislocation network,
because the misfit dislocations have to move together with
the advancing reaction front. The mobility of the disloca-
tions, in turn, depends on the mode of dislocation move-
ment (conservative glide or diffusive climb), so that, finally,
interface mobility and reactivity depend on the Burgers
vector geometry of the misfit dislocations. The Burgers
© 2004 Carl Hanser Verlag, Munich, Germany
vector geometry, in turn, depends on the sign and amount
of the lattice misfit, but also on the stress conditions initi-
ally prevailing at the reactive interface. Structure and chem-
istry of reactive interfaces in ceramics are, thus, closely in-
terrelated.
Z. Metallkd. 95 (2004) 4
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Fig. 11. Cross-sectional scheme of two mech-
anisms of dislocation generation, (a) on flat
YSZ surface areas, and (b) near a pit rim.
Tilted black dislocation symbols “T” denote
out-of-plane Burgers vectors, non-tilted grey
symbols in-plane ones.
The authors are thankful to Drs. W. Blum, A. Graff, C. J. Lu, H. Sieber,
P. Werner, N. D. Zakharov, and M. Zimnol for their respective experi-
mental contributions to this work. Thanks are due to Professors U. Gö-
sele and J. Heydenreich for continuous support, and to Professor
H. Schmalzried for many fruitful discussions.
Work supported by DFG via SFB 418 at Martin-Luther-Universität
Halle – Wittenberg.
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[6] M. Martin, in: V.V. Boldyrev (Ed.), Reactivity of solids – past,
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[12] C.J. Lu, S. Senz, D. Hesse: Phil. Mag. A 81 (2001) 2705.
[13] C.J. Lu, S. Senz, D. Hesse: Phil. Mag. Letters 82 (2002) 167.
[14] C.J. Lu, S. Senz, D. Hesse: Surface Science 515 (2002) 507.
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(Received October 29, 2003; accepted February 3, 2004)
Correspondence address
Priv.-Doz. Dr. Dietrich Hesse
Max-Planck-Institut für Mikrostrukturphysik
Weinberg 2, D-06120 Halle (Saale), Germany
Tel.: +49 345 5582 741
Fax: +49 345 5511 223
E-mail: hesse@mpi-halle.de
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