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Annu. Rev. Mater. Res. 2003. 33:55–90 doi: 10.1146/annurev.matsci.33.013102.

094710 Copyright c 2003 by Annual Reviews. All rights reserved

SOLID-STATE REACTIVITY AT HETEROPHASE INTERFACES
Monika Backhaus-Ricoult
CNRS-Centre d’Etudes de Chimie M´ tallurgique, 94407 Vitry sur Seine, France and e Department of Materials Science and Engineering, Cornell University, Ithaca, New York 14853; email: Monika.@ccmr.cornell.edu

Key Words interfaces, solid state reactions, shape, interface chemistry, precipitation s Abstract Chemical reactivity at heterophase interfaces is reviewed with a special focus on metal-oxide and oxide-oxide interfaces. Equilibrium chemistry of interfaces is discussed in terms of processes at the macroscopic and atomic level. The dependency on thermodynamic and crystallographic variables is described and illustrated by experimental results. Any reaction-related motion of an interface is associated with numerous transport and reaction steps that include not only atom transfer across the interface, chemical reactions between species and defects and phase transitions, but also steps accommodating lattice mismatch and volume changes. Faceting and morphology evolution of interfaces are included in the considerations.

INTRODUCTION
Multiphase materials (composites, thin films, bonded, wetted or coated materials, complex devices) find more and more use in a wide range of applications, such as electronic devices, fuel cells, sensors, catalysts, and structural materials. Frequently, the overall materials and device performances are strongly affected by the particular interface properties. This is especially true in nanotechnology, where progress goes hand in hand with an increasing density of interfaces. Mechanical properties such as adhesion, strength, fracture toughness and thermocycling behavior, electric properties and optical properties, all depend on both local chemistry at the interface and its stability in time at the operating conditions, which can include chemical, thermal, electrical, and/or mechanical solicitations. Therefore, not only is basic knowledge of the structure and chemistry of interfaces at the atomic level needed, but also a broad understanding of their chemical reactivity at the macroscopic and microscopic level. The scope of this article is to review chemical reactivity at interfaces. Most of the described phenomena are general. However, due to the large variety of heterophase materials, special focus is placed on metal-oxide and oxide-oxide interfaces. Metal-oxide interfaces have the particularity that the phases in contact
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differ considerably in bonding, defect chemistry, and properties, thus promoting a large variety of chemical processes. Oxide-oxide interfaces, in contrast, separate quite similar phases with a common oxygen sublattice; they are used here to illustrate relaxation and ordering phenomena in the course of solid-state reactions. Specific aspects of metal and semiconductor interfaces are not treated herein. A number of excellent monographs and conference proceedings exist on solid-state reactions (1, 2), solid-state thermodynamics (3, 4), and interface characteristics at the atomic level (5–8). However, microscopic and macroscopic phenomena have rarely been linked. Therefore, we make a special effort to describe the chemical reactivity of or at interfaces in terms of the atomic reaction steps of structural and chemical transformations, with their associated relaxation phenomena, and relate them to macroscopic thermodynamics and kinetics. First, continuum thermodynamics for two-phase multicomponent systems are reviewed. In the second section, structural defects and chemical inhomogeneity are introduced as typical equilibrium features of interfaces. Evolution of interface chemistry and energy with oxygen chemical potential, temperature, relative orientation, and type of interface are discussed in detail for metal-oxide interfaces and illustrated by selected experimental results. In the third section, reactivity at heterophase interfaces is discussed in terms of the individual microscopic reaction steps at the interface and long-range transport to and away from the interface. The various reactions steps are illustrated for particular interfaces. Finally, global reaction kinetics of solid-state reactions are discussed.

TWO-PHASE COEXISTENCE ACCORDING TO CONTINUUM THERMODYNAMICS
Coexisting phases are in thermodynamic equilibrium when temperature, hydrostatic pressure, and chemical component potentials are uniform and continuous across the interface [for charged species, the electrochemical potential is continuous, for stressed solids, the generalized diffusion potential is also continuous (9)]. A number of geometric presentations, such as phase diagrams, derived from thermodynamic considerations, illustrate the stability range of extended phases and phase mixtures in multicomponent systems. Diagrams of the molar Gibbs energy G(x1,. . .,xn) as a function of composition (Figure 1a) can be used to determine the compositions of the two coexisting stable phases for a globally unstable composition (common tangent construction) (1). Diagrams of second kind phases, e.g., T-composition and µO2-composition diagrams, illustrate the different phase fields as a function of an intrinsic variable and composition (see Figure 1b). In diagrams of third type of phase, such as the Gibbs phase triangle, information on phase stabilities is presented as a function of two extrinsic variables (Figure 1c). The number of independent thermodynamic state variables necessary to describe the coexistence of two phases in a multicomponent system is given by the extended Gibbs phase rule (10, 11), which relates the thermodynamic degrees of

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Figure 1 (a) Presentation of the evolution with composition of the Gibbs free energy for alloy and oxide phases; the common tangent construction determines coexisting alloy and oxide compositions. (b) Phase diagram demonstrating the stability domains of alloy and oxide phase as function of the oxygen chemical potential; coexisting compositions are interconnected by a dotted line. (c) Gibbs phase triangle illustrating the extension of the various phase fields and the coexisting compositions. (d ) Presentation of the interface free energy for a topotaxial fcc metal-oxide system as function of the interface plane orientation. (e) Dependency of the interface free energy γ as function of orientation for a two-dimensional section (the energy envelope is formed by the length of vector γ for every specific orientation) together with the corresponding two-dimensional Wulff shape (obtained by the tangent construction). ( f ) Interface orientation diagram for a topotaxial fcc metal-oxide interface presented in form of a stereographic triangle. Coexisting orientations are interconnected by orientation tie lines.

freedom to the number of components and coexisting phases. In a ternary system, from a chemical perspective, an interface is univariant. Thus a specific ternary metal-oxide interface (at constant temperature and pressure) is chemically not fully determined by the simple coexistence of metal and oxide phase; its local chemistry depends on the oxygen chemical potential. The thermodynamic properties of an interface in a crystalline material also depend on its detailed atomic structure. For a general interface, its five macroscopic geometrical variables must be considered. They describe the relative orientation or misorientation of the two crystals in contact (three degrees of freedom) and the

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orientation of the interfacial plane (two degrees of freedom). For a metal-oxide interface in a specific ternary system, six variables would thus have to be specified. Although an infinite number of relative orientations can be imagined for two crystal lattices, only a very restricted number of low-energy interfaces form upon precipitation, thin film growth, etc. Their orientations are characterized by the parallelism of dense planes and/or dense directions in both structures and can be rationalized by considering their elastic strain energy, symmetry, and/or coincidence site densities in the interfacial plane. At fixed chemical potential and fixed relative crystal orientation, the free interface energy per unit area, γ , varies with the plane position, Figure 1d. Depending on its anisotropy, the interface energy can vary smoothly with orientation or show a number of deep energy cusps. High-energy interfaces are not stable; they decompose under faceting into lower-energy interfaces. As a consequence, the stable geometric interface configurations do not occupy (at fixed component chemical potentials) the entire five-dimensional space but are restricted to a smaller subset that derives from the thermodynamic relative stability of the interfaces. The relative size of those subset orientations depends on the anisotropy of the interface energy (for extreme anisotropy, it is reduced to a set of symmetrically equivalent points). Confined particles, precipitates, and liquid inclusions are preferentially bounded by interfaces with low energy. For an embedded crystallite of given volume, the Wulff construction (12) determines from the γ ( N ) plot the equilibrium shape minimizing the total free interface energy, i.e., the Wulff shape (see Figure 1e). For negligible elastic energy contributions, the same Wulff shape is obtained from the convexified ξ -plot with ξ ( A) = A γ ( A) (13–15); nonconvex portions of the ξ -plot correspond to unstable interface orientations that would decompose into stable ones (the self-intersections on the convexified ξ -plot). Cahn & Carter (14) noticed the formal analogy of interface thermodynamics and bulk phase thermodynamics of multicomponent systems and transposed the well-developed formalism in Gibbs thermodynamics for bulk phase equilibria to surfaces and interfaces. Main equations of Gibbs thermodynamics thus provided descriptions for faceting, Gibbs adsorption, interface phase transitions, and interface roughening (15–17). Familiar presentations of bulk phase diagrams were adapted to surfaces and interfaces in the form of ξ -diagrams or Wulff plots (presenting the variation of interfacial energy as a function of orientation) and N -diagrams (14). N -diagrams are analogs of phase diagrams with interface orientation N replacing the composition. In those diagrams, two- and three-phase regions represent missing orientations in the Wulff shape, and tie lines interconnect coexisting orientations (see Figure 1f ). In analogy to phase diagrams, N -diagrams can be determined from experimental observations of equilibrium shapes. In order to visualize equilibrium shapes with minimum surface energy for solids of arbitrary crystallographic symmetry, computational tools (18) have been developed. The ξ -diagram approach was successfully applied to the distribution of glass phase in ceramics (19, 20). ξ -diagrams of the unwetted grain boundaries and the

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two wetted surfaces (sum) were superposed in order to determine grain boundary orientations that were entirely, partially or not at all wetted by the glass phase; the so-derived predictions were compared with experimental observations in polycrystalline alumina-containing anorthite glass. Combined ξ -diagrams can be applied to a variety of problems (wetting or infiltration). In special cases, hints on the morphological arrangement of the phases can be derived from the relative energy considerations, e.g., in Reference (19), the lowest-energy location of a pore in a system of matrix and faceted precipitate was determined. Interface state diagrams were used to illustrate precipitate shape evolution with thermodynamic parameters, such as temperature and chemical component potentials or composition, and to display stability domains of interfaces [solid incoherent metal precipitates or pores in an oxide host matrix (20, 21), oxide precipitates in alloys (22), pores in alumina (23)]. For many solid metal-oxide systems, the experimental Wulff shape is fully faceted, thus indicating well-developed cusps in the interface energy. For liquid metal inclusions in oxides, almost perfect faceting was observed close to the melting point (24), whereas at higher temperature, precipitate shape became more rounded (21). Similar interface roughening with temperature was reported for lead inclusions in an aluminum matrix (25). In the ξ -concept, changes in interfacial energy for small inclinations from planar interfacial facets are described by a torque term (derived from the shape of the energy cusp near the equilibrium orientation) (15). However, edges and corners, where, respectively, two or three interfacial equilibrium facets meet, cannot be handled in the formal ξ -concept owing to considerable elastic energy contributions. For large particles with flat interface facets, the elastic energy contributions remain negligible; for nano-size particles, they play a crucial role. For precipitates and supported particles of few nanometers in size, deviations from the regular Wulff shape were reported (24, 26, 27). Occasionally, a quantum size effect was noticed for very small precipitates. Precipitates formed with a large preference in distinct magic sizes, which match a multiple of the coincidence site cell of the two crystal lattices and thus exhibit very low elastic strain energy (28, 29).

Interface Equilibrium Structure and Chemistry
A structural interface can be considered a transition zone between two crystals with its proper (relaxed) structure and sites of different energies; it usually spreads over several atomic distances. It is associated with a local variation in charge distribution and chemical composition. As a consequence, at the interface itself and in its proximity, stoichiometry may vary compared with that of the bulk crystals. Modifications in the chemical composition can be understood in terms of intrinsic segregation (system closed for matter exchange with the environment) or Gibbs adsorption (system open for matter exchange with the environment) to the interface. In the immediate vicinity of the interface (within a few lattice planes, in the interface core), the chemical composition changes abruptly and then evolves continuously over the more extended space charge layer (Figure 2).

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In order to determine the local interface chemistry, both a global and a local approach are needed to handle the various interactions in the solid solutions and the energy distribution of the interface in question.
INTERFACE ATOMIC STRUCTURE For a precise description of the interface structure at the atomic level, the translational state of the crystal lattices must be indicated by three additional microscopic geometric degrees of freedom. Interfaces in real systems are always in the lowest energy translational state. Artificial model interfaces have to be brought into it by structural relaxation. A particular interface is fully characterized by information on its relaxed atomic structure, its electronic charge density distribution, and the total energy of the system. Minimum energy configurations of interfaces have been calculated in various systems for selected orientation relationships and imposed chemical interface compositions. Different approaches, such as molecular dynamics or first principle (ab initio) calculations have been used; interfaces have been modeled through clusters or periodic slabs. First principle methods have been developed over the past ten years; they apply to density functional theory and local density approximations or Hartree Fock theory. Details of these approaches can be found in review articles (30, 31). Simulations have been realized for many interfaces; here several examples of interfaces between transition metals and MgO (32–35), Al2O3 (36–38), and MgAl2O4 (39, 40) are mentioned. Lattice structure and mismatch induce a periodicity in the interface structure. Depending on lattice mismatch and elastic constants in both phases, the atom displacement fields extend more or less into the crystals, thus leading to interfaces with different coherency. A coherence degree between 0 and 1 would provide a precise classification; however, usually only coherent, semi-coherent, and incoherent interfaces are distinguished. Coherent interfaces have an epitaxial strain field that alters the relative phase stability and the equilibrium compositions at the interface compared with the stressfree coexistence of the phases. The long-range character of elastic stress makes the interface equilibrium composition depend on the dimensions of the system. Such effects were especially observed for thin films and nanoparticles. Influence of coherent strain on the equilibrium shape of coherent precipitates was considered very early by Eshelby (41) and has been further developed (42, 43). Semi-coherent interfaces are composed of alternating regions of good and bad lattice match, described by a mismatch dislocation network. Each misfit dislocation has a core and a surrounding strain field. It is very difficult to handle the inhomogeneous distribution of strain at semi-coherent interfaces (32). Incoherent interfaces exhibit a large mismatch between the two adjacent crystals that is accommodated by geometric misfit dislocations, the strain field of which is negligible (very weak adhesion). Incoherent interfaces are usually faceted along low-energy interfaces. CHARACTERISTIC INTERFACIAL BUILDING UNITS AND POINT DEFECTS At the interface, the two crystals in contact impose their inherent constraints on lattice,

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charge, and chemistry; therefore, the equilibrium interface is not simply a combination of the two bulk lattices along the interfacial plane. In addition to the regular species and defects of the bulk phases (vacancies, interstitials, electronic defects), the interface may exhibit characteristic interfacial equilibrium point defects (44). For transition metal-oxide interfaces, structural vacancies and interfacial charge transfer clusters likely constitute such typical interfacial point defects (44, 45). Structural vacancies correspond to vacant cationic or anionic sites in the terminating oxide plane at the interface and form because of electroneutrality (44–46). Interfacial charge transfer clusters are associates of species and/or defects of both phases; they are stabilized at the interface by interactions between the two phases. They can have oxide character when charge transfer occurs between the transition metal and oxygen, or metallic character when charge transfer occurs between transition metal and oxide metal. The different types of interfacial point defects are schematically presented in Figure 3a for polar and mixed topotaxial interfaces (no consideration of lattice mismatch) in the three ranges of oxygen activity. Even though the characteristic interfacial defects may be of different specific nature at other interfaces, the general concept of interfacial clusters with covalent or ionic interactions can be transposed. Similar to regular bulk defect concentrations, interfacial defect concentrations depend on temperature, composition, oxygen chemical potential, etc. Concentrations of metallic charge transfer clusters (and oxygen deficiency) increase with decreasing oxygen activity, whereas concentrations of oxide charge transfer clusters (and interfacial oxygen excess) increase with increasing oxygen activity. The typical evolution with oxygen chemical potential of the different interfacial defect concentrations and the interfacial stoichiometry at a transition metal-oxide interface is depicted in Figure 3b. The interface stoichiometry follows an S-shaped curve, as known from bulk oxides with multivalent cations, but covers a much larger range (on the order of 1). The main interface defects differ for mixed (terminating oxide plane occupied by a stoichiometric mixture of cations and anions) and polar (terminating oxide plane solely occupied by either cations or anions) metal-oxide interfaces. Whereas in the adsorption-free (stoichiometric) state, mixed interfaces exhibit only very low concentrations of specific interfacial defects, because of electroneutrality

Figure 3 (b) Schematic evolution of the local interface stoichiometry with oxygen chemical potential within the thermodynamic stability range of the interface.

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polar interfaces have an extremely high concentration of structural vacancies (Every second atom site in the terminating oxide plane remains unoccupied!) In accordance with their combined character, non-stoichiometric mixed interfaces exhibit a smaller portion of structural vacancies in the terminating oxide plane.
INTERFACE CORE COMPOSITION Interface defects may be stabilized by chemical interactions between the two phases in contact, and compared with the bulk, different rules of local conservation of lattice sites, atoms, and charge apply at the interface; thus the local chemical composition in the core of the interface can differ from that of the coexisting bulk phases and at times be even outside of the bulk phase stability range. The chemical composition of the interface core region is formed by intrinsic segregation or Gibbs adsorption of the uncharged and charged species to the interface. Solid solution behavior of the interface phase and energy topography of the interface are the parameters that determine its qualitative and quantitative core nature. SPACE CHARGE LAYER Regular crystals contain small concentrations of point defects such as vacancies, interstitials, and electronic carriers that are statistically distributed in the bulk. Close to the interface, chemical composition and defect distribution become non-uniform. The intrinsic segregation of charged defects and species to the interface core region imposes an electric surface charge on the ionic half crystal, which, through the coupling with the associated electric field, imposes a redistribution of the charged defects in proximity of the interface within the so-called space charge layer. The typical thickness of this layer is on the order of the Debye-Hueckel length. The exact concentration profiles of the charged species in this layer can be derived from the equilibrium condition of electrochemical potential constancy over the entire ionic crystal, including the space charge layer. Local enrichment or depletion in charged species is caused by the local difference in electrical potential compared with the undisturbed bulk. The type of space charge depends on the type of charged species enriched in the interface core layer. The absolute charge diminishes across the space charge layer. A detailed description of space charge layers in ionic crystal can be found elsewhere (47). At transition metal-oxide interfaces, any presence of Gibbsian oxygen excess or deficiency can be associated with an electric double layer at the interface, with excess positive charges in one half crystal and excess negative charge in the other half (see Figure 2). The interfacial charge in the oxide half crystal gives rise to the formation of a space charge layer in the oxide crystal. Its character depends on the interfacial defect clusters present at the interface.

Dependency of Interfacial Composition and Energy on µO2
Whereas it is well known from point defect and lattice thermodynamics (48) how non-stoichiometry of bulk compounds changes with temperature, pressure, and component chemical potentials, it is less well known, how local interface

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composition depends on those thermodynamic variables. In the following, theoretic approaches, models, and experimental results on that subject are presented. The main focus is on the oxygen chemical potential-dependency because the temperature-dependency is similar to that encountered for bulk compounds.
FIRST PRINCIPLE CALCULATIONS Grand canonical assemblies still remain inaccessible for ab initio calculations; however, information on the most stable interface stoichiometry and type of terminating oxide plane at imposed experimental conditions are facts that can be derived from calculations. In Reference 49, a thermodynamic cycle was used to express the interface free energy in terms of the energy of a metal-oxide slab (accessible via first principle calculations) and well-known thermodynamic quantities, such as energies of formation and heat capacities. Free energies of the metal-oxide slab and of the metal and oxide surfaces were calculated under relaxation of the atomic structure and, together with the macroscopic thermodynamic data, used to determine the oxygen chemical potential-dependency of the surface and interface free energies. The calculation was repeated for various interfaces with different interface chemistry and thus provided interfacial separation and adhesion energies for interfaces with different stoichiometry. The calculations were conducted for alumina-niobium (0001)//(111) interfaces; those results are illustrated in Figure 4. They reveal that the stoichiometric alumina basal surface is stable over the entire stability range of the interface. Niobium surfaces exhibit adsorption of oxygen prior to bulk oxidation. Comparison of the free energies of the different interfaces shows that, over a broad range of intermediate oxygen

Figure 4 Presentation of free energies obtained by ab initio calculation for niobiumalumina interfaces (50; courtesy of M. Finnis): (a) surface of niobium metal and alumina with different surface terminations; (b) the work of separation of different interfaces; (c) interface free energies for stoichiometric, oxygen-excess, and oxygendeficient niobium-alumina interfaces; (d ) adhesion energy.

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activities, the stoichiometric interface has the lowest free energy; only close to the limits of the stability range two oxygen-terminated and aluminium-terminated interfaces, respectively, exhibit lower free energies. Even with having the lowest energy, the stoichiometric interface is not stable in respect to the chemically unrelaxed free surfaces. Evaluation of the work of separation showed that over almost the entire stability range, the aluminum-terminated interface is the mechanically most stable interface (This statement is greatly simplified because plastic dissipative processes play an important role during fracture and may alter the mechanically stability compared with the work of adhesion.) Systematic variations of interface plane, oxygen activity, and temperature for a large number of systems cannot be handled easily by ab initio calculations. In order to respond to this demand, a number of phenomenological approaches were developed that evaluate the influence of crystallographic and thermodynamic variables on the basis of empirical interaction parameters.
PHENOMENOLOGICAL MODELS

Gibbs adsorption model The Gibbs adsorption model is a continuum thermodynamics approach suited for liquid surfaces and interfaces; it needs to be revised when applied to crystalline interfaces, where adsorption-related volume changes can relax only when matter, charge, and lattice conservation in the two crystals are respected. It should be emphasized that the crystal lattice is not an extensive thermodynamic variable, and lattice sites cannot be treated like chemical species. The general concept of Gibbs adsorption was applied to transition metal-oxide interfaces in order to describe the wetting behavior of oxide surfaces by liquid transition metals and the changes in precipitate equilibrium shapes with oxygen chemical potential (50–53). The stability range of a metal-oxide interface is likely divided in three oxygen activity domains with characteristic adsorption behavior: a neutral domain with a stoichiometric interface covering intermediate oxygen activities, a domain with interfacial oxygen excess in the upper oxygen activity range, and a domain with interfacial oxygen deficiency in the lower oxygen activity range. For a specific system, the relative thermodynamic stabilities of metal and oxide determine whether all three domains are present within the interface stability range. The Gibbsian excess for a precise interface can be determined for known adsorption energies and interaction parameters of the interfacial species. Because chemical adsorption can be understood in terms of bond formation at the interface, i.e., transition metal-oxygen bonds at high oxygen activity and transition metaloxide bonds at low-oxygen activity, adsorption energies were approximated by the formation enthalpies of the corresponding bulk phases (50, 52, 54). At a specific interface, however, adsorption may be non-uniform in energy and depend on the particular interface structure. There is a definite difference in situations where local oxygen excess is established by adsorption of an excess oxygen atom to a structural oxygen vacancy compared with situations where it is obtained by desorption

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of a cation from a regular cation site in the oxide. Therefore, different adsorption energies were used for polar and mixed interfaces, thus providing a much larger Gibbsian excess at polar interfaces [see (50)]. High local interfacial defect concentrations combined with a restricted number of interfacial defect sites suggest that the interactions between the interface defects must be taken into account. Several such corrections include an adsorption entropy (50), an elastic energy contribution related to volume changes upon adsorption (44, 45), and a strong repulsive interaction parameter in the solution model (54). Most assumptions successfully describe the onset of adsorption but not the range close to saturation. Interfacial point defect model In another phenomenologicl approach, the core interface chemistry was derived from an extended point defect model (44, 45), where instead of the sharp Gibbs adsorption plane, a two- to three-lattice-planesbroad chemical interface was considered. In this approach, the interfacial zone was artificially divided in several slabs, which are all in equilibrium and respect the formal lattice thermodynamics. Formation, conservation, and coupling equations were established for the interface with its characteristic interface point defects (structural vacancies, oxide clusters, and metallic clusters) and for the species in the bulk phases. Defect interactions were considered and treated as correction terms in the defect formation energies. The adsorption isotherms were directly obtained from the interfacial point defect concentrations. Figure 5a presents predicted Gibbs adsorption isotherms for O- and Al-terminated polar and mixed α-alumina-Cu interfaces.

Figure 5 (a) Solid Cu-α alumina interface at 1200 K; Model predictions on the interfacial Gibbsian oxygen excess as function of oxygen activity at a polar, oxygenterminated, mixed, and an aluminum-terminated interface. Different assumptions were made for the Gibbs adsorption energy; the continuous line was obtained by using the bulk formation enthalpies of the corresponding bulk phases, the discontinuous line with an additional adsorption entropy, and the dotted line with an additional contribution of elastic energy related to volume changes upon adsorption.

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The characteristic crystallographic features of an interfaces (atom distribution and density in the interfacial plane) and especially its polar, mixed neutral, and mixed polar character were introduced in the modeling of Gibbs adsorption in (44, 50), and Gibbsian excess was compared for different interfaces. Figure 5b presents an example of that approach with the absolute excess concentrations for crystallographically different Cu-α-alumina interfaces as a function of the oxygen activity. Adsorption isotherms With a more or less simplified set of thermodynamic data, adsorption isotherms were obtained for Cu-MgO (50), Cu-α-alumina (44), Cu-γ alumina (45), and Fe-α-alumina (M. Backhaus-Ricoult, unpublished results) solid metal-solid oxide interfaces, oxide-liquid metal interfaces (44, 21), and glass-metal interfaces (56, 57). Model predictions show good agreement with the experimental onset of oxygen adsorption, demonstrating thereby that the adsorption energies are effectively close to the corresponding bulk oxide formation enthalpies (a variation of ±10% in the energy value would shift the adsorption onset by some orders of magnitude in oxygen activity) (51). Discrepancies between model predictions and experiments for high Gibbsian excess are related to non-ideal defect interactions. Most adsorption models do not attribute any importance to the crystallographic characteristics of the terminating metal plane. However, experimental results on iron precipitate equilibrium shape in solid alumina reveal its influence: The equilibrium shape of liquid iron precipitates in an α-alumina matrix was found to reflect the R3c symmetry of the host matrix, whereas that of solid Fe precipitates exhibited only the common symmetry (R3c ⊗ bcc) (58). Solid iron precipitate interface facets with prismatic alumina planes {1120} parallel to dense iron planes were slightly larger than those parallel to low-density iron planes and evolved differently with oxygen activity, thus also demonstrating a small dependency on the metal plane crystallography. Evolution of the interfacial energy with µO2 Integration of the Gibbsian excess over the oxygen chemical potential yields the relative change in specific free interface energy γ (aO2) = dµO [− O(hkl, aO2) + B(hkl, aO2)]. The interfacial free energy decreases substantially in the oxygen excess and oxygen deficiency domains (Figure 5c); the absolute value depends on the Gibbsian excess and the stability of the interfacial defect clusters. For MgO-Cu and alumina-copper interfaces at their upper limit of the stability range, phenomenological modeling predicts a decrease in relative free energy on the order of 1 J/m2. Predictions on the evolution of relative interfacial energy can be compared directly with experimental wetting data. They can also be compared with the evolution of precipitate equilibrium shape with oxygen activity. Evolution of the space charge layer with µO2 Interfacial Gibbsian oxygen excess imposes a local charge density on the terminating oxide plane, which is then

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responsible for the formation of a space charge layer in the oxide. It is especially interesting that for intrinsic behavior of the oxide an inversion of the type of space charge occurs with oxygen chemical potential. Interfacial excess oxygen (in the high oxygen activity domain) undergoes charge transfer with the transition metal, imposes a negative surface charge on the oxide, and thus causes a space charge layer in which the concentrations of negatively charged defects are smaller and concentrations of positively charged defects are larger than in the bulk. In case of interfacial oxygen deficiency at low oxygen activity, electron transfer at the interface between excess metal in the oxide and the transition metal imposes a positive surface charge on the oxide, and concentrations of positively charged defects are increased, whereas the opposite is true for the negatively charge defects. In the large adsorption-free range at intermediate oxygen activity, the metaloxide interface is free of any net charge, and no intrinsic space charge layer is present. In Figure 6a,b,c, defect concentrations in the space charge region are schematically presented (oxide with intrinsic Schottky-type disorder) for oxygen excess, stoichiometric, and oxygen-deficient metal-oxide interface. For Cu-MgO interfaces, space charge layers have been calculated as function of oxygen activity, see Figure 6d,e,f [MgO is considerably doped with copper over a broad range of oxygen activity when coexisting with metallic copper and exhibits extrinsic behavior (50).]

Experimental Observations
CHARACTERIZATION TECHNIQUES In an effort to determine interface structure and chemistry, a large variety of techniques, such as atom or tomographic probe, electron energy loss spectroscopy (EELS), high resolution electron microscopy (HREM), X-ray spectroscopy, Auger spectroscopy, perturbed angular correlation spectroscopy, coulometric titration, electronic conductivity measurements, etc., have been used. Even in materials with very high interface densities such as internally oxidized alloys or nanocomposites, the global interface area is limited to about 500 m2/m3 or 1–10 ppm of interfacial atoms in the entire volume, which is not sufficient for many bulk characterization techniques with excellent performances for probing local atom environments (M¨ ssbauer spectroscopy, EXAFS, o etc.). Transmission electron microscopy (TEM) techniques (on cross-sectional thin foils) with very high spatial resolution, surface analysis techniques such as Auger, secondary ion mass spectroscopy (SIMS) combined with continuous surface ablation, and atom probe field ion microscopy (or tomographic probe) are methods most successfully applied to study the local interface chemistry.

STUDIED SYSTEMS For Ag-MgO interfaces, oxygen adsorption was followed by titration (54). For Cu-MgO (50, 59, 60), Cu-SiO2 (56, 57), Ag-MgO (61), and CuAl2O3 (62, 55) interfaces, systematic variations with oxygen chemical potential

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in the interface electronic states were detected by EELS. For the MgO-Cu system, changes in equilibrium shape with oxygen activity of small MgO precipitates in a copper matrix and of small copper inclusions in MgO were observed (51, 60), demonstrating the dependency of interface free energy and interface chemistry on the oxygen chemical potential. A similar dependency on oxygen activity was found for the wetting behavior of various oxides by liquid transition metals (52, 63).

Figure 6 Space charge layer characteristics for transition metal-oxide (intrinsic Schottky disorder) interfaces; (a) at high oxygen activity, (b) in the stoichiometric range, (c) at low oxygen activity, (d–f ) defect concentrations in the oxide at an MgOCu interface at 900◦ C and indicated oxygen activities according to Gibbs adsorption modeling.

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Figure 6 (Continued )

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ELNES–RESULTS ON THE INTERFACE ELECTRONIC STRUCTURE Several systematic studies of the interfacial electronic structure were conducted by EELS. For many of those studies, atomically flat, low-energy metal-oxide interfaces had been produced by internal oxidation of the corresponding alloys at well-defined temperature and oxygen chemical potential and for long reaction times. The local interface chemistry was studied on thin foils. Typically, spectra were acquired in the VG HB501UX STEM with a cold field emission gun at an operating voltage of 100 kV, a probe size of 0.22 nm, a collection semi-angle of the spectrometer of 10 mrad, an energy dispersion of 0.7 eV/ch, and an emission current of 100–200 pA (60). Spectra were usually acquired in the spot or line scan mode, while the probe was discontinuously stepped across the interface with interstep distances between 0.125 and 1.2 nm (60, 62) or obtained by a difference technique (i.e., subtracting area spectra including the interface from others) (61). Interfacial near-edge fine line structures (ELNES) of all studied metal-oxide interfaces exhibited a dependency on the oxygen chemical potential, at which the interface was brought into equilibrium. In Figure 7, ELNES of various Cu-oxide interfaces are assembled to illustrate the systematic modifications. It is common to all investigated systems that interfaces produced and equilibrated in the adsorption-free intermediate oxygen activity range show no modification in the interfacial electronic structure. In the oxygen-rich domain of the stability range, interfacial ELNES was always found to be modified compared with the adjacent bulk phases. The typical modifications illustrated in Figure 7 are analyzed in more detail here: The interfacial Cu-L edges in Figure 7a show the stepped spectrum of metallic copper; however, the three small oscillations characteristic of metallic copper are no longer present. Instead, additional intensity in the near-edge region concentrates in a broad L3 peak. A small increase in Cu L2 intensity at 953 eV compared with that of metallic copper is usually also noticed. Shape and energy location of the L3 peak depend on the kind of oxide and the interfacial plane. In the case of Cu-MgO interfaces, the L3 line is sharp and located exactly at the energy of the Cu L3 white line of cuprite (933 eV) (60), whereas for alumina-copper interfaces, the peak is broadened and shows a chemical shift by 1–2eV (62). The L3 peak is even broader at Cu-silica glass interfaces (56). For the same system and for the same relative orientation of the crystals, intensity and chemical shift of the L3 peak depended on the interface structure. For topotaxial Cu-MgO interfaces, no difference in chemical shift was noticed, but the L3 peak intensity was much larger for {111} polar interfaces than for {001} mixed interfaces (59). This observation was interpreted in terms of a higher Gibbsian excess at polar interfaces compared with mixed interfaces (50). The chemical shift was found to increase and the L2,3 peak intensities to decrease in ¯ a series of studied α-alumina-copper interfaces from {1120}α-alumina//{100}Cu to ¯ α-alumina//Cu, reflecting a dependency of Gib{0001}α-alumina//{001}Cu to {1123} bsian excess on both interface polarity and plane density (62).

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Figure 7 Interfacial ELNES at Cu-MgO, Cu-γ alumina, Cu-α alumina, and Cu-silica glass interfaces (interface type and oxygen activity are indicated for each spectrum, interfaces were obtained by internal oxidation at 900◦ C) and ELNES of the corresponding bulk phase: (a) Cu L2,3, (b) O K, (c) Al L and Cu M, (d ) Si L and Cu M, (e) Mg L and Cu M.

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At high oxygen activity, all studied interfaces exhibiteda pre-peak or broadening for the first O K main peak in their interface spectra, (Figure 7b), but the intensity of those features again depended on oxygen activity, metal-oxide system, and exact interfacial plane. The strongest modification in the spectrum was observed at the upper limit of the interface stability range (900◦ C, aO2 = 10−8) for polar {111} interfaces between γ -alumina, magnesia, or silica glass and copper (62, 56, 59). In all cases, the well-defined oxygen pre-peak was located at around 533 eV, the energy of the strong first peak of bulk Cu2O. The same prepeak was observed with much lower intensity for a γ -alumina-copper interface obtained at aO2 = 10−13 and for a magnesia-copper interface brought into equilibrium at aO2 = 10−14, revealing a decrease in pre-peak intensity with decreasing oxygen chemical potential. In agreement with the modifications in the Cu L edge, the pre-peak intensity was lower at mixed {001} than at polar {111} Cu-MgO interfaces. For transient alumina and α-alumina-copper interfaces, no results are available at the upper limit of the stability range. At slightly lower oxygen activity, no defined O pre-peak was found, but the second ELNES features of the O K peak were systematically shifted to lower energy, suggesting mixed Cu-Al-O bonding (65). The characteristic modifications in Cu L ELNES suggest that interfacial copper is partially oxidized to its Cu1+ state. The presence of a low-energy prepeak in the O K-edge reflects copper-oxygen bonding at the interface. Unfilled Cu 3d states of oxidized copper hybridize with O 2p states under formation of hybrid states that are located in the band gap at lower energy than the regular alumina states (31). At Cu-fcc oxide interfaces, the Cu- and O-interfacial ELNES features closely match those of bulk cuprite. At copper- α-alumina interfaces, oxygen ELNES suggests mixed Cu-O-Al bonding with a strong covalent component. At Cu-MgO interfaces, no modification in Mg L ELNES compared with bulk magnesia was observed. For Cu-alumina interfaces, neither chemical shift nor new fine structural features were observed in interfacial Al L2,3 compared with bulk alumina. However, at α-alumina-copper interfaces, a decrease in the aluminum coordination was indicated by a change in the interfacial Al L2,3 ELNES (appearance of double peak as first peak) (62); for γ -alumina-copper interfaces, no such change in coordination was observed at the interface. At very low oxygen activity, few experimental results are available owing to the difficulty of preparing such interfaces. The only comparable result was obtained for topotaxial Cu-MgO interfaces equilibrated at the lower limit of the stability range (1000◦ C, aO2 = 10−38) (59). Interfacial ELNES did not reveal any change in the O K edge but showed modifications in Cu L and Mg L ELNES. The threshold of the interfacial copper absorption edge was not modified compared with that of metallic copper; however, the signal intensity was lowered over a broad range of energy, 934–948 eV, revealing metallic bonding across the interface and a global increase in its electron density.

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EVOLUTION WITH µO2 OF THE ATOMIC STRUCTURE OF THE INTERFACE Even though the atomic structure of many interfaces was studied by HREM, only a few systematic studies were made as a function of thermodynamic variables (60). The interfacial rigid body displacement at polar and mixed MgO-Cu interfaces (atomically flat, incoherent) was studied as a function of the processing oxygen chemical potential. The results indicate a systematic variation: Stoichiometric polar {111}Cu//{111}MgO interfaces (obtained by internal oxidation of (Cu,Mg) at 900◦ C, 100 h, aO2 = 10−14) showed a rigid body displacement, which was inbetween that of the two bulk phases, whereas the same interface equilibrated at higher oxygen activity [obtained by internal oxidation of (Cu,Mg) at 900◦ C, 100 h, aO2 = 10−8] exhibited a contraction of about 20%. The latter was explained by an attraction of oxidized interfacial copper atoms into the terminating oxygen layer of the oxide. The mixed {001}Cu//{001}MgO interface at high oxygen activity, in contrast, suffered expansion compared with the neutral reference state. This was related to the mixed character of the terminating (001) oxide plane, which can achieve relative oxygen excess only by Mg-desorption and then suffers under a strong repulsion between the less shielded oxygen ions. It was assumed that in case of the mixed interface, the repulsive forces between the oxygen ions overcompensated the attractive interaction between oxidized Cu-atoms and terminating oxide layer. WETTING BEHAVIOR AND ITS DEPENDENCY ON µO2 Wetting of oxides by liquid transition metals strongly depends on the oxygen chemical potential, showing poor wetting over a wide intermediate range in oxygen activity and increasingly better wetting at higher oxygen activities. This can be related to the decrease in the relative free interfacial energy in presence of Gibbsian oxygen excess. Wetting angles have been systematically measured for a number of different systems. In the Cu-alumina system (53, 63–66), they range from 130 to 110◦ . In Figure 8, experimental results on γ sl-γ sv (66) are compared (fitted by vertical shift because γ sv is constant according to Figure 4) with the model predictions (44). Good general agreement is obtained; differences between experimental results and model predictions are probably due to a slight surface deviation in the experiment from the alumina basal plane. PRECIPITATE EQUILIBRIUM SHAPE VARIATIONS WITH µO2 Experimental results on the shape evolution with oxygen activity of liquid copper inclusions within a MgO matrix at T = 1400◦ C were obtained from TEM projections (24). The liquid metal inclusions (typically 100 nm in size) adopted cubo-octahedral shape with additional slight {110}-edge truncation. Their shape evolved with oxygen activity, promoting {111} facets at high oxygen activity (Figure 9a). The specific free energy ratios exhibited a plateau range framed by two decreasing branches at low and high oxygen activity, which reflect the domains of Gibbsian excess. The experimental results matched the modeling predictions. Solid magnesia precipitates (typically 50–100 nm in size) in a Cu matrix exhibited a similar evolution of their morphology with oxygen chemical potential

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Figure 8 Comparison of the decrease in specific free interface energy of an Al2O3liquid Cu interface at T = 1400 K obtained by Gibbs absorption modeling to γ sl-γ sv data obtained from wetting angle measurements (63).

(60) Figure 9b. The precipitate shape was studied by TEM on thin foils and by scanning electron microscopy (SEM) on electropolished bulk sample sections In an intermediate oxygen activity range, precipitates exhibited almost cubic shape; for oxygen activity above 10−15, octahedral facets were observed to increase in size, yielding an almost perfect octahedron at the upper limit of the stability range. Equilibration of precipitates in the lower oxygen activity range was difficult from an experimental point of view. The only (approximate) observation, made at the lower limit of the stability range, demonstrated an increase in {111}-facet size. By consecutively applying different oxygen activities, it was shown that precipitates reversibly changed their shape at 900◦ C. Precipitates formed at aO2 = 10−8 and then exposed to aO2 = 10−12 or 10−15 slowly changed shape by increasing their {001} facet size during the second annealing. Whereas chemical and crystallographic phase limitations clearly indicated the modified morphology, defect arrays in the copper phase at {001} facets and in magnesia at {111} facets, respectively, still reflected the original precipitate shape (60).

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Dependency of Interface Chemistry on the Interfacial Structure
Experimental results on the interface chemistry at different interfacial planes were described above. In summary, Gibbsian excess is always higher at polar than at mixed interfacial planes [ELNES and HREM studies at {111} and {001} MgOCu interfaces; ELNES studies at Cu-alumina interfaces with basal, prismatic, and pyramidal alumina interfacial planes]. For the same type of plane polarity, the Gibbsian excess also depends on the atom density in the terminating oxide plane.

IMPURITY SEGREGATION TO METAL-OXIDE INTERFACES
For a number of systems, detailed studies have been performed to measure impurity segregation to interfaces. Here we illustrate different driving forces for such segregation with typical examples. Solute atoms can segregate to the interface to form more stable bonds. A typical example for such behavior is the irreversible trapping of hydrogen to Ag-MgO (67), Cu-silica (N. Ashcroft, private communication), and Cu-alumina (68) interfaces that leads to the formation of stable hydroxyl groups at the interface. Solute atoms in alloys are surrounded by an elastic strain field; its associated energy may act as driving force to expel solute atoms from the bulk alloy to the interface. This is illustrated with the examples of the formation of a monolayer of silver at MgOCu(Ag) interfaces (69) and the Sb-enrichment at MnO-Ag(Sb) interfaces (70). Impurity segregation also depends on the coherency of the interface.

INFLUENCE OF SIZE
In metal-ceramic or ceramic nanocomposites, a number of size-related unusual property changes have been reported, such as enhanced electric conductivity for mixtures of AgJ (AgCl or AgBr) and Al2O3 (71), enhanced ionic conductivity in BaF2-CaF2 multilayer stacks (72), shift in optical absorption for metallic nanoparticles in glasses (73), and abnormal electrical behavior of semiconducting embedded nanoparticles as used in nano-electronics. The causes for these size effects have been discussed in detail elsewhere (74–77) and are summarized in the following. An increased interface/volume ratio yields a high relative concentration of atoms at edge and corner sites. Those atoms contribute an additional elastic energy to the total energy, thus producing irregularities in behavior or properties, which depend on the interfacial energy. If the spacing between interfaces in the nanocomposite approaches the Debye length, space charge layers start to overlap. For very small distances between the interfaces, the electrical potential profiles are considerably flattened in the

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overlapping area. As a consequence, concentrations of electrically charged species in the space charge layer are modified in nanomaterials, and electric and mass transport properties differ from bulk materials. A very high density of interfaces in the material may not only modify the characteristics of the space charge layer, but also affect the chemical composition in the core of the interfaces. At extremely small particle sizes, the standard chemical potentials µ◦ can be affected by size. Although effects on ions remain negligible, they may become important for electronic carriers. Delocalized electrons are affected sooner by a confinement effect than are the heavier localized ions. In quantum dots, quantum wires, and quantum wells, the electrons of semiconducting CdS, PbS or metallic phases are more or less delocalized; similar to the free electron in a box (of length L), the space refinement imposes the energy level, and the chemical potential differences µ◦ also depend on size as µ◦ ∝ 1/L2. Ions are hardly affected by such size effect because their radius of interaction is restricted by close neighbors. Modifications in their chemical potential would be associated with important modifications in the structure, changes in bond length, and bond symmetry. In the case of NaCl crystals, structural modifications were observed only for clusters composed of less than 10 molecules (78, 79).

PROCESSING- AND HISTORY-CONTROLLED NON-EQUILIBRIUM CHEMISTRY AT INTERFACES
In order to demonstrate a systematic variation of interfacial chemistry with processing parameters, we present here only one representative example of α-aluminacopper interfaces, which was obtained by diffusion bonding in UHV at 1400◦ C and molecular beam epitaxy (MBE) Cu-deposition on differently pretreated (0001) and ¯ (1120) α-alumina surfaces (80–82). The interface electronic structure was found to differ for the interfaces, showing features similar to those observed for certain equilibrium interfaces. The pretreatment of the alumina surface seems to impose the non-equilibrium interface chemistry. A vacuum-annealed crystal alumina surface is typically covered by a layer of adsorbed oxygen; MBE-deposited copper encounters an oxygen-rich surface, incorporates that oxygen at the interface (as non-equilibrium oxygen excess), and thus shows the strong Cu–O ionic bond usually found for Gibbsian oxygen excess. Ar-sputtered alumina surfaces are depleted in oxygen and rich in aluminum. When copper was grown on such surfaces, it thus encountered an aluminum-rich substrate and formed Cu–Al bonds at the interface.

REACTIVITY AT METAL-OXIDE INTERFACES Interface Shape Evolution: Faceting, Wulffing
Although nanometer-sized particles can easily change shape and even completely or partly reorient because a larger number of their atoms are located at edge and corner sites, and because diffusion distances are short (see Gleiter’s experiments on

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the rotation of spherical nanoparticles on a substrate plate) (83), micrometer-sized particles are easily frozen in a non-equilibrium state due to kinetic barriers. While this problem is already encountered for large precipitates, inclusions, pores, and particle surfaces, it is even more severe for macroscopic flat interfaces, where any change in interface shape occurring through micro-faceting results in an increase in interfacial area. Generally, for the evolution of interface shape, long-range transport is necessary together with mechanisms that allow formation of new facets and destruction of existing ones. The driving force for such mass transport is the difference in chemical component potential between coexisting facets. In equilibrium, all facets exhibit the same chemical potential. For a given volume, every deviation from the equilibrium Wulff shape is associated with a change in the total free interface energy and thus results in deviations of the component chemical potentials at the different facets from their equilibrium chemical potential. The difference in chemical potential between coexisting non-equilibrium interfaces acts as a driving force for all shape evolution. Every shape evolution is based on an interfacial reaction at the receding facet; matter transport (of the crystal building units) from the receding to the growing facet and incorporation of the unit at the growing facet. Numerous reaction steps at the atomic level contribute to shape evolution. Diffusional transport from one facet to another can occur through either bulk phase or along the interface. Facets can only grow or retreat if interfacial ledges move or if new ledges are formed regularly and/or existing ones destroyed. Depending on the rate-controlling step, diffusion-controlled, attachment-limited and ledgenucleation-controlled kinetics are distinguished. Very little theoretical work has been realized on shape evolution of interfaces that is not associated with a chemical reaction. However, a number of recent investigations have addressed a broad range of problems involving shape changes of faceted pores. For small-faceted particles or pores, ledge nucleation is associated with an extremely high-energy barrier (84, 85) that does not allow even a 1-nm size pore to evolve. Intersecting dislocations strongly promote step nucleation and allow relatively large particles to evolve in shape in reasonable time (86). For the cases of rate-controlling diffusion along the interface and rate-controlling attachment processes, the shape evolution for several different fully faceted, two-dimensional polygons was computed (87, 17). The theoretical results were applied to the pore shape evolution in alumina (23) and compared with experimental observations (88, 89, 23). Whereas the above describes shape evolution at constant volume, the computational tool surface evolver (90) describes shape evolution of fully faceted crystals upon growth. The program is based on a least time principle; thus, with time, fast growing facets disappear from the shape.

Solid-State Reactions at the Interface
Heterophase systems evolve through solid state reactions by a combination of matter transport in the two phases and across the interface toward their chemical

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equilibrium. Matter transport in the solid phases occurs via mobile point defects and species through the lattice, along dislocations, grain boundaries or interfaces, under the driving force of the field gradient of one or more thermodynamic variables. The interface has reached its local thermodynamic equilibrium when chemical and point defect equilibria are locally established. This often requires annihilation or creation of point defects, especially those participating in long-range diffusional transport. At the interface, chemical reactions take place between species and defects; they are often associated with structural transformations and volume changes. In general, the interplay of numerous microscopic reaction steps is necessary to displace an interface.
DIFFUSION STEPS Diffusional transport via point defects can be described by irreversible thermodynamics (2, 91). The driving forces can be of multiple nature (chemical potential gradients, temperature gradients, stress gradients, or electric fields).

Interface Reaction Steps
(a) Transfer of species across the interface. When structural units are transferred across the interface from one crystal to another, they often change their identity. They can undergo the transfer as a pair or as individual species, and are affected by the interface resistance according to their charge and kind. We have described above in detail the atomic and electric structure of the interface with its core double layer and an extended space charge layer in the ionic bulk crystals. As depicted in the scheme of Figure 2, core layers and space charge layers exhibit characteristic profiles of the chemical potential of the species and of the electric potential and thus either help or hinder a species to cross the interface. Like any usual site change in the bulk lattice, the transfer across the interface is also associated to an energy barrier. The barrier height is affected by the interface core chemistry. For charged species, its height is either diminished or raised by the electric potential difference across the double layer. The transfer of individual species is coupled (structural unit) by the crystal constraints. Interface-transfer controlled reactions have been reported for the phase transformation of α/βAg2S upon undercooling (2). (b) Relaxation of point defect concentrations and establishment of point defect equilibria. Defect equilibrium concentrations depend on chemical composition, temperature, and stress. Local changes in chemical composition or stoichiometry in the diffusion zones next to the interface or at the interface itself perturb the local point defect equilibria and lead to local point defect super- or undersaturation. Thus defect relaxation has to take place. Different types of point defects demonstrate various relaxation modes and rates. Although intrinsic defect equilibria usually reestablish quickly, relaxation of extrinsic defect concentrations that depend on a chemical component activity may be sluggish, especially if only a restricted number of relaxation sites are provided (for example inner and outer sample surfaces that act as sinks or sources for defects).

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A typical example for sluggish defect relaxation was demonstrated with deviations from the cation vacancy equilibrium concentrations in simple CoO-NiO interdiffusion zones (2, 92, 93). That solid-state reactions may strongly change with the density of point defect equilibration sites was shown for the spinel formation between two oxides (94, 95). Very different reaction scale morphologies and kinetics were obtained when the system was either closed or open at one or both interfaces for oxygen and oxide compound. For a completely closed system, coupling of the cation fluxes directly imposes an oxygen potential gradient in the growing spinel. In an open system, where oxygen accesses both interfaces, the cation fluxes are not coupled and contribute according to the cation diffusivities to the spinel growth. In an asymmetric case with one closed and one open interface, it was reported that under certain conditions extremely high oxygen activities can build up at the interface (corresponding to hydrostatic pressure of 100 kbar). Explosive pore formation or spellation of the entire spinel layer were observed in experiments (95). (c) Ordering of chemical species after transfer across the interface. After their transfer across the interface, the species may have to reorganize in the crystal lattice and re-equilibrate between different lattice sites. This is illustrated again by the example of the spinel formation reaction, where, at the wustite/spinel interface, the cations have to redistribute on octahedral and tetrahedral sites of the oxygen sublattice. From simple relaxation processes in bulk spinels, the time necessary for such cation reorganization has been evaluated (96). (d ) Structural transformation. Most solid-state reactions are accompanied by changes in lattice parameter, symmetry, or even their entire structure, and the interface can move only when the structural constraints for the phase transformation are satisfied and the inherent structural defects are able to move along with the interface. In case of coherent interfaces, the moving interface has to drag its strain field along. With movement, it can minimize its energy by optimizing its shape. It is difficult to theoretically handle the motion of coherent interfaces (97, 98) because the coherency elastic stress alters the mobility of the diffusing species and modifies the diffusion equations and its boundary conditions. Relative phase stabilities and coexisting equilibrium compositions are affected by the stress and may differ from the stress-free state. Thus stress can enhance or diminish interface velocities. Due to the long-range nature of elastic strain, geometric boundary conditions also gain importance for the solid-state reaction: Growth kinetics depend on the crystallographic orientation of the crystals and on the crystal dimensions. The instantaneous strain field varies continuously, thus altering the reaction rate laws and the thermodynamic boundary conditions. Phases were even observed initially to dissolve and later to renucleate and grow, thus providing a very complicated evolutionary reaction path. The influence of elastic stresses on the growth of thin film diffusion couples is a typical example of such behavior; it was evaluated for the reaction sequences observed in Ni-Si thin film diffusion couples (97). The lattice mismatch at semi-coherent interfaces requires the presence of mismatch-accommodating line defects at the interface: misfit dislocations with

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Burgers vectors lying in the interfacial plane and accommodating differences in lattice parameter; misorientation dislocations with Burgers vector components perpendicular to the interface, accommodating deviations of the interfacial plane from an ideal habit plane; disconnections (combined ledge and dislocation character); and ledges with heights of several atomic layers. A certain density of these line defects is necessary to meet crystal and interface plane geometry. A moving semi-coherent interface has to drag along its network of interfacial dislocations. This is possible only if sources or sinks of lattice molecules, in the case of negative and positive misfit, respectively, allow for continuous transformation of the receding into the growing lattice. Depending on interface velocity, habit plane, and dislocation glide planes, different mechanisms can contribute to the interface motion. The mechanism with the fastest dissipation of Gibbs energy always dominates. Dislocation climb permits vacancies (vacancy pairs) and interstitials (interstitial molecules) to be injected into the growing lattice. For dense lattices, the latter mechanism can be unfavorable because of the associated elastic strain. In that case, alternative mechanisms dominate. Glide of dislocations in the interfacial plane can take place if the Burgers vector of the misfit dislocations has a component in one of the slip planes. It has already been shown that ledge formation and motion have relatively high activation energies; this may be the reason, why steps are rarely observed to accommodate the structural transformation upon slow interface motion. For high interface velocities and strong macroscopic curvature of the interfacial plane, however, high densities of ledges are observed [99; M. BackhausRicoult, unpublished results on morphologically unstable, moving (Fe, Mn, Cr)3 O− (Fe, Cr, Mn)2 O3 interfaces)]. Spontaneous formation of interfacial steps and 4 their lateral propagation was also reported for Ni/NiSi2 interfaces (100). Even though disconnections usually have lower formation energy than lattice steps, they were observed only in displacive (martensitic) phase transformations (101). In such transitions (102), the glissile movement of disconnections was induced by important shear stresses. The nature of the interfacial defects accommodating the interface movement between MgO and growing spinel was systematically studied by Hesse as function of the lattice misfit (103–105). Even though the topotaxial oxides both had fcc oxygen sublattices and the reaction occurred via simple cation counter diffusion, sign and size of the misfit imposed very different mechanisms of interface motion. For very small lattice misfit, the interface was coherent and the oxygen sublattice of the receding crystal became that of the growing crystal without any oxygen transport. In the case of negative misfit, misfit dislocations moved by climbing into the MgO crystal, emitting oxygen vacancies into the lattice. In the case of positive misfit, the moving interfacial plane was found to adopt a slight inclination and move by glide of dislocations in the interfacial plane (in a situation, where dislocation climb would have been associated with an energetically unfavorable injection of oxygen interstitials in the dense oxide lattice of the spinel). The three situations are schematically depicted and illustrated by HREM

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Figure 10 Illustration of the atomic mechanisms accommodating lattice mismatch upon the motion of MgO/spinel interfaces (105; courtesy of D. Hesse): (a) no lattice misfit, (b) positive lattice misfit, (c) negative lattice misfit.

images of moving interfaces between MgO and different spinels in Figure 10a–c (105). At non-epitaxial oxide-oxide interfaces, partial dislocations were observed to take part in the transformation of a hexagonal into a cubic oxide lattice (106). For the reduction of FeAl2O4 spinel precipitates to metallic iron and alumina, interface motion is associated with large velocities, considerable volume changes, and important chemical reorganization. Atoms were shown to move over the interface in an unorganized manner, creating either large inhomogeneous stresses or amorphous-like disorder in the reaction zone (107). (e) Reaction- (or diffusion-) related volume changes. At incoherent interfaces, purely geometric misfit dislocations accommodate the lattice mismatch. Motion of the incoherent interface, however, is again associated with the transformation of receding into growing lattice, and thus local volume changes upon the reaction have to be accommodated at the interface. Because the elastic deformation of most materials is restricted, interface can move only when plastic deformation

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mechanisms are activated (108). Depending on material, temperature, and stress, plastic deformation takes place by different mechanisms: diffusion (controlled by the slowest diffusing species), glide, climb of bulk dislocations, or viscous flow. For growing metallic copper or nickel particles in an MgO matrix, emission of dislocation loops at particle edges and formation of dislocation helices and high dislocation densities in the oxide showed that the interface motion was accommodated by dislocation climb in the oxide (Figure 10d ) (109, 110). For growing iron or chromium precipitates in an alumina matrix (at 1500– 1700◦ C), no such dislocations were observed, and it was deduced that reactionrelated volume changes were accommodated by diffusional creep (Figure 10e) (109). Under certain experimental conditions (especially at low temperature), plastic deformation becomes insufficient. The interface motion is then either completely suppressed or stresses are released by fracture of the interface or pore formation (Figure 10f ) (110). For planar, macroscopically extended interfaces, reaction stresses can also be compensated by a viscous displacement of an entire crystal, especially when an external stress is applied perpendicular to the interface (typical situation in reaction couples). Experimental observations of loss of contact in reaction couples are often a direct sign of reaction-related volume changes. In particular cases, contact loss at the interface and its reestablishment by the applied mechanical stress can occur periodically (111).

KINETICS
Solid state reaction kinetics are determined by the complex interplay of the contributing reaction and transport steps. In order to predict the kinetics, the system of coupled differential equations with its boundary conditions has to be solved. Some simplified analogy with electric circuits was introduced (112) by handling the different diffusion steps through analogs of serial resistances, i.e., space charge layers through capacitors and chemical reactions through parallel resistances. Even for multistep mechanisms it was easy to view the different limiting cases. For long-reaction times, when diffusion becomes the rate-controlling reaction step and thermodynamic equilibrium is well established, the interface between two bulk phases is observed to move with the square root of time, yielding parabolic reaction kinetics: s2 = kdiffusion · t (kdiffusion —parabolic rate constant, t—time, s—interface displacement). Especially in initial stages of solid-state reactions, deviations from the parabolic growth law are observed, although for new phase formation, incubation periods can also be observed.

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If the reaction energy is not entirely dissipated in the bulk phases, kinetics deviate from the parabolic behavior. For short reaction times, the interface then often follows a linear law, s = kreaction · t (kreaction—reaction rate constant), indicating that the interface reaction controls the reaction rate. Even though the micro-mechanism-related kinetics are often coupled and can be complex, a simple linear law is obtained as long as the deviations from the local thermodynamic equilibrium at the interface remain small. In an intermediate regime, both diffusion and chemical reaction contribute to the reaction rate; then a mixed rate law is observed of type s = −kdiffusion /kreaction + kdiffusion · t/ s. For spinel formation between alumina and NiO or CoO, differences in the activation energy of the reaction rate constants were observed to produce a strong dependency of the reaction rate on the type of alumina interfacial plane (113, 114). The differences in activation energy can be understood in terms of the atomic mechanisms, in which the hexagonal is transformed into a cubic lattice.

Interface Reaction-Rate Controlled Reactions
Different theoretical approaches have been developed to describe the interface motion when interfacial kinetic barriers inhibit the establishment of local thermodynamic equilibrium at the interface [main phase field approach with an interface of extended thickness and a phase field with a large gradient (115); irreversible thermodynamics with their linear combinations of generalized fluxes and forces (116); or for very high interface velocities and large deviations from the local equilibrium, more generalized balance equations for mass, energy, and momentum (117)]. An alternative may be the introduction of the microscopic reaction steps in the form of boundary conditions in the coupled diffusion problem.

Diffusion-Controlled Reactions
If local thermodynamic equilibrium is established at the interface and everywhere in the bulk and if chemical potential gradients are the only driving forces and diffusion is rate-limiting, then the sequence, morphology and thickness of newly formed reaction products can be predicted to some extent from the thermodynamics and the diffusion kinetics. Product scale morphologies related to nucleation, mechanical stresses and morphological instabilities exceed this simplified approach.
DIFFUSION REACTION PATH In a binary system, interdiffusion profiles can be easily deduced from the diffusion coefficients, and the sequence of the reaction product is indicated by the phase diagram. In ternary and higher systems, however, the sequence of reaction products depends not only on the thermodynamics of the system, but also on the kinetics of transport in the present phases. The composition sequence in a ternary diffusion/reaction couple, called a diffusion (reaction) path,

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is usually presented in an isothermal Gibbs phase triangle. Kirkaldy & Brown (118) related the diffusion path to the set of four composition-dependent interdiffusion coefficients. In an ideal ternary solution, the diffusion path is S-shaped; non-negligible nondiagonal chemical diffusion coefficients make it asymmetric. In a two-phase ternary system, the diffusion path can be determined by solving the coupled diffusion problem with its boundary conditions. This has been undertaken for various simplifications (119–124). It has been shown that the reaction path depends strongly on the starting compositions and on the chemical diffusion coefficients in the present phases. It was also demonstrated that the set of Fick’s equations does not always provide a unique solution; one, two, or three solutions can be found for planar interface geometry when the diffusion path penetrates a miscibility gap (virtual diffusion path) and supersaturated solutions are encountered. Because the calculation of the reaction path requires a large set of thermodynamic and kinetic data and is very laborious, a prediction of the sequence of product phases through simple criteria was tried. As expected, the purely thermodynamic criterion suggesting that reaction products form in the order of their formation energies (125) and the purely kinetic criterion of maximum reaction rate (126) failed. The rule that intrinsic diffusion of an element takes place only in the direction, in which its chemical potential decreases (127) is also not generally valid. Prediction of the precise reaction path is made especially difficult, if reaction products do not form as a sequence of planar layers but arrange in complicated microstructural patterns, for which no simple description of transport exists. Because complex microstructures frequently form in ternary and higher systems as the result of interface morphological instability in respect to diffusional transport, great care has to be taken when predicting diffusion paths for multicomponent systems, that have the thermodynamic ability to form several different phases. The NiAl2O4 spinel formation at Ni-Al2O3 interfaces has been widely studied (55, 128–132). The thermodynamic formation condition indicates that a critical oxygen activity is needed in the metal to form a spinel as a reaction product at the interface. Because this threshold oxygen activity is below the solubility limit of oxygen in metallic nickel, spinel formation can occur at the interface without oxidation of bulk nickel. However, whether the spinel forms depends on the precise starting compositions of the nickel-alumina diffusion couple and the adopted diffusion path in the nickel phase field (Figure 11). For starting alloy compositions with high aluminum and low oxygen content, no spinel forms because the diffusion path connects to a nickel-alumina tie line. For starting alloy compositions with low oxygen content, the diffusion path in the nickel phase field connects to a nickel-spinel tie line, thus indicating that the spinel forms as a reaction product.
KINETICALLY INDUCED INSTABILITY OF THE INTERFACE MORPHOLOGY In ternary and higher systems, a moving interface may evolve in its morphology. Experimental evidence for such evolution was reported for many systems: for simple

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Figure 12 Illustration of diffusion-induced morphological instability in ternary interdiffusion couples in the (Fe,Mn,Cr)-spinel-(Fe,Mn,Cr)-sesquioxide system: (a) phase diagram at 1400◦ C; (b) reaction couple with planar initial interface; (c) illustration of the interface morphologies obtained for different starting compositions; (d ) illustration of the morphological instability criterion, with being the critical stability parameter. For > 0, planar interfaces are unstable in respect to perturbations, for < 0, they are stable.

interdiffusion couples in two-phase ternary systems (121) (see Figure 12), for many solid state reactions; but also for driven binary oxides in an oxygen chemical potential, temperature, or electric field gradient (133, 134). Common to all those examples is the fact that the reaction path of the system runs through a metastable region (supersaturated solution). In a first hypothesis, it was suggested that thermodynamic instability is a necessary and sufficient criterion for such morphological instability, but a detailed examination of the growth rate of nonplanar interfaces by perturbation theory has shown that thermodynamic instability is only a necessary but not sufficient criterion. Wagner related the appearance of complicated microstructural patterns upon alloy oxidation to the fact that in ternary systems, nonplanar interfaces are no longer iso-activity lines, and thus in certain cases promote the growth of microscopic perturbations of a planar interface (135). A mathematical approach to investigate the morphological stability of a surface or interface was first developed by Mullins & Sekerka (136). Analytical solutions and computer simulations have been derived for many specific situations, such as the conditions necessary for the formation of dendrite, cellular, or sea-weed patterns. With application of the morphological stability analysis to planar interfaces in isothermal diffusion couples, a simple criterion for the appearance of diffusioninduced morphological instability can be derived, which imposes for the local

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fluxes at the moving interface that the main transporting flux in the growing phase is larger then the corresponding flux in the receding phase. Because morphological instability is a kinetic phenomenon, it usually develops in first reaction stages and for large deviations from equilibrium. For (nondriven) diffusion-controlled reactions, the interface velocity usually decreases with time, thus allowing more and more three-dimensional transport, which diminishes the anisotropy of the nonplanar interface and flattens it. Purely diffusion-induced instability can be suppressed by a large anisotropic interfacial energy. Elastic effects, such as elastic coherency strain or elastic solution strain, in contrast, promote the tendency of an interface to become nonplanar. The large variety of morphologies that can form upon solid state reactions can be illustrated with the example of displacement reactions at metal-oxide interfaces (A+BO=AO+B), where two reaction products form simultaneously. The limiting morphologies are an arrangement in layers (137) according to the Jost mechanism and in lamellae according to the Wagner mechanism (138). In addition, various agglomerated and dispersed morphologies were observed (139). In some cases, the morphological distribution of the reaction products does not simply result from the diffusional transport. Nucleation phenomena and reaction stresses can lead to very specific microstructures. This was shown for a number of displacement reactions (140, 141), for which a periodic arrangement of the reaction products in space and time was observed. In some cases, such patterns were explained by high nucleation barriers, which give rise to the formation of Liesegang-bands (142). In other cases, a periodic formed by reaction-related build up of stress build up and its release by fracture (141). ACKNOWLEDGMENTS I thank M. Finnis, Belfast University, and D. Hesse, MPI Halle, for providing figures of their work for this review and also thank C. W. Carter, MIT, for helpful discussions on Wulffing. I further acknowledge the CNRS, Corning Incorporated, the Department of Materials Science and Engineering, Cornell University, and especially R. Dieckmann, for providing all conditions necessary to spend a sabbatical stay at Cornell University.
The Annual Review of Materials Research is online at http://matsci.annualreviews.org

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Figure 2 (a) Schematic presentation of a γ -alumina-copper interface with interfacial oxygen excess. (b) Schematic presentation of the electric double layer in the interface core and the space charge layer with its modified defect concentration for a transition metal-oxide interface. (c) Evolution of the electrochemical, chemical, and electric potential across the metal-oxide interface.

Figure 3 (a) Presentation of the characteristic interface point defects at oxygenterminated, cation-terminated, and mixed metal-oxide (M-AO) interfaces. Reading from left to right, oxygen-deficient, stoichiometric, and oxygen-excess interfaces are presented.

Figure 5 (b) Aluminum and oxygen excess concentrations at crystallographically different Cu-alumina interfaces; (c) decrease in specific free interface energy relative to the adsorptionfree state presented for different interfaces as function of oxygen activity.

Figure 11 Dependency of the reaction path in a ternary system on the starting composition illustrated by the reaction between nickel and alumina, where, depending on the initial oxygen content in the nickel alloy, spinel can forms as reaction product.

Figure 9 Evolution of the precipitate equilibrium shape with oxygen activity: selected TEM projections of precipitates together with the associated three-dimensional shape; experimental and Gibbs adsorption model predictions are summarized in the graph presenting the interface free energy ratios for {111} and {001} facets. (a) Liquid Cuinclusions in MgO, T = 1400◦ C; (b) MgO precipitates in a solid Cu matrix, T = 900◦ C.

Figure 9 (Continued )