Time-Dependent Interfacial Reaction Mechanism in a Spinel-Forming Solid State Reaction Studied by TEM

1996 ◽  
Vol 466 ◽  
Author(s):  
P. Werner ◽  
H. Sieber ◽  
R. Huxebrand ◽  
D. Hesse

ABSTRACTInterfacial reaction mechanisms were investigated in case of topotaxial formation of MgIn2O4 spinel on MgO crystals, which is an appropriate model system for thin film solid state reactions in ceramics. The reaction interface MgO/MgIn2O4(001), which is characterized by a large lattice misfit (+4.2%) between these cubic crystals, was investigated by transmission electron microscopy (TEM). Thin spinel films (thickness t< 0.5μm) consist of domains tilted off (≈3.5°) the exact cube-to-cube orientation into four directions, while thicker films (t> 1μm) show an accurate (001) orientation. High-resolution electron microscopy (HREM) showed that this time-dependent orientation behavior correlates with the atomic scale structure of the interface, especially with the different types of misfit dislocations. Based on these results, the misfit accommodation mechanism at the propagating reaction front in this spinel system is discussed including transitions between glide and climb processes.

Author(s):  
David J. Smith

The era of atomic-resolution electron microscopy has finally arrived. In virtually all inorganic materials, including oxides, metals, semiconductors and ceramics, it is possible to image individual atomic columns in low-index zone-axis projections. A whole host of important materials’ problems involving defects and departures from nonstoichiometry on the atomic scale are waiting to be tackled by the new generation of intermediate voltage (300-400keV) electron microscopes. In this review, some existing problems and limitations associated with imaging inorganic materials are briefly discussed. The more immediate problems encountered with organic and biological materials are considered elsewhere.Microscope resolution. It is less than a decade since the state-of-the-art, commercially available TEM was a 200kV instrument with a spherical aberration coefficient of 1.2mm, and an interpretable resolution limit (ie. first zero crossover of the contrast transfer function) of 2.5A.


1985 ◽  
Vol 56 ◽  
Author(s):  
C. CHOI ◽  
N. OTSUKA ◽  
L. A. KOLODZIEJSKI ◽  
R. L. GUNSHOR-a

AbstractStructures of CdTe-Cd0.6Mn0.4Te superlattices which are caused by the lattice mismatch between suterlattice layers have been studied by high resolution electron microscopy (HREM). In thin-layer superlattices, the crystal lattice in each layeris elastically distorted, resulting in the change of the crystal symmetry from cubic to rhombohedral. The presence of the small rhombohedral distrotion has been confirmed through a phase contrast effect in HREM images. In a thick-layer superlattice, the lattice mismatch is accommodated by dissociated misfit dislocations. Burgers vectors of partial misfit dislocations have been identified from the shift of lattice fringes in HREM images.


1986 ◽  
Vol 77 ◽  
Author(s):  
Mary Beth Stearns ◽  
Amanda K. Petford-Long ◽  
C.-H. Chang ◽  
D. G. Stearns ◽  
N. M. Ceglio ◽  
...  

ABSTRACTThe technique of high resolution electron microscopy has been used to examine the structure of several multilayer systems (MLS) on an atomic scale. Mo/Si multilayers, in use in a number of x-ray optical element applications, and Mo/Si multilayers, of interest because of their magnetic properties, have been imaged in cross-section. Layer thicknesses, flatness and smoothness have been analysed: the layer width can vary by up to 0.6nm from the average value, and the layer flatness depends on the quality of the substrate surface for amorphous MLS, and on the details of the crystalline growth for the crystalline materials. The degree of crystallinity and the crystal orientation within the layers have also been investigated. In both cases, the high-Z layers are predominantly crystalline and the Si layers appear amorphous. Amorphous interfacial regions are visible between the Mo and Si layers, and crystalline cobalt suicide interfacial regions between the Co and Si layers. Using the structural measurements obtained from the HREM results, theoretical x-ray reflectivity behaviour has been calculated. It fits the experimental data very well.


1993 ◽  
Vol 8 (9) ◽  
pp. 2112-2127 ◽  
Author(s):  
A. Bardal ◽  
O. Eibl ◽  
Th. Matthée ◽  
G. Friedl ◽  
J. Wecker

The microstructures of YBa2Cu3O7−δ (YBCO) thin films grown on Si with Y-stabilized ZrO2 (YSZ) and Y2O3 buffer layers were characterized by means of high-resolution electron microscopy. At the Si–YSZ interface, a 2.5 nm thick layer of regrown amorphous SiOx is present. The layer is interrupted by crystalline regions, typically 5 to 10 nm wide and 10 to 50 nm apart. Close to the crystalline regions, {111} defects are present in the Si substrate. The typical defect observed is an extrinsic stacking fault plus a perfect dislocation close to the stacking fault which terminates extra {111} planes in the upper part of the Si. These defects are probably formed by condensation of Si self-interstitials created during oxide regrowth. Precipitates are present in the Si close to the Si–YSZ interface and indicate that in-diffusion of Zr has occurred. The YSZ–Y2O3 interface is atomically sharp and essentially planar and contains no second phases. Perfect misfit dislocations with Burgers vector 1/2〈110〉 are present at this interface along with unrelaxed elastic misfit stresses. The Y2O3–YBCO interface is atomically sharp and planar, but contains steps. (001) stacking faults are present in the YBCO above these steps; the faults are, however, healed a few unit cells away from the interface. By HREM analysis of ultrathin specimen areas, the atomic layer of the YBCO closest to the Y2O3 was found to be a barium-oxygen layer.


1989 ◽  
Vol 159 ◽  
Author(s):  
A. Catana ◽  
M. Heintze ◽  
P.E. Schmid ◽  
P. Stadelmann

ABSTRACTHigh Resolution Electron Microscopy (HREM) was used to study microstructural changes related to the CoSi/Si-CoSi/CoSi2/Si-CoSi2/Si transformations. CoSi is found to grow epitaxially on Si with [111]Si // [111]CoSi and < 110 >Si // < 112 >CoSi. Two CoSi non-equivalent orientations (rotated by 180° around the substrate normal) can occur in this plane. They can be clearly distinguished by HRTEM on cross-sections ( electron beam along [110]Si). At about 500°C CoSi transforms to CoSi2. Experimental results show that the type B orientation relationship satisfying [110]Si // [112]CoSi is preserved after the initial stage of CoSi2 formation. At this stage an epitaxial CoSi/CoSi2/Si(111) system is obtained. The atomic scale investigation of the CoSi2/Si interface shows that a 7-fold coordination of the cobalt atoms is observed in both type A and type B epitaxies.


1990 ◽  
Vol 202 ◽  
Author(s):  
A. Catana ◽  
P.E. Schmid

ABSTRACTHigh Resolution Electron Microscopy (HREM) and image calculations are combined to study microstructural changes related to the CoSi/Si-CoSi/CoSi2/Si-CoSi2/Si transformations. The samples are prepared by UHV e-beam evaporation of Co layers (2 nm) followed by annealing at 300°C or 400°C. Cross-sectional observations at an atomic scale show that the silicidation of Co at the lower temperature yields epitaxial CoSi/Si domains such that [111]Si // [111]CoSi and <110>Si // <112>CoSi. At about 400°C CoSi2 nucleates at the CoSi/Si interface. During the early stages of this chemical reaction, an epitaxial CoSi/CoSi2/Si system is observed. The predominant orientation is such that (021) CoSi planes are parallel to (220) CoSi2 planes, the CoSi2/Si interface being of type B. The growth of CoSi2 is shown to proceed at the expense of both CoSi and Si.


1991 ◽  
Vol 6 (8) ◽  
pp. 1744-1749 ◽  
Author(s):  
L. Hultman ◽  
D. Hesse ◽  
W-A. Chiou

Mg–Ti–spinel formation along the interface of epitaxial TiN(100) films to MgO(100) substrates has recently been investigated by transmission electron microscopy (TEM) in the diffraction-contrast mode in samples grown at substrate temperatures higher than 800 °C and in such post-annealed at 850 °C. This phenomenon has now been investigated by high resolution electron microscopy of cross-sectional samples, at an acceleration voltage of 300 kV. Emphasis is given to the TiN/spinel and the spinel/MgO interfaces with respect to their structure and morphology. The results obtained confirm the previously drawn conclusions on the atomic mechanism of the solid state reaction during the spinel-forming process: The spinel, which most likely is of the composition Mg2TiO4, forms by counterdiffusion of the cations Ti4+ and Mg2+ in the rigid oxygen frame provided by the fcc oxygen sublattice of MgO. The latter is completely taken over by the spinel lattice. This “host” character of the MgO substrate lattice for the topotaxial growth of the spinel lattice and the coherency of the solid state reaction with respect to the lattices of all the phases involved are demonstrated. Misfit dislocations at the TiN/MgO, TiN/spinel, and the spinel/MgO interfaces, as well as antiphase boundaries of the cation sublattice of the spinel phase, have also been observed.


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