skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: The two-phase region in 2(ZnSe) {sub x} (CuInSe{sub 2}){sub 1-} {sub x} alloys and structural relation between the tetragonal and cubic phases

Abstract

The two-phase region in the system 2(ZnSe) {sub x} (CuInSe{sub 2}){sub 1-} {sub x} covers the chemical composition range 0.10<x{<=}0.36, in which a tetragonal and a cubic phase are coexisting. The structural relation between both phases was determined by selected area diffraction (SAD) and transmission electron microscopy (TEM). Both crystal structures are very similar and the extremely small mismatch of the lattice constants of the tetragonal phase and the embedding cubic matrix phase allows for the grain boundaries to be virtually strain-free and, therefore, without notable dislocations. The tetragonal phase forms grains of flat discus-like shape in the ambient cubic matrix, with the short discus axis parallel to the tetragonal c-axis. TEM experiments proved that the discus-shaped tetragonal particles are collinear with the (100){sub cub}, (010){sub cub} and (001){sub cub} planes of the cubic phase. Cooling and annealing experiments revealed a near-equilibrium state only to be realized for small cooling rates less than 2 K/h and/or for a long-time annealing with subsequent rapid quenching. Only then there will be no cation ordering in both, the tetragonal domains and the parental cubic matrix phase. If, however, the samples are kept in a state far away from the equilibrium condition both phasesmore » reveal Stannite-type cation ordering. Within the composition range of 0{<=}x{<=}0.10 only tetragonal 2(ZnSe) {sub x} (CuInSe{sub 2}){sub 1-} {sub x} -alloys exist. At concentration rates above 36 mol% 2(ZnSe) only cubic structured solid solutions of ZnSe and CuInSe{sub 2} are found to be stable. However, in the range 36 mol% to about 60 mol% 2(ZnSe) tiny precipitates with Stannite-like structure exist, too.« less

Authors:
 [1];  [2];  [2];  [3];  [2]
  1. Institute of Mineralogy, Crystallography and Materials Science, University of Leipzig, Scharnhorststr. 20, 04275 Leipzig (Germany). E-mail: wagner@chemie.uni-leipzig.de
  2. Institute of Mineralogy, Crystallography and Materials Science, University of Leipzig, Scharnhorststr. 20, 04275 Leipzig (Germany)
  3. Faculty for Physics and Earth Science, Nuclear Solid State Physics, University of Leipzig, Linnestr. 5, D-04103 Leipzig (Germany)
Publication Date:
OSTI Identifier:
20784807
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 178; Journal Issue: 12; Other Information: DOI: 10.1016/j.jssc.2005.09.009; PII: S0022-4596(05)00412-3; Copyright (c) 2005 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; ANNEALING; COPPER SELENIDES; CUBIC LATTICES; DISLOCATIONS; GRAIN BOUNDARIES; INDIUM SELENIDES; LATTICE PARAMETERS; PHASE DIAGRAMS; SOLID SOLUTIONS; TETRAGONAL LATTICES; TRANSMISSION ELECTRON MICROSCOPY; ZINC SELENIDES

Citation Formats

Wagner, G., Lehmann, S., Schorr, S., Spemann, D., and Doering, Th. The two-phase region in 2(ZnSe) {sub x} (CuInSe{sub 2}){sub 1-} {sub x} alloys and structural relation between the tetragonal and cubic phases. United States: N. p., 2005. Web. doi:10.1016/j.jssc.2005.09.009.
Wagner, G., Lehmann, S., Schorr, S., Spemann, D., & Doering, Th. The two-phase region in 2(ZnSe) {sub x} (CuInSe{sub 2}){sub 1-} {sub x} alloys and structural relation between the tetragonal and cubic phases. United States. doi:10.1016/j.jssc.2005.09.009.
Wagner, G., Lehmann, S., Schorr, S., Spemann, D., and Doering, Th. Thu . "The two-phase region in 2(ZnSe) {sub x} (CuInSe{sub 2}){sub 1-} {sub x} alloys and structural relation between the tetragonal and cubic phases". United States. doi:10.1016/j.jssc.2005.09.009.
@article{osti_20784807,
title = {The two-phase region in 2(ZnSe) {sub x} (CuInSe{sub 2}){sub 1-} {sub x} alloys and structural relation between the tetragonal and cubic phases},
author = {Wagner, G. and Lehmann, S. and Schorr, S. and Spemann, D. and Doering, Th.},
abstractNote = {The two-phase region in the system 2(ZnSe) {sub x} (CuInSe{sub 2}){sub 1-} {sub x} covers the chemical composition range 0.10<x{<=}0.36, in which a tetragonal and a cubic phase are coexisting. The structural relation between both phases was determined by selected area diffraction (SAD) and transmission electron microscopy (TEM). Both crystal structures are very similar and the extremely small mismatch of the lattice constants of the tetragonal phase and the embedding cubic matrix phase allows for the grain boundaries to be virtually strain-free and, therefore, without notable dislocations. The tetragonal phase forms grains of flat discus-like shape in the ambient cubic matrix, with the short discus axis parallel to the tetragonal c-axis. TEM experiments proved that the discus-shaped tetragonal particles are collinear with the (100){sub cub}, (010){sub cub} and (001){sub cub} planes of the cubic phase. Cooling and annealing experiments revealed a near-equilibrium state only to be realized for small cooling rates less than 2 K/h and/or for a long-time annealing with subsequent rapid quenching. Only then there will be no cation ordering in both, the tetragonal domains and the parental cubic matrix phase. If, however, the samples are kept in a state far away from the equilibrium condition both phases reveal Stannite-type cation ordering. Within the composition range of 0{<=}x{<=}0.10 only tetragonal 2(ZnSe) {sub x} (CuInSe{sub 2}){sub 1-} {sub x} -alloys exist. At concentration rates above 36 mol% 2(ZnSe) only cubic structured solid solutions of ZnSe and CuInSe{sub 2} are found to be stable. However, in the range 36 mol% to about 60 mol% 2(ZnSe) tiny precipitates with Stannite-like structure exist, too.},
doi = {10.1016/j.jssc.2005.09.009},
journal = {Journal of Solid State Chemistry},
number = 12,
volume = 178,
place = {United States},
year = {Thu Dec 15 00:00:00 EST 2005},
month = {Thu Dec 15 00:00:00 EST 2005}
}
  • The cubic-tetragonal phase transition of 14 mol% ErO[sub 1.5]-ZrO[sub 2] was investigated through high-temperature powder X-ray diffraction. A new tetragonal form without tetragonality, t[double prime]-ZrO[sub 2], was taken into consideration, although only two forms of t- and t[prime]-ZrO[sub 2] have previously been distinguished. The metastable t[double prime]-ZrO[sub 2], which could be obtained by rapid quenching of 14 mol% ErO[sub 1.5]-ZrO[sub 2] melts, partially changed into t[prime]-ZrO[sub 2] through a thermal activation process above 500C. The t[prime]-ZrO[sub 2] continuously changed into t[double prime]-ZrO[sub 2] or transformed into cubic phase at about 1,200C. The t[prime]-t[double prime] change occurred reversibly below 1,100C.
  • The influence of crystal mixing on the structural phase transitions in Rb{sub 1{minus}x}Cs{sub x}CaF{sub 3} (0{lt}x{lt}1) fluoroperovskite crystals has been studied by thermal expansion and EPR measurements of Ni{sup 2+} and Ni{sup 3+} paramagnetic probes. A cubic-to-tetragonal phase transition has been detected in crystals with x=0, 0.1, 0.21, 0.27, and 0.35. The critical temperature and the tetragonal distortion decrease as x increases. No transition was observed for x{ge}0.44. This transition shows a weak first-order component in the x=0 and 0.1 samples, which is progressively smeared out for x{gt}0.1, indicating a spatial distribution of the critical temperature in those crystals withmore » high ionic substitution rate. In RbCaF{sub 3}, another structural phase transition was observed at 20 K with a thermal hysteresis between 20 and 40 K. This transition has not been found in any of the mixed crystals.« less
  • The tetragonal-to-cubic phase transition of rapidly quenched 12 mol% ErO[sub 1.5]-ZrO[sub 2] was investigated in situ using high-temperature X-ray diffraction. Rapid quenching of the melt yielded a small oxygen ion displacement and a small tetragonality, axial ratio c/a. Although the tetragonality of the as-quenched specimen increased with temperature up to about 1,000C, it became independent of temperature on cooling to room temperature from about 1,000C and reheating up to 1,000C. The tetragonality decreased continuously with temperature above 1,000C and became unity at about 1,400C. The atomic coordination z for the oxygen ion, which expresses the displacement from its ideal sitemore » in the fluorite-type structure, increased with temperature and became 1.4 at about 1,400C. The tetragonality increased with annealing time through a thermal activation, which could explain the compositional dependence of the tetragonality in rapidly quenched ZrO[sub 2]-RO[sub 1.5] samples (R = rare earths).« less
  • A structural phase transition between the cubic (space group, Fm3m) and tetragonal (space group, P4[sub 2]/nmc) phases in a zirconia-ceria solid solution (Zr[sub 1[minus]x]Ce[sub x]O[sub 2]) has been observed by Raman spectroscopy. The cubic-tetragonal (c-t[double prime]) phase boundary in compositionally homogeneous samples exist at a composition X[sub 0] (0.8
  • The C11b phase crystalline structure (structure type MoSi{sub 2}, space group I4/mmm) in the Zr{sub 2}Cu{sub (1-x)}Pd{sub x} (x = 0, 0.25, 0.5, 0.75 and 1) alloys was examined in situ using high temperature X-ray diffraction (HTXRD) and Rietveld refinement of the data obtained at a constant heating rate. While the cell volume increases with increasing Pd as expected by the larger atomic radii, the coefficients of thermal expansion (CTEs) do not follow a uniform trend. The bonding in the basal plane is more elastically rigid than along the c-axis for all compositions. The CTE is more anisotropic for Zr{submore » 2}Pd than for Zr{sub 2}Cu, which is consistent with the first-principles calculations that illustrate the rigidity of c-axis relatively to a-axis to be the less for Zr{sub 2}Pd. The CTE of the a-axis for Zr{sub 2}Pd is in fact negative over the temperature range measured.« less