Cooling of Melts: Kinetic Stabilization and Polymorphic Transitions in the KInSnSe4 System

Inorganic Chemistry

Volumn 43, Issue 7, 2004, Pages 2237-2239

  Hwang, Seong Ju ^a,b   Iyer, Ratnasabapathy G ^a   Trikalitis, Pantelis N ^a   Ogden, Andrew G ^a   Kanatzidis, Mercouri G ^a  

^a MICHIGAN STATE UNIVERSITY   (United States)

^b Konkuk University   (South Korea)

Author keywords

[No Author keywords available]

Indexed keywords

INDIUM; POTASSIUM ION; TIN;

ARTICLE; COOLING; CRYSTALLIZATION; CRYSTALLOGRAPHY; HEATING; KINETICS; MELTING POINT; NONPHOTOCHEMICAL QUENCHING; SOLID STATE; STOICHIOMETRY; THERMODYNAMICS;

EID: 1842459418     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic0351545     Document Type: Article

References (13)

1. (a) Kanatzidis, M. G. Chem. Mater. 1990, 2, 353.
2. (b) Kanatzidis, M. G.; Sutorik, A. C. Prog. Inorg. Chem. 1995, 43, 151.
3. (c) Kanatzidis, M. G. Curr. Opin. Solid State Mater. Sci. 1997, 2, 139.
4. Breshears, J. D.; Kanatzidis, M. G. J. Am. Chem. Soc. 2000, 122, 7839.
5. 4 suitable for single-crystal X-ray investigation were obtained by forming a melt at 850 °C and cooling at -10 °C/min to room temperature.
6. 2Se, In, Sn, and Se. The starting materials were vacuum-sealed in a fused silica tube, thoroughly melted in a torch flame, and allowed to rapidly cool in air. The cooling rate from the melt temperature to ∼200 °C is estimated approximately at ∼ -600 °C/min. At room temperature (rt), transparent reddish plate crystals could be isolated.
7. 3.8". The EDS results are good to ±3-4%.
8. 2, GOF = 1.185. R1 = 1.72%, wR2 = 4.36% for I > 2σ(I). An empirical absorption correction was done using SADABS, (b) and the full anisotropic structure refinement was carried out using the SHELXTL programs.
9. max = 28°, 17307 total reflections, 4198 unique reflections with R(int) = 0.0854, refinement on F2, GOF = 0.936. R1 = 4.46%, wR2 = 13.76% for I > 2σ(I). Sn and In sites are not distinguishable with X-ray diffraction, but they can be inferred by the observed bond lengths and bond valence sum calculations.
10. 2, R(int) = 0.0817, GOF = 1.296, R1 = 6.4%, wR2 = 10.56 for I > 2σ(I). In/Sn atoms occupy the same crystallographic sites.
11. Eisenmann, B.; Jakowski, M.; Schaefer, H. Mater. Res. Bull. 1982, 17, 1169.
12. Transformation occurs in the solid state at ∼650 °C for 24 h and is confirmed with powder X-ray diffraction.
13. 4 (0.4 < × < 1.6), led consistently to the α-form. This suggests the layered form cannot tolerate a large number of vacancies. It also betrays an exceptional ability of the tetragonal T1Se structure type to accommodate an extensive number of vacancies on the crystallographic sites occupied by the alkali metals and also nucleate rapidly.