Structural transformation of Sb-based high-speed phase-change material.

The crystal structure of a phase-change recording material (the compound Ag(3.4)In(3.7)Sb(76.4)Te(16.5)) enclosed in a vacuum capillary tube was investigated at various temperatures in a heating process using a large Debye-Scherrer camera installed in BL02B2 at SPring-8. The amorphous phase of this material turns into a crystalline phase at around 416 K; this crystalline phase has an A7-type structure with atoms of Ag, In, Sb or Te randomly occupying the 6c site in the space group. This structure was maintained up to around 545 K as a single phase, although thermal expansion of the crystal lattice was observed. However, above this temperature, phase separation into AgInTe(2) and Sb-Te transpired. The first fragment, AgInTe(2), reliably maintained its crystal structure up to the melting temperature. On the other hand, the atomic configuration of the Sb-Te gradually varied with increasing temperature. This gradual structural transformation can be described as a continuous growth of the modulation period γ.

Crystallization of the chalcogenide compound Sb8Te3.

The crystallization of a sputtered Sb(8)Te(3) film was examined in an X-ray powder diffraction experiment. An as-sputtered, amorphous Sb(8)Te(3) film crystallized during heating into a structure of Sb-Te homologous series modulated along the stacking direction. During heating the lattice parameters and the modulation period γ were found to change significantly and continuously; this observation suggests a continuous change in the stacking sequence. A superspace analysis revealed that with heating the modulation period γ increased to a value that seemed to be determined by the atomic composition. Once γ reached this value it remained unchanged with cooling. A three-dimensional projection of the converged four-dimensional superspace structure corresponded to the homologous Sb(8)Te(3) structure.

Structural investigation of GeSb6Te10 and GeBi6Te10 intermetallic compounds in the chalcogenide homologous series.

The crystal structures of GeSb(6)Te(10) and GeBi(6)Te(10) were scrutinized using an X-ray powder diffraction method, which revealed that these compounds crystallize in trigonally distorted cubic close-packed structures with a 51-layer period (R3m). Each layer consists of a triangular atomic net; Te atoms occupy their own specific layers, whereas Ge, Sb and Bi atoms are located in the other layers. In these pseudobinary compounds, random atomic occupations of Ge and Sb/Bi are observed and the layers form two kinds of elemental structural blocks by their successive stacking along the c axis. These compounds can be presumed to be isostructural. It is known that the chemical formula of the chalcogenide compounds with the homologous structures found in these pseudobinary systems can be written as (GeTe)(n)(Sb(2)Te(3))(m) or (GeTe)(n)(Bi(2)Te(3))(m) (n, m: integer); the GeSb(6)Te(10) and GeBi(6)Te(10) investigated in this study, which correspond to the case in which n = 1 and m = 3, naturally have 3 x l = 51-layer structures according to a formation rule l = 2n + 5m commonly found in the compounds of these chalcogenide systems (l represents the number of layers in the basic structural unit). Calculations based on the density functional theory revealed that these materials are compound semiconductors with very narrow band gaps.

Structures of stable and metastable Ge2Bi2Te5, an intermetallic compound in a GeTe-Bi2Te3 pseudobinary system.

Ge(2)Bi(2)Te(5) in the GeTe-Bi(2)Te(3) pseudobinary system has two single-crystalline phases: a metastable phase with an NaCl-type structure and a stable phase with a nine-layer trigonal structure. In the metastable phase, the structure consists, in the hexagonal notation, of infinitely alternating stacks of Te and Ge/Bi layers at equal intervals along the c axis. On the other hand, in the stable phase those two layers are stacked alternately nine times to form an NaCl block. The blocks are then piled to construct a nine-layered trigonal structure with cubic close-packed stacking. Both ends of each block are covered with Te layers, contrary to the infinite alternation of Ge/Bi and Te layers in the structure of the metastable phase. The Ge/Bi layers in the metastable phase contain as much as 20 at. % vacancies; on the other hand, those in the stable phase are filled with atoms. These two crystalline phases in Ge(2)Bi(2)Te(5) have identical atomic configurations to the two corresponding phases found in Ge(2)Sb(2)Te(5).

Single structure widely distributed in a GeTe-Sb2Te3 pseudobinary system: a rock salt structure is retained by intrinsically containing an enormous number of vacancies within its crystal.

GeTe(1-x)-Sb2Te3(x) sputtered amorphous film was crystallized into a simple NaCl-type structure through instantaneous laser irradiation over a wide composition range from x = 0 to at least 2/3. When the ratio of Sb2Te3 increases, a vacancy is generated at every Na site for two Sb atoms. The fraction of vacancies, v(x), changes according to x/(1 + 2x), and the cubic root unit cell volume varies with a strong correlation to v(x). Through these created vacancies, valence electrons provided by adjacent Ge/Sb and Te atoms remain constant regardless of the composition, ensuring that these electrons occupy predominantly the bonding molecular orbitals. This results in crystal chemical stability, with the closed shell p-p bondings in the valence electrons arranging the crystal's atomic configuration into an NaCl-type structure.

Extremely long period-stacking structure in the Sb-Te binary system.

The crystal structure of the delta-phase in the Sb-Te binary system has been determined by synchrotron powder diffraction. It is clearly shown that many intermetallic compounds, which have different stacking periods depending on compound composition, exist in this phase. These structures are based on the cubic ABC stacking structure, and two kinds of fundamental structural units form an intergrowth along the stacking direction at the atomic level. The chemical formulae of these compounds are expressed as Sb(2n)Te3, where n is an integer and the number of stacking layers is 2n + 3. There is a relationship of inverse proportionality between the stacking period and the Te concentration.