Study on Single Crystal Growth by Solid State Recrystallization using Defect Sulfide Spinel Compounds

利用缺陷硫化物尖晶石化合物固态重结晶生长单晶的研究

• 批准号: 03452294
• 负责人: OHACHI Tadashi
• 金额: $ 0.96万
• 依托单位: DOSHISHA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-03452294/
• 关键词: sulfide spinel compounds; Solid state reaction; Solid state Crystal growth; defect type spinel

Solid state recrystallization method to grow large single crystal of silver or copper defect sulfide spinel compounds was studied. These sulfide spinel compounds have large atomic transport through solid state because of electronic and ionic mixed conductors.The purpose of this study was to clarify the mechanism of the solid state recrystallization and grow single crystal of defect spinel compounds of silver or copper defect sulfide spinel.Single crystals of normal sulfide spinel, MIn_5S_8 (M=Cu,Ag) and defect spinels, MIn_7S_<11>, MIn_9S_<14>, MIn_<11>S_<17> and MIn_<21>S_<32> were grown by a horizontal Bridgman method and successive annealing at high temperature. This method is a suitable way to grow large single crystals, which have different liquidus and solidus.The crystal structures were analyzed by a X-ray diffraction method. According to the increment of the number of defect vacancy in the unit cell, lattice constants of Cu-In-S series and Ag-In-S series were linearly increased and decreased respectively.X-ray Photoelectron Spectroscopy (XPS) is used to analyze the valence of Cu, Ag and In ions. Cu and Ag take +1 valence and In takes +3 valence.By a solid-vapor reaction, chemical diffusion coefficients of metallic atom in solid state were determined. With increasing the number of vacancies, chemical diffusion coefficient of them increase.

研究了用固相再结晶法生长银或铜缺陷尖晶石化合物大单晶的方法。本文采用水平布里奇曼法和高温连续退火法生长了正常硫化物尖晶石MIn_5S_8（M=Cu，Ag）和缺陷尖晶石MIn_7S_，MIn_9S_，MIn_S_4和MIn_S_5单晶，研究了它们的固态再结晶机理，并生长<11><14><11><17><21><32>了缺陷尖晶石单晶。该方法适合于生长具有不同液相线和固相线的大单晶体，并用X射线衍射方法分析了晶体结构。Cu-In-S系列和Ag-In-S系列的晶格常数分别随晶胞中缺陷空位数的增加而线性增加和减小，用X射线光电子能谱（XPS）分析了Cu、Ag和In离子的价态。Cu和Ag以+1价存在，In以+3价存在，通过固-气反应，测定了金属原子在固态下的化学扩散系数。随着空位数的增加，空位的化学扩散系数增大。

项目成果

T.OHACHI;K.ASAHI;Y.OKANO,and I.TANIGUCHI: "Single Crystal Growth of Cu-In-S and Ag-In-S Spinels" J.Crystal Growth.

T.OHACHI；K.ASAHI；Y.OKANO 和 I.TANIGUCHI：“Cu-In-S 和 Ag-In-S 尖晶石的单晶生长”J.Crystal Growth。

岡野 陽子,旭 憲一,大鉢 忠,谷口 一郎: "空隙欠陥型銀・銅硫化物スピネル化合物の格子定数" 同志社大学理工学研究報告. 34. (1993)

Yoko Okano、Kenichi Asahi、Tadashi Ohbachi、Ichiro Taniguchi：“空隙缺陷银/硫化铜尖晶石化合物的晶格常数”，同志社大学科学与工程研究报告34。（1993）

T.Ohachi,M.Hiramoto Y.Yoshihara,and I.Taniguchi: "Silver Atomic Trap Measurement in Ag_2 by Coulometric Method" Solid State Oonics. 51. 191-196 (1992)

T.Ohachi、M.Hiramoto Y.Yoshihara 和 I.Taniguchi：“通过库仑法测量 Ag_2 中的银原子陷阱”固态 Oonics。

T. Ohachi: "Growth and Transport Properties of Superionic Conductors" Proceedings of Asian-Pacific Society for Advanced Materials (APSAM)-92.

T. Ohachi：“超离子导体的生长和输运特性”亚太先进材料学会 (APSAM) 会议记录-92。

大鉢 忠,旭 憲一,谷口 一郎: "水平ブリッジマン法による銀・銅硫化物スピネル学結晶の成長" 同志社理工学研究報告.

Tadashi Ohbachi、Kenichi Asahi、Ichiro Taniguchi：“水平布里奇曼法生长银和铜硫化物尖晶石晶体”同志社科学与工程研究报告。