Li_2O-SiO_2系透明結晶化ガラス中でのCr^<4+>イオンの生成と光吸収及び発光スペクトル
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The formation mechanism, optical absorption and emission spectra of Cr^<4+> ions-containing Li_2O-SiO_2 system transparent glass-ceramics were investigated. In this material, the main crystalline phase was Li_2O・2SiO_2, and the percent crystallinity and crystal size were 67-72 and 20-33 nm, respectively. The remarkable change in color and absorption spectra was observed upon crystallization. The characteristic emission of tetrahedrally coordinated C^_<4+> ions was identified in the near infrared region, 1000-1600 nm. It was found that tetrahedrally coordinated Cr^<4+> ions exist in this transparent glass-ceramics from absorption and emission measurement. The Cr^<4+> ions exist in residual high SiO_2 glassy phase, and their ligand field parameters are estimated to be: 10Dq = 10,610 cm^<-1>, B = 690 cm^<-1> and Dq / B = 1.54. This Dq / B Value is just below the crossing point of ^3T_2 and ^1E levels (Dq / B = 1.6). The Cr^<4+> ions in Li_2O-SiO_2 system transparent glass-ceramics occupy the little stronger ligand field sites than those in aluminate glass reported previously (Dq / B = 1.2). It is considered that the Cr^<4+> ions can be formed by the reduction of Cr_<6+> ions (chromate ion [CrO_4]^<2->) associated with decreasing the basicity of residual glassy phase during crystallization. In this process the behavior of Li^+ ions plays a significant role. The [CrO_4] formed is equivalent to [SiO_4] and substitutes [SiO_4] sites in the residual high SiO_2 glassy phase.
- 社団法人日本セラミックス協会の論文
- 2004-09-01
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