Copper(I) Halide Nanoparticle-dispersed Glasses Prepared by Copper Staining
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Tatsuya Suetsugu, Takeshi Ohtani, Toshihiko Einishi, and Takashi Tarumi Isuzu Glass Co., Ltd., Minami-Tsumori, Nishinari, Osaka 557-0063, Japan
Tetsuo Yazawa University of Hyogo, Himeji 671-2201, Japan (Received 21 December 2004; accepted 25 May 2005)
Copper(I) chloride and bromide nanoparticle-dispersed glasses were prepared by means of a conventional copper staining. The staining was performed by the following process: copper stain was applied on the surfaces of Cl−- or Br−-ion-containing borosilicate glasses, and the glasses were heat-treated at 510 °C for various times. Typical exciton bands observed in the absorption spectra of the glasses after the heat treatment indicated that CuCl and CuBr particles were formed in the surface region of the glasses. The average sizes of the CuCl and CuBr particles in the glasses heat-treated for 48 h were estimated at 4.8 and 2.7 nm, respectively. The nanoparticles were also characterized by x-ray diffraction and transmission electron microscopy. Depth profiles of Cu and CuBr concentration in the glass heat-treated for 48 h were measured. Copper decreased in concentration monotonously with depth, reaching up to 60 m, while the CuBr concentration had a maximum at about 25 m in depth.
I. INTRODUCTION
Copper halide nanoparticle-dispersed glasses have received much attention with respect to quantum-size effects and nonlinear optical properties of the semiconductor nanoparticles.1–11 The glasses are also applied to optical sharp-cut filters using nanoparticle exciton absorption.12 The literature describes some methods for preparation of the copper halide nanoparticle-dispersed glasses: a conventional annealing method in which copper halide particles are precipitated from a glass matrix containing Cu+ and halide ions,3 a sol-gel method,13–17 a sputtering method, 18–21 and an ion-implantation method22–26 in which Cu+ and halide ions are implanted at the energy of the ions, which is adjusted so that depth profiles of the both ions overlap. Among them, the annealing method is the simplest process for preparing the bulk glasses. To apply these materials for optoelectronic devices such as optical waveguides, however, thin films or layers are more suitable. From this point of view, the sol-gel, sputtering, and ion-implantation methods are superior, although these methods need strict reaction
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Address correspondence to this author. e-mail: [email protected] DOI: 10.1557/JMR.2005.0295 2480
http://journals.cambridge.org
J. Mater. Res., Vol. 20, No. 9, Sep 2005 Downloaded: 31 Mar 2016
conditions to control the valence of copper ions (for the sol-gel method) or large equipment including vacuum chambers (for the sputtering and the ion-implantation methods). We previously reported an alternative preparation method of CuBr nanoparticle-dispersed glass layers in which copper ions are incorporated into glass surfaces containing Br− ions using copper staining.27 Staining is a conventional and convenient method for coloration of glasses.28,29 The coloration mechanism in silver staini
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