JPH03174337A - Glass containing deposited superfine particles of cucl and cubr and production thereof - Google Patents
Glass containing deposited superfine particles of cucl and cubr and production thereofInfo
- Publication number
- JPH03174337A JPH03174337A JP3747990A JP3747990A JPH03174337A JP H03174337 A JPH03174337 A JP H03174337A JP 3747990 A JP3747990 A JP 3747990A JP 3747990 A JP3747990 A JP 3747990A JP H03174337 A JPH03174337 A JP H03174337A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- cubr
- cucl
- precipitated
- ultrafine particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011521 glass Substances 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000002245 particle Substances 0.000 title abstract description 12
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims abstract description 34
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims abstract description 23
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 23
- 239000011882 ultra-fine particle Substances 0.000 claims description 47
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Inorganic materials O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 abstract 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 description 15
- 238000000034 method Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 239000010949 copper Substances 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- -1 alkali borate Chemical class 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000015654 memory Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 101100348017 Drosophila melanogaster Nazo gene Proteins 0.000 description 1
- 229910015017 LiaO Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical class Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、ＣｕＣｌ、ＣｕＢｒ超微粒子析出ガラス及び
その製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to CuCl, CuBr ultrafine particle precipitated glass and its manufacturing method.
［従来の技術］
従来、黄色〜赤色のシャープカット色ガラスフィルター
として用いられていた、ＣｄＳ、 ＣｄＳｅなどの半導
体超微粒子が析出したガラスが、最近高い非線形光学特
性を有する事が示され、高調波光の発生、位相共役光の
発生、光双安定性を利用した超高速光スィッチ、メモリ
ーなどの非線形光学材料として注目されている。超微粒
子析出ガラスが高い非線形光学特性を有する理由は、半
導体超微粒子中の励起子が、ガラスの作る深いポテンシ
ャルによって３次元的に閉じ込ぬられる量子閉じ込め効
果によるものと考えられている。[Prior art] Glass with precipitated semiconductor ultrafine particles such as CdS and CdSe, which was conventionally used as yellow to red sharp-cut color glass filters, has recently been shown to have high nonlinear optical properties, and has been used as a filter for harmonic light. It is attracting attention as a nonlinear optical material for use in the generation of phase conjugate light, generation of phase conjugate light, ultrafast optical switches that utilize optical bistability, memories, etc. The reason why ultrafine particle precipitated glass has high nonlinear optical properties is thought to be due to the quantum confinement effect in which excitons in semiconductor ultrafine particles are three-dimensionally confined by the deep potential created by the glass.
このような半導体超微粒子が析出したガラスは、前述し
たＣｄ５−ＣｄＳｅ系の超微粒子析出ガラスが知られて
いる。As a glass on which such semiconductor ultrafine particles are precipitated, the above-mentioned Cd5-CdSe-based ultrafine particle precipitated glass is known.
一方、最近ＣｕＣ１を微粒子化することにより、非常に
高い非線形光学効果が生じる可能性が理論的に予言され
ている。また、ＣｕＣ１を析出させたガラスは、ソ連で
過去報告されてはいるが、そのガラスの組成等の詳細に
ついては一切明らかにされていない。On the other hand, it has recently been theoretically predicted that a very high nonlinear optical effect may be produced by making CuC1 into fine particles. Further, although glass on which CuC1 is precipitated has been reported in the Soviet Union in the past, details such as the composition of the glass have not been disclosed at all.
しかしながら、このＣｄ５−ＣｄＳｅ系の超微粒子析出
ガラスでは、従来の非線形光学材料に見られないような
高い非線形光学効果を示すものの、前述した超高速光ス
ィッチ、メモリーなどの非線形光学材料として用いるに
はその特性が充分ではなく、非常に高い出力のレーザー
光源を用いなくては動作しないという課題があった。However, although this Cd5-CdSe-based ultrafine particle precipitated glass exhibits a high nonlinear optical effect not seen in conventional nonlinear optical materials, it cannot be used as a nonlinear optical material for the aforementioned ultrahigh-speed optical switches, memories, etc. The problem was that its characteristics were not sufficient, and it required a very high output laser light source to operate.
他方、特公昭４６−３４６４号公報には、重量％表示で
５ｉＯｚ ４０〜７０％、Ｂａ５ｓ １０〜２６％、
Ａ１１ａｓ４〜２６％、Ｂｉｏ ３〜２５％の基礎ガ
ラスにＣｕＣ１゜ＣｕＢｒ粒子を析出した紫外線吸収ガ
ラスが開示されている。On the other hand, in Japanese Patent Publication No. 46-3464, 5iOz 40-70%, Ba5s 10-26%,
An ultraviolet absorbing glass in which CuC1°CuBr particles are precipitated on a base glass of 4 to 26% A11as and 3 to 25% Bio is disclosed.
しかしながら、かかるガラスはＣｕＣ１等の超微粒子が
析出し難いという課題があった。However, such glass has a problem in that ultrafine particles such as CuC1 are difficult to precipitate.
［発明の解決しようとする課題］
本発明は、従来技術が有していた上記課題を解消し、半
導体レーザーのようなコンパクトの光源により作動する
ことの予想される超微粒子析出ガラスの提供を目的とす
る。[Problems to be Solved by the Invention] The purpose of the present invention is to solve the above-mentioned problems that the prior art had and to provide an ultrafine particle precipitated glass that is expected to be operated by a compact light source such as a semiconductor laser. shall be.
［課題を解決するための手段］
本発明は、
モル％表示で本質的に
ＳｉＯ□ ｌＯ〜７０％
Ｂ、０． ３０〜９０％
ＬＬ、Ｏ＋Ｎａ＊Ｏ＋に、０ ０．１〜５０％ＣｕＣ１
＋ＣｕＢｒ ０．０１〜１０％からなり、ＣｕＣ１
及び／又はＣｕＢｒ超微粒子を析出してなるＣｕＣｌ、
ＣｕＢｒ超微粒子析出ガラスおよび、
モル％表示で本質的に
ＳｉＯ□ ｌＯ〜７０％
ＩＩ −ｎ −’Ｊ ｎ 〜Ｑｎ’１
Ａｌ＊Ｏｓ ０．０１〜４０％ＬｉｇＯ
＋ＮａａＯ＋Ｋｔ０ ０．１〜５０％ＣｕＣ１＋ＣｕＢ
ｒ Ｏ，０１〜１０％からなり、ＣｕＣ１及び
又はＣｕＢｒ超微粒子を析出してなるＣｕＣｌ、ＣｕＢ
ｒ超微粒子析出ガラス並びにそれらのガラスの製造法を
提供するものである。[Means for Solving the Problems] The present invention is characterized in that SiO□1O~70% B, 0. 30-90% LL, O+Na*O+, 0 0.1-50% CuC1
+CuBr 0.01-10%, CuC1
and/or CuCl formed by precipitating CuBr ultrafine particles,
CuBr ultrafine particle precipitated glass and essentially SiO□ 1O~70% II-n-'Jn~Qn'1 Al*Os 0.01~40%LigO in mol%
+NaaO+Kt0 0.1~50%CuC1+CuB
CuCl, CuB consisting of r O, 01 to 10% and precipitated with CuCl and/or CuBr ultrafine particles
The present invention provides ultrafine particle precipitated glasses and methods for producing these glasses.
本発明における第１のガラスは、５ｔｏ２が１０モル％
未満の場合は、ＣｕＣｌ、ＣｕＢｒ超微粒子の析出が得
られ難く、逆に７０％を超えた場合は、ガラスの生成温
度が高くなり、Ｃｕ及びＣＩ、Ｂｒ成分が揮散してしま
いいずれも好ましくない。The first glass in the present invention contains 10 mol% of 5to2.
If it is less than 70%, it is difficult to obtain precipitation of CuCl and CuBr ultrafine particles, and conversely, if it exceeds 70%, the glass formation temperature becomes high and Cu, CI, and Br components volatilize, which is not preferable. .
また、Ｂ２０．は３０〜９０モル％の範囲以外では、Ｃ
ｕＣｌ、ＣｕＢｒ超微粒子の析出が得られ難く、好まし
くない。Also, B20. is outside the range of 30 to 90 mol%, C
It is difficult to obtain precipitation of uCl and CuBr ultrafine particles, which is not preferable.
また、ＬｉｘＯ，Ｎａ１ｌ、 ＫａＯは、単一成分で用
いられても、２種類以上混合して用いられてもかまわな
いが、合計量が０．１〜５０モル％の範囲以外はＣｕＣ
ｌ、ＣｕＢｒ超微粒子の析出は得られ難く、好ましくな
い。In addition, LixO, Na1l, and KaO may be used as a single component or in a mixture of two or more types, but CuC
l. Precipitation of CuBr ultrafine particles is difficult to obtain and is not preferred.
そして、これらの範囲のうち、ＳｉＯ□ ２０〜６０モ
ル％、Ｂ２０，３５〜７０モル％、（ＬｉａＯ＋Ｎａ１
Ｏ＋に２０）が０．５〜２０モル％よりなるガラスは、
均一で制御された粒径のＣｕＣｌ、ＣｕＢｒ超微粒子が
容易に析出しつるので特に好ましい。Among these ranges, SiO□ 20 to 60 mol%, B20, 35 to 70 mol%, (LiaO+Na1
Glass consisting of 0.5 to 20 mol% of 20) in O+ is
It is particularly preferred because ultrafine CuCl and CuBr particles with a uniform and controlled particle size are easily precipitated.
さらに、銅、塩素及び臭素はＣｕＣ１＋ＣｕＢｒ換算で
０．０１−１０モル％含有する場合にＣｕＣ１、ＣｕＢ
ｒ超微粒子が析出することも見出した。銅、塩素及び臭
素がＣｕＣ１＋ＣｕＢｒ換算で０．０１モル％未満の場
合は、ＣｕＣ１微粒子が析出せず、逆に銅、塩素及び臭
素はＣｕＣ１＋ＣｕＢｒ換算で１０モル％を超える場合
は、ＣｕＣｌ、ＣｕＢｒは析出するが析出した粒子の大
きさを制御することが困難であるため、いずれも好まし
くない。Furthermore, when copper, chlorine and bromine are contained in 0.01-10 mol% in terms of CuC1+CuBr, CuC1, CuB
It was also found that ultrafine particles were precipitated. If copper, chlorine, and bromine are less than 0.01 mol% in terms of CuC1+CuBr, CuC1 fine particles will not precipitate, and conversely, if copper, chlorine, and bromine exceed 10 mol% in terms of CuC1+CuBr, CuCl and CuBr will precipitate. However, since it is difficult to control the size of the precipitated particles, neither is preferable.
本発明における第２のガラスは、５ｉＯａ、Ｂ＊Ｏｚ。The second glass in the present invention is 5iOa, B*Oz.
ＬｉｚＯ＋ＮａｚＯ＋ＫａＯ，ＣｕＣ１は第１のガラス
と同一の範囲にあり、Ａ１□０．を０．０１〜４０モル
％含有する。LizO+NazO+KaO, CuC1 is in the same range as the first glass, A1□0. Contains 0.01 to 40 mol%.
ＡＩＪｓが０．０１モル％未満ではガラスの耐候性が低
いのでかかる用途に使用する場合に好ましくない。一方
、Ａｌ２Ｏ，が４０％を越えると、ガラス化し難くなる
ので好ましくない、 Ａｌ□０３の含有量は上記範囲中
０．１〜３０モル％の範囲がより好ましい。If the AIJs content is less than 0.01 mol%, the weather resistance of the glass will be low, which is not preferable for use in such applications. On the other hand, if Al2O exceeds 40%, it becomes difficult to vitrify, which is undesirable.The content of Al□03 is more preferably in the range of 0.1 to 30 mol% within the above range.
上記成分に対し、ＳｎＯ，５ｎＯｚ、 ５ｂｚＯｓ、
Ｓｂ３０ｇを総量で５％以下添加することにより Ｃｕ
Ｃ１゜ＣｕＢｒ超微粒子が更に析出し易くなるので好ま
しい。For the above components, SnO, 5nOz, 5bzOs,
By adding 30g of Sb in a total amount of 5% or less, Cu
C1°CuBr ultrafine particles are more easily precipitated, which is preferable.
本発明のＣｕＣｌ、ＣｕＢｒ超微粒子析出ガラスの製造
に際し、用いられる原料としては、例えば次の物質があ
げられる。Examples of raw materials used in producing the CuCl, CuBr ultrafine particle precipitated glass of the present invention include the following substances.
ケイ素原料としては、例えば二酸化ケイ素などのケイ素
の酸化物の他、窒化物、有機ケイ素化合物や、ケイ酸ア
ルカリなどのケイ酸塩も他のアルカリ化合物と混合して
用いることができる。As the silicon raw material, for example, in addition to silicon oxides such as silicon dioxide, nitrides, organosilicon compounds, and silicates such as alkali silicates can be used in combination with other alkali compounds.
ホウ酸原料としては、ホウ酸（Ｈ，ＢＯ，） 、無水ホ
ウ酸（Ｂ＊Ｏｓ）などの酸化物の他、窒化物、有機ホウ
素化合物や、ホウ酸アルカリなどのホウ酸塩も他のアル
カリ化合物と混合して用いることができる。Boric acid raw materials include oxides such as boric acid (H, BO, ) and boric anhydride (B*Os), as well as nitrides, organic boron compounds, borates such as alkali borate, and other alkalis. It can be used in combination with other compounds.
アルカリ金属の原料としては、例えば炭酸塩が代表的で
あるが、水酸化物、塩化物等の他のアルカリ化合物を適
宜用いつる。As a raw material for the alkali metal, carbonate is typically used, but other alkali compounds such as hydroxide and chloride may be used as appropriate.
銅及び塩素並びに臭素の原料としては、例えばＣｕＣｌ
、ＣｕＣ１＊、 ＣｕＢｒ、 ＣｕＢｒａなどの銅の塩
化物、臭化物の他、銅は銅単体あるいは銅の酸化物、水
酸化物、硫酸塩等の無機塩や有機塩を用いることができ
る。また、塩素はアルカリ塩化物、アルカリ臭化物、塩
化アンモニウム、臭化アンモニウムや他の添加成分の塩
化物、臭化物として供給することも可能である。更に、
塩素、臭素は単体あるいは塩化物、臭化物の気体として
ガラスと反応させ導入することも可能である。Examples of raw materials for copper, chlorine, and bromine include CuCl
In addition to copper chlorides and bromides such as , CuC1*, CuBr, and CuBra, copper alone or inorganic salts and organic salts such as copper oxides, hydroxides, and sulfates can be used. Further, chlorine can also be supplied as an alkali chloride, an alkali bromide, ammonium chloride, ammonium bromide, or other additive components such as chlorides and bromides. Furthermore,
Chlorine and bromine can be introduced alone or as a chloride or bromide gas by reacting with glass.
アルミニウム原料としては、水酸化アルミニウム、アル
ミナなどの水酸化物、酸化物の他、窒化物、有機アルミ
ニウム化合物なども用いることができる。As the aluminum raw material, in addition to hydroxides and oxides such as aluminum hydroxide and alumina, nitrides and organic aluminum compounds can also be used.
本発明のＣｕＣｌ、ＣｕＢｒ超微粒子が析出しつるガラ
スの製造手段としては、特に制限はなく、例えば諸原料
を所定量秤量して混合し、これを１２００〜１６００℃
で５分〜ｌＯ時間加熱溶融し、所定形状に成形せしめる
方法が用いられる。ガラス原料に塩化物等揮発し易いも
のを用いるため、予め構成成分の一部でガラスを形成し
ておき、残りの成分の原料を加え再度ガラス化する方法
が好ましい。またＣＶＤ等気相からガラスを得る方法、
ゾルゲル法等液相からガラスを得る方法も可能である。There are no particular restrictions on the method for producing the vine glass in which ultrafine particles of CuCl and CuBr are precipitated according to the present invention.
A method is used in which the material is melted by heating for 5 minutes to 10 hours and molded into a predetermined shape. In order to use a material that easily volatilizes, such as chloride, as the glass raw material, it is preferable to form glass with some of the constituent components in advance, and add the raw materials for the remaining components to vitrify it again. Also, a method of obtaining glass from a gas phase such as CVD,
A method of obtaining glass from a liquid phase such as a sol-gel method is also possible.
本発明のＣｕＣｌ、ＣｕＢｒ超微粒子の析出方法として
は、成形されたガラスを一旦室温まで冷却し次いで加熱
して所定温度に保持して超微粒子析出する方法と成形さ
れたガラスを冷却課程で所定温度に保持し超微粒子を析
出する方法とがある。前者の方法は析出する超微粒子の
大きさ等を制御し易いので、本発明の方法として好まし
い。The method for precipitating the CuCl and CuBr ultrafine particles of the present invention includes a method in which the formed glass is cooled once to room temperature and then heated and held at a predetermined temperature to precipitate the ultrafine particles. There is a method in which ultrafine particles are precipitated by holding it at a temperature. The former method is preferable as the method of the present invention because it is easy to control the size of the precipitated ultrafine particles.
超微粒子を析出する温度は４００〜８００℃の範囲であ
り、４００℃未満では目的とする超微粒子が析出し難い
ので好ましくない。一方かかる温度が８００℃を越える
とガラスが軟化したり、ガラスに失速を生ずるので好ま
しくない。The temperature at which the ultrafine particles are precipitated is in the range of 400 to 800°C, and temperatures below 400°C are not preferred because the desired ultrafine particles are difficult to precipitate. On the other hand, if the temperature exceeds 800° C., the glass may soften or stall, which is not preferable.
成形されたガラスを４００〜８００℃で５分〜１００時
間保持することにより、５〜１０００人のＣｕＣ１及び
／又はＣｕＢｒ超微粒子が析出する。加熱方法としては
特に制限はなく、抵抗加熱型電気炉で加熱したり、バー
ナー等で加熱したり、あるいはマイクロ波、光等の電磁
波で加熱することも可能である。By holding the shaped glass at 400 to 800°C for 5 minutes to 100 hours, 5 to 1000 CuCl and/or CuBr ultrafine particles are precipitated. There are no particular limitations on the heating method, and heating with a resistance heating type electric furnace, heating with a burner, etc., or heating with electromagnetic waves such as microwaves and light is also possible.
さらに、かかる処理によって析出したＣｕＣ１゜ＣｕＢ
ｒ超微粒子の粒径は、５〜１０００入であることが好ま
しい。粒径が５λ未満の場合、Ｃｕ Ｃｌ ＋ＣｕＢｒ
超微粒子内にに励起子が形成されにくく、１０００人を
超える場合は、期待している励起子の微粒子内への閉じ
込め効果が弱くなってしまうので好ましくない、この範
囲のうち１０〜５００人の粒径の場合、ＣｕＣ１超微粒
子等の励起子の光吸収が、高エネルギー側にシフトし励
起子の顕著な閉じ込め効果が推測され特に好ましい。Furthermore, CuC1°CuB precipitated by such treatment
The particle size of the r ultrafine particles is preferably 5 to 1000 particles. If the particle size is less than 5λ, Cu Cl + CuBr
It is difficult for excitons to be formed within the ultrafine particles, and if the number exceeds 1000, the expected effect of confining excitons within the microparticles will be weakened, which is undesirable. In the case of particle size, the light absorption of excitons such as CuC1 ultrafine particles is expected to shift to the high energy side and a remarkable confinement effect of excitons is expected, which is particularly preferable.
また、析出したＣｕＣ１超微粒子等の析出量は、０．０
１〜１０体積％が好ましい、 ０．０１体積％未溝の場
合、ＣｕＣ１超微粒子等に由来する非線形光学効果が充
分発現されず、１（１体積％を超える場合、前記範囲の
粒径の範囲に制御して析出させることが困難となるため
望ましくない。In addition, the amount of precipitated CuC1 ultrafine particles was 0.0
1 to 10% by volume is preferable. If 0.01% by volume is ungrooved, the nonlinear optical effect derived from CuC1 ultrafine particles etc. will not be sufficiently expressed. This is not desirable because it becomes difficult to control the precipitation.
［実施例］
実施例１
ガラス作製時に表の組成になるように原料を計４００ｇ
秤量し、よく混合した。これを白金坩堝に入れ１４００
℃で２時間溶融した後、ステンレス板上に流し出して組
成の異なる１６種類のガラスを得た。[Example] Example 1 When producing glass, a total of 400 g of raw materials were used to make the composition as shown in the table.
Weighed and mixed well. Put this in a platinum crucible for 1400
After melting at ℃ for 2 hours, the mixture was poured onto a stainless steel plate to obtain 16 types of glasses with different compositions.
このガラスを４６０℃に４時間保持し、超微粒子の析出
を行った。この超微粒子析出ガラスを１ＩＩＩｌ以下の
厚さに研磨してサンプルを作成し、そのサンプルの７７
にでの吸光スペクトルを測定した。３５０〜４００ｎＩ
ｌのＣｕＣｌ、ＣｕＢｒ、Ｃｕ（ＣＩ、Ｂｒ）励起子吸
収構造を測定し、その吸光度を求めるとともにそのピー
ク位置を測定した。This glass was held at 460° C. for 4 hours to precipitate ultrafine particles. A sample was prepared by polishing this ultrafine particle precipitated glass to a thickness of 1IIIl or less.
The absorption spectrum was measured. 350-400 nI
The exciton absorption structure of CuCl, CuBr, Cu (CI, Br) was measured, and its absorbance was determined and its peak position was measured.
析出した微粒子の粒径（ａ （人））は、透過型電子顕
微鏡で観察することにより求めた。The particle size (a (person)) of the precipitated fine particles was determined by observation with a transmission electron microscope.
また、析出した超微粒子の濃度はＣｕＣ；１及び／又は
ＣｕＢｒ単結晶の励起子の吸収係数、４．５×ＩＱ８ｃ
ｍ−’ （半値幅５ ｍｅＶ）から換算し求めた。In addition, the concentration of the precipitated ultrafine particles is the exciton absorption coefficient of CuC; 1 and/or CuBr single crystal, 4.5 × IQ8c
m-' (half width 5 meV).
これらの測定値を表１に示した。These measured values are shown in Table 1.
同表から明らかなように１０〜５００人の粒径のＣｕ（
１等の超微粒子が０．０１〜ｌＯ％効率よく析出してお
り、非常に高い非線形光学効果が予想される。As is clear from the same table, Cu (
Ultrafine particles of 1st grade are precipitated with an efficiency of 0.01 to 10%, and a very high nonlinear optical effect is expected.
［比較例］
本発明以外の組成を有する６種類のガラスについて、実
施例１と同様にしてサンプルを作成しＣｕＣ１等の超微
粒子析出し同様の測定を行なった。それらの組成、測定
結果を同様のサンプルＮｏ、１７〜２２に示した。[Comparative Example] Samples were prepared in the same manner as in Example 1 for six types of glasses having compositions other than those of the present invention, and the same measurements were performed on precipitation of ultrafine particles such as CuC1. Their compositions and measurement results are shown in similar samples Nos. 17-22.
なお同表に記載の添加物はそれぞれガラス原料に添加さ
れ、その添加量はガラス１００モル％に対し添加された
量を示す。The additives listed in the same table are each added to the glass raw material, and the amount added indicates the amount added to 100 mol% of the glass.
［発明の効果］
本発明によるＣｕＣｌ、ＣｕＢｒ超微粒子が析出したガ
ラスは、非常に高い非線形光学効果を有することが期待
される。また、ＡＩｔｏｓを所定量含有させることによ
り、非線形光学効果を低下することなく耐候性に優れた
ガラスが得られる。[Effects of the Invention] Glass on which CuCl and CuBr ultrafine particles according to the present invention are precipitated is expected to have extremely high nonlinear optical effects. Furthermore, by containing a predetermined amount of AItos, a glass with excellent weather resistance can be obtained without reducing the nonlinear optical effect.
更に、本発明によればＣｕＣ１等の超微粒子が低温で多
量に析出され、上記非線形光学効果を有するガラスを容
易に製造することができる。Furthermore, according to the present invention, ultrafine particles such as CuC1 are precipitated in large quantities at low temperatures, making it possible to easily produce glass having the above-mentioned nonlinear optical effect.
Claims (4)
Ｃｌ＋ＣｕＢｒ０．０１〜１０％ からなり、ＣｕＣｌ及び／又はＣｕＢｒ超微粒子を析出
してなるＣｕＣｌ、ＣｕＢｒ超微粒子析出ガラス。(1) Essentially SiO_210-70% B_2O_330-98% Li_2O+Na_2O+K_2O0.1-50%Cu in mol%
A CuCl and CuBr ultrafine particle precipitated glass consisting of Cl+CuBr0.01 to 10% and precipitated with CuCl and/or CuBr ultrafine particles.
Ｃｌ＋ＣｕＢｒ０．０１〜１０％ からなり、ＣｕＣｌ超微粒子を析出してなるＣｕＣｌ、
ＣｕＢｒ超微粒子析出ガラス。(2) Essentially SiO_210-70% in mol% B_2O_330-90% Al_2O_30.01-40% Li_2O+Na_2O+K_2O0.1-50%Cu
CuCl consisting of Cl + CuBr0.01-10% and formed by precipitating CuCl ultrafine particles,
CuBr ultrafine particle precipitation glass.
Ｃｌ＋ＣｕＢｒ０．０１〜１０％ からなるガラスを所定形状に成形し、次いで成形したガ
ラスを４００〜８００℃に５分間〜１００時間保持し、
ガラス中にＣｕＢｒ超微粒子を析出するＣｕＣｌ、Ｃｕ
Ｂｒ超微粒子析出ガラスの製造法。(3) Essentially SiO_210-70% B_2O_330-90% Li_2O+Na_2O+K_2O0.1-50%Cu in mol%
Glass consisting of Cl + CuBr0.01-10% is formed into a predetermined shape, and then the formed glass is held at 400-800°C for 5 minutes to 100 hours,
CuCl, Cu precipitates CuBr ultrafine particles in glass
A method for producing Br ultrafine particle precipitated glass.
ｌ＋ＣｕＢｒ０．０１〜１０％ からなるガラスを所定形状に成形し、次いで成形したガ
ラスを４００〜８００℃に５分間〜１００時間保持し、
ガラス中にＣｕＢｒ及び／又はＣｕＢｒ超微粒子を析出
するＣｕＣｌ、ＣｕＢｒ超微粒子析出ガラスの製造法。(4) Essentially SiO_210-70% B_2O_330-90% Li_2+Na_2O+K_2O0.1-50% CuC in mol%
A glass consisting of l+CuBr0.01 to 10% is formed into a predetermined shape, and then the formed glass is held at 400 to 800°C for 5 minutes to 100 hours,
A method for producing CuCl and CuBr ultrafine particle precipitated glass, in which CuBr and/or CuBr ultrafine particles are precipitated in glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3747990A JP2881911B2 (en) | 1989-03-30 | 1990-02-20 | CuCl, CuBr ultrafine particle precipitated glass and method for producing the same |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7676589 | 1989-03-30 | ||
| JP1-76765 | 1989-03-30 | ||
| JP1-240581 | 1989-09-19 | ||
| JP24058189 | 1989-09-19 | ||
| JP3747990A JP2881911B2 (en) | 1989-03-30 | 1990-02-20 | CuCl, CuBr ultrafine particle precipitated glass and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03174337A true JPH03174337A (en) | 1991-07-29 |
| JP2881911B2 JP2881911B2 (en) | 1999-04-12 |
Family
ID=27289486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3747990A Expired - Fee Related JP2881911B2 (en) | 1989-03-30 | 1990-02-20 | CuCl, CuBr ultrafine particle precipitated glass and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2881911B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03187951A (en) * | 1989-12-15 | 1991-08-15 | Hoya Corp | Semiconductor-containing glass |
| JPH0418501A (en) * | 1990-04-10 | 1992-01-22 | Isuzu Seiko Glass Kk | Colored glass |
| JP2011116633A (en) * | 2009-10-27 | 2011-06-16 | Tokyo Univ Of Science | Light-emitting glass, light-emitting device equipped with the light-emitting glass, and method for producing light-emitting glass |
-
1990
- 1990-02-20 JP JP3747990A patent/JP2881911B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03187951A (en) * | 1989-12-15 | 1991-08-15 | Hoya Corp | Semiconductor-containing glass |
| JPH0418501A (en) * | 1990-04-10 | 1992-01-22 | Isuzu Seiko Glass Kk | Colored glass |
| JP2011116633A (en) * | 2009-10-27 | 2011-06-16 | Tokyo Univ Of Science | Light-emitting glass, light-emitting device equipped with the light-emitting glass, and method for producing light-emitting glass |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2881911B2 (en) | 1999-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Beall et al. | Transparent glass-ceramics | |
| Layton et al. | Nucleation and Crystallization of NaNbO3 from Glasses in the Na2O‐Nb2O5‐SiO2 System | |
| Todorović et al. | Lithium-niobate ferroelectric material obtained by glass crystallization | |
| JPH11228180A (en) | Li2o-al2o3-sio2 based glass ceramics | |
| US5024974A (en) | Glass having ultrafine particles of CuCl and/or CuBr precipitated therein and process for its production | |
| Li et al. | Crystallization behavior of transparent Na2O-Al2O3-SiO2 glass-ceramic containing rare-earth oxides | |
| Ram et al. | IR and Raman studies and effect of γ radiation on crystallization of some lead borate glasses containing Al 2 O 3 | |
| Ito et al. | Transparency of LiTaO 3-SiO 2-Al 2 O 3 glass-ceramics in relation to their microstructure | |
| US3762936A (en) | Manufacture of borosilicate glass powder essentially free of alkali and alkaline earth metals | |
| Poirier et al. | Crystallization of monoclinic WO3 in tungstate fluorophosphate glasses | |
| Nordmann et al. | Crystallization behaviour and microstructural evolution of a Li2O–Al2O3–SiO2 glass derived from spodumene mineral | |
| JPH04275946A (en) | Blue/gray transparent glass ceramic article and method for manufacture thereof | |
| JPH03174337A (en) | Glass containing deposited superfine particles of cucl and cubr and production thereof | |
| JPH04275947A (en) | Transparent blue/black glass ceramic article and method for manufacture thereof | |
| Machida et al. | Effect of starting materials of nucleation agents on crystallization of CaO–Al2O3–SiO2 glass | |
| Zan et al. | New chalcohalide glasses from the Sb2S3-MXn system | |
| DE3925486A1 (en) | EARTH ALKALIALUMINOBORATE GLASS CERAMICS | |
| JPH05238774A (en) | Glass composition for low temperature sintered base plate and base plate obtained therefrom | |
| de Oliveira et al. | The effect of the addition of ZrSiO4 on the crystallization of 30Li2O70SiO2 powdered glass | |
| US20120135236A1 (en) | Coloured Glass Flakes | |
| Masai et al. | Glass-Ceramics Containing Nano-Crystallites of Oxide Semiconductor | |
| JPH0664936A (en) | Production of glass capable of sharply cutting ultraviolet ray | |
| Dakui et al. | Kinetic study of the crystallization of ZrF4 BaF2 LaF3 AlF3 glasses | |
| JPH0748140A (en) | Production of glass sharply cutting ultraviolet rays | |
| Tkalčce et al. | Influence of Dopants on Nucleation and Growth of High‐Quartz Solid Solution in Lithium Aluminosilicate Glass |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |