JPH02221130A - Semiconductor doped glass - Google Patents
Semiconductor doped glassInfo
- Publication number
- JPH02221130A JPH02221130A JP4271289A JP4271289A JPH02221130A JP H02221130 A JPH02221130 A JP H02221130A JP 4271289 A JP4271289 A JP 4271289A JP 4271289 A JP4271289 A JP 4271289A JP H02221130 A JPH02221130 A JP H02221130A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- sol
- cds
- gel
- nonlinear optical
- 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.)
- Pending
Links
- 239000011521 glass Substances 0.000 title claims abstract description 25
- 239000004065 semiconductor Substances 0.000 title description 2
- 230000003287 optical effect Effects 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 6
- -1 silicon alkoxide Chemical class 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract 3
- 239000010703 silicon Substances 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims 1
- 238000003980 solgel method Methods 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 description 8
- 239000013081 microcrystal Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011882 ultra-fine particle Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006063 cullet Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/006—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Melting And Manufacturing (AREA)
Abstract
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は非線形光学効果を示すガラス体に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a glass body exhibiting nonlinear optical effects.
［従来の技術］
従来の半導体ドープガラスの代表はＣｄ５ｘＳ ｅ ＋
−ｗ ドープガラスであった。これは、Ｃｄ５ Ｘ Ｓ
ｅ ＋−＋＋の微結晶をホウケイ酸ガラスに混入した
もので、詳細は、Ｊ、Ａｐｐｌ、Ｐｈ、ｙｓ６１ （
１２）、１５Ｊｕｎｅ １９８７ ｐ５３９９
＋Ｑｕａｎｔｕｍ ｃｏｎｆｉｎｅ−＋ｎ ｅ ｎ
ｔ ｅ ｆ ｆ ｅ ｃ ｔ ｓ ｏ ｆ ｓ
ｅ ｍ ｉ ｃ 。[Prior art] A typical example of conventional semiconductor doped glass is Cd5xS e +
-w It was doped glass. This is Cd5
e +-++ microcrystals mixed into borosilicate glass. Details are given in J, Appl, Ph, ys61 (
12), 15June 1987 p5399
+Quantum confine-+n e n
t e f f e c t so f s
em ic.
ｎｄｕｃｔｉｎｇ ｍ１ｃｒｏｃｒｙｓｔａｌ −１
ｉｔｅｓ ｉｎ ｇｌａｓｓ” に記載されてい
る。このガラスはシャープカットフィルタとして従来よ
りＣｏｒｎ ｉ ｎｇ社や５ｈｏｔｔ社より市販されて
いるものである。また製法は、母ガラス組成のガラス原
料のカレットに、ＣｄＯ，ＣｄＳ、Ｓ、Ｓｅを数重量パ
ーセント加え、１３００〜１４００℃で溶融し、成形し
、４５０〜５５０°Ｃでアニールすることで除歪して均
一なガラス体とし、Ｃｄ Ｓ ｘ Ｓ ｅ ｌ−Ｘの微
結晶をガラス中に生成させるため５７５〜７５０℃で０
．５〜４時間加熱するというものであった。nducting m1crocrystal-1
This glass has been commercially available as a sharp-cut filter from Corning and 5hott.The manufacturing method involves adding CdO to a cullet of glass raw material with a mother glass composition. , CdS, S, and Se in several weight percent, melted at 1300 to 1400°C, molded, and annealed at 450 to 550°C to remove strain and make a uniform glass body, Cd S x Se l- 0 at 575-750℃ to generate microcrystals of X in the glass.
．． The plan was to heat it for 5 to 4 hours.
〔発明が解決しようとする課題１
しかし、重連の従来技術では、ホウケイ酸ガラス中に溶
融しているＣｄ、Ｓ、Ｓｅの元素なＣｄ５Ｓｅ＋□の化
合物に反応させ微結晶に析出させる必要が有り、５７５
〜７００℃のアニールが必要であった。そのため、析出
してくる微結晶の粒径や１粒径分布等をコントロールし
づらいため、非線形定数を一定にするのが困難であった
。[Problem to be Solved by the Invention 1] However, in the conventional technique of multiplexing, it is necessary to react with the compound of Cd5Se+□, which is the elements of Cd, S, and Se, melted in borosilicate glass and precipitate it into microcrystals. , 575
An anneal of ~700°C was required. Therefore, it is difficult to control the grain size, grain size distribution, etc. of the precipitated microcrystals, making it difficult to keep the nonlinear constant constant.
そこで本発明はこのような問題点を解決するもので、そ
の目的とするところは、容易に粒径コントロールのでき
るプロセスを提供するところにある。Therefore, the present invention is intended to solve these problems, and its purpose is to provide a process in which particle size can be easily controlled.
［課題を解決するための手段１
本発明の半導体ドープガラスは、少なくともシフコンア
ルコキシドを主原料とするゾル−ゲル法によるガラスの
製造方法におけるゾル溶液中にＣｄＳ、Ｓ及びＳｅの微
粉末を加え、よく分散した後、ゲル化、乾燥し、焼結す
ることでガラスとし、非線形光学効果を示すガラスとす
ることを特ｉ敦とする。[Means for Solving the Problems 1] The semiconductor-doped glass of the present invention is produced by adding fine powders of CdS, S and Se to a sol solution in a method for producing glass by a sol-gel method using at least Schifcon alkoxide as a main raw material. After being well dispersed, it is gelled, dried, and sintered to form a glass, and the special feature is that the glass exhibits a nonlinear optical effect.
〔作 用１
本発明の上記の構成によれば、ゾル中にＣｄＳやＳ、Ｓ
ｅの微粉末を添加しているため、その粉末の粒径を制御
することでガラス中のＣｄ５ｘＳ ｅ ＋−ｍの粒径を
制御することができる。従って、従来の溶融ガラスから
Ｃｄ５Ｓｅ系−ｘの微結晶を析出させる方法をとらなく
ても、容易に出発原料の粒径のコントロールで、制御で
きるため、大きな長所が有る。[Function 1] According to the above configuration of the present invention, CdS, S, and S are present in the sol.
Since fine powder of Cd5xS e +-m is added, the particle size of Cd5xS e +-m in the glass can be controlled by controlling the particle size of the powder. Therefore, this method has a great advantage because it can be easily controlled by controlling the particle size of the starting material without using the conventional method of precipitating Cd5Se-based microcrystals from molten glass.
［実 施 例］
以下に、実施例を示すことでさらに詳しく本発明を説明
する。[Examples] The present invention will be explained in more detail by showing examples below.
実施例１
エチルシリケート１モルに、Ｏｌ規定の塩酸水溶液を１
８０ｒｒ＋Ｊｌ！加え、よく撹拌し加水分解した。この
ゾルに、ＣｄＳ、Ｓ、Ｓｅの超微粒子（粒径１００μｍ
）をそれぞれ０，０５モルづつ加λた。これをよく分散
し、均一なコロイド状にし、０．１規定のアンモニア本
を加え、ゾルのｐＨ値を５．２に調整した。このゾルを
ポリプロピレン製容器に入れ放置した。１時間後ゲル化
し、その後−昼夜放置した。ゲルを入れであるプラスチ
ック容器のフタに穴を開け、６０℃の恒温槽に入れた。Example 1 To 1 mol of ethyl silicate, 1 mol of ol normal hydrochloric acid aqueous solution was added.
80rr+Jl! The mixture was added and stirred thoroughly for hydrolysis. Ultrafine particles of CdS, S, and Se (particle size 100 μm) are added to this sol.
) were added in an amount of 0.05 mol each. This was well dispersed to form a uniform colloid, and 0.1N ammonia was added to adjust the pH value of the sol to 5.2. This sol was placed in a polypropylene container and left to stand. It gelled after 1 hour and was then allowed to stand overnight. A hole was made in the lid of a plastic container containing the gel, and the container was placed in a constant temperature bath at 60°C.
１０日後乾燥が終了しドライゲルが作成できた。続いて
、ドライゲルを電気炉中で熱処理し、１３００℃に昇温
して焼結した。これで、赤色の透明なガラスが得られた
。After 10 days, drying was completed and a dry gel was completed. Subsequently, the dry gel was heat-treated in an electric furnace, heated to 1300° C., and sintered. A red transparent glass was now obtained.
このガラスは非線形光学効果を示す、Ｃｄ５Ｓｅ系のシ
リカガラスになっていた。This glass was Cd5Se-based silica glass that exhibits a nonlinear optical effect.
〔発明の効果ｊ
以上述べたように発明によれば１粒子径をコントロール
しである、ＣｄＳ、Ｓ、Ｓｅの超微粒子を、エチルシリ
ケートの加水分解ゾルに添加することで、ゾル−ゲル法
により、非線形光学効果を示す半導体ドープガラスとす
ることができる。この方法により、Ｃｄ５Ｓｅの粒子径
の揃った粒子を含むガラスを作製することができる６従
って、優れた非線形光学効果を示す、半導体ドープガラ
スを作製することができるという効果を有する。[Effects of the invention j As described above, according to the invention, by adding ultrafine particles of CdS, S, and Se with controlled particle diameters to a hydrolyzed sol of ethyl silicate, the sol-gel method can be used. , it can be a semiconductor-doped glass that exhibits nonlinear optical effects. By this method, it is possible to produce a glass containing Cd5Se particles with uniform particle diameters. 6 Therefore, it is possible to produce a semiconductor-doped glass that exhibits an excellent nonlinear optical effect.
以上that's all
Claims (1)
ゲル法によるガラスの製造方法における、ゾル溶液中に
ＣｄＳ、Ｓ及びＳｅの微粉末を加え、よく分散した後、
ゲル化し、乾燥し、焼結することでガラスとし、非線形
光学効果を示すガラスとすることを特徴とする半導体ド
ープガラス。A sol whose main raw material is at least silicon alkoxide.
In the glass manufacturing method using the gel method, after adding fine powders of CdS, S and Se to the sol solution and well dispersing them,
A semiconductor-doped glass characterized by being made into a glass by gelling, drying, and sintering, and exhibiting a nonlinear optical effect.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4271289A JPH02221130A (en) | 1989-02-22 | 1989-02-22 | Semiconductor doped glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4271289A JPH02221130A (en) | 1989-02-22 | 1989-02-22 | Semiconductor doped glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02221130A true JPH02221130A (en) | 1990-09-04 |
Family
ID=12643685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4271289A Pending JPH02221130A (en) | 1989-02-22 | 1989-02-22 | Semiconductor doped glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02221130A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1285888A2 (en) | 2001-08-22 | 2003-02-26 | Schott Glas | Method for the production of optical glasses and colored glasses at low temperatures |
| DE10140566A1 (en) * | 2001-08-18 | 2003-03-06 | Schott Glas | Process for removing bubbles from glass bodies comprises preparing a porous glass body, and hot isostatically pressing the glass body at a temperature at which the body has a specified viscosity |
| DE10141103A1 (en) * | 2001-08-22 | 2003-03-13 | Schott Glas | Production of optical glass and colored glass used for cut-off filters comprises dissolving a starting material in a liquid medium to form a suspension, forming a green body, drying, and sintering the green body in the liquid phase |
-
1989
- 1989-02-22 JP JP4271289A patent/JPH02221130A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10140566A1 (en) * | 2001-08-18 | 2003-03-06 | Schott Glas | Process for removing bubbles from glass bodies comprises preparing a porous glass body, and hot isostatically pressing the glass body at a temperature at which the body has a specified viscosity |
| EP1285888A2 (en) | 2001-08-22 | 2003-02-26 | Schott Glas | Method for the production of optical glasses and colored glasses at low temperatures |
| DE10141103A1 (en) * | 2001-08-22 | 2003-03-13 | Schott Glas | Production of optical glass and colored glass used for cut-off filters comprises dissolving a starting material in a liquid medium to form a suspension, forming a green body, drying, and sintering the green body in the liquid phase |
| US7140202B2 (en) | 2001-08-22 | 2006-11-28 | Schott Ag | Method for manufacturing optical glasses and colored glasses at low temperatures |
| DE10141103B4 (en) * | 2001-08-22 | 2007-01-18 | Schott Ag | Process for producing optical glasses and colored glasses at low temperatures |
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