JPH04204426A - Nonlinear optical material and production thereof - Google Patents
Nonlinear optical material and production thereofInfo
- Publication number
- JPH04204426A JPH04204426A JP33592190A JP33592190A JPH04204426A JP H04204426 A JPH04204426 A JP H04204426A JP 33592190 A JP33592190 A JP 33592190A JP 33592190 A JP33592190 A JP 33592190A JP H04204426 A JPH04204426 A JP H04204426A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- semiconductor
- thin film
- nonlinear optical
- target
- 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
- 239000000463 material Substances 0.000 title claims abstract description 71
- 230000003287 optical effect Effects 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000004065 semiconductor Substances 0.000 claims abstract description 99
- 239000010409 thin film Substances 0.000 claims abstract description 77
- 239000001257 hydrogen Substances 0.000 claims abstract description 58
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 58
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000004544 sputter deposition Methods 0.000 claims abstract description 31
- 239000007789 gas Substances 0.000 claims abstract description 30
- 150000004767 nitrides Chemical class 0.000 claims abstract description 30
- 239000010419 fine particle Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 20
- 239000000758 substrate Substances 0.000 abstract description 7
- 150000002431 hydrogen Chemical class 0.000 abstract description 5
- 239000012212 insulator Substances 0.000 abstract description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 16
- 239000011521 glass Substances 0.000 description 14
- 229910052581 Si3N4 Inorganic materials 0.000 description 10
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 10
- 229910010271 silicon carbide Inorganic materials 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 7
- 150000001247 metal acetylides Chemical class 0.000 description 7
- 239000002096 quantum dot Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000005388 borosilicate glass Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910004613 CdTe Inorganic materials 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910001510 metal chloride Inorganic materials 0.000 description 3
- 229910052580 B4C Inorganic materials 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910000673 Indium arsenide Inorganic materials 0.000 description 2
- 229910000661 Mercury cadmium telluride Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- -1 Zn5e Inorganic materials 0.000 description 2
- 229910007709 ZnTe Inorganic materials 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 2
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 description 2
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- 229910004262 HgTe Inorganic materials 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000001552 radio frequency sputter deposition Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は非線形光学効果を利用した光デバイスの基礎を
なす非線形光学材料およびその製造方法に関するもので
、とくに非晶質薄膜材料として窒化物ないしは炭化物を
用いた非線形光学材料ならびにその製造方法に関するも
のである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a nonlinear optical material that forms the basis of an optical device that utilizes nonlinear optical effects, and a method for manufacturing the same. This invention relates to nonlinear optical materials using carbides and methods for producing the same.
［従来の技術］
従来、この種の技術としては、例えばジャーナル オブ
ザ オプティカル ソサエティ オブアメリカ第７３
巻第６４７頁（Ｊｏｕｒｎａｌ ｏｆ ＋ｂｅＯｐｔｉ
ｃａＩ ５ｏｃｊｅｔｙ ｏｆ Ａｍｅｒｉｃａ ７３
． ６４７（１９８３）） に記載されているＣｄＳ
Ｓｅ をホウケイ酸ガラスに１−ｘ
ドープしたカットオフフィルタガラスを非線形光学材料
に用いるものがある。このカットオフフィルタガラスは
ＣｄＳ Ｓｅ とホウケイ酸ガラ ｌｘ
ス材料を白金ルツボに入れ１６００℃程度の高温で溶融
し作製している。[Prior art] Conventionally, this type of technology has been described, for example, in the Journal of the Optical Society of America No. 73.
Volume 647 (Journal of +beOpti
caI 5ocjety of America 73
．． 647 (1983))
A cut-off filter glass obtained by doping borosilicate glass with 1-x Se is used as a nonlinear optical material. This cut-off filter glass is produced by placing CdS Se and borosilicate glass lx materials in a platinum crucible and melting them at a high temperature of about 1600°C.
また、ジャーナル オブ アプライド フィジックス
第６３巻 第９５７頁（Ｊｏｕｒｎａｌ ｏｆ Ａｐｐ
ｌｉｅｄＰｈｙｓｉｃｓ ６３． ９５７（１９８８）
）に開示されているようなＣｄＳ微粒子ドープ薄膜ガラ
スがある。この薄膜ガラスはターゲットにコーニング社
製“７ｏ５９ガラス” （Ｂａ含有ホウケイ酸系ガラス
）と、ＣｄＳとを用い高周波マグネトロンスパッタ法に
より、“７０５９ガラス”中にＣｄＳを２〜４重量％分
散させたものである。Also, Journal of Applied Physics
Volume 63, page 957 (Journal of App
LiedPhysics 63. 957 (1988)
There is a thin film glass doped with CdS fine particles as disclosed in ). This thin film glass is made by using Corning's "7o59 glass" (Ba-containing borosilicate glass) as a target and CdS and dispersing 2 to 4% by weight of CdS in "7059 glass" by high-frequency magnetron sputtering. It is.
［発明が解決しようとする課題］
半導体微粒子の有する非線形光学効果を利用した非線形
光学材料においては、半導体含有量が多く、半導体組成
が化学量論性に優れ、半導体の化学的ないしは物理的損
傷が少なく、半導体微粒子がマトリックス中に均一に分
散し粒子径分布も小さいものほど、良好な非線形光学効
果を期待できる。[Problem to be solved by the invention] A nonlinear optical material that utilizes the nonlinear optical effect of semiconductor fine particles has a large semiconductor content, a semiconductor composition with excellent stoichiometry, and is free from chemical or physical damage to the semiconductor. The more uniformly the semiconductor fine particles are dispersed in the matrix and the smaller the particle size distribution, the better the nonlinear optical effect can be expected.
しかしながら、従来の半導体微粒子ドープガラスからな
る非線形光学材料ないしはその製造方法においては、次
のような課題があった。However, conventional nonlinear optical materials made of glass doped with semiconductor fine particles and their manufacturing methods have the following problems.
（１）溶融法を用いた場合：ＣｄＳ ５ｅｔ−Ｘとホ
ウケイ酸ガラスを１６００’Ｃ以上の高温で溶融して作
製するために、ＣｄＳ ５ｅｔ−エなどの半導体微粒
子の表面が雰囲気ガスやホウケイ酸ガラスと反応して酸
化など化学変化をおこす。このために半導体組成の制御
が極めて難しいものとなる。さらにＣｄＳ ５ｅｌ−１
をホウケイ酸ガラスに２〜４重量％以上均質に分散させ
ることが困難である。すなわち、半導体をガラス中に２
〜４重量％程度以上含有させると、冷却速度が遅いため
、半導体の粒径が非常に大きくなって微粒子として゛存
在し得なくなり、ガラスを失透させたり、半導体の光吸
収端近傍の発光スペクトル強度を低下させたりして、非
線形光学効果の発現に悪影響を及ぼす。このため、半導
体微粒子をガラス中に２〜４重量％程度以上均一に分散
させることは困難である。(1) When using the melting method: Since CdS 5et-X and borosilicate glass are melted at a high temperature of 1600'C or higher, the surface of semiconductor particles such as CdS 5et-X is exposed to atmospheric gas or borosilicate glass. Reacts with glass and causes chemical changes such as oxidation. This makes controlling the semiconductor composition extremely difficult. Furthermore, CdS 5el-1
It is difficult to homogeneously disperse 2 to 4% by weight or more of borosilicate glass. In other words, 2 semiconductors are placed in glass.
If the content exceeds about 4% by weight, the cooling rate is slow, so the particle size of the semiconductor becomes so large that it cannot exist as fine particles, which may cause devitrification of the glass or change the emission spectrum near the optical absorption edge of the semiconductor. This adversely affects the expression of nonlinear optical effects by lowering the intensity. For this reason, it is difficult to uniformly disperse semiconductor fine particles in glass in an amount of about 2 to 4% by weight or more.
（２）スパッタ法を用いた場合二酸化物であるガラス中
に半導体微粒子をドープして作製するので（１）と同様
に半導体表面が酸化され易くなる。(2) When the sputtering method is used, the semiconductor surface is easily oxidized as in (1) because semiconductor fine particles are doped into glass, which is a dioxide.
また、ガラス薄膜の形成に時間がかかり、と（に、スパ
ッタリング速度の小さなＳｉＯ２ガラスの形成の場合は
厚膜を形成するのが困難である。（例えば、ＳｉＯ２な
どでは１ミクロンの厚さに堆積するのに約１〜１０時間
を要する。）
さらに、以上の２つの製造方法は酸化物中に半導体微粒
子をドープすることであるが、酸化物の替わりに窒化物
や炭化物の非晶質薄膜中に半導体微粒子をドープするこ
とも考えられる。しかしながら、窒化物や炭化物を作製
する場合、非晶質材料の禁制帯幅中にダングリングボン
ドによる多数の準位を形成してしまい、半導体微粒子を
ドープしても量子効果を発現させることが困難であり、
良好な非線形光学特性を有する非線形光学材料が得られ
ないと言う欠点かあった。In addition, it takes time to form a thin glass film, and it is difficult to form a thick film with SiO2 glass, which has a low sputtering rate. (It takes about 1 to 10 hours to complete the process.) Furthermore, the above two manufacturing methods involve doping semiconductor particles into an oxide, but instead of doping an oxide with an amorphous thin film of nitride or carbide. It is also possible to dope semiconductor particles into the semiconductor particles.However, when producing nitrides and carbides, many levels due to dangling bonds are formed in the forbidden band of the amorphous material, making it difficult to dope semiconductor particles. However, it is difficult to produce quantum effects even if
One drawback was that a nonlinear optical material with good nonlinear optical properties could not be obtained.
本発明は、上記の欠点を解決し、半導体微粒子の表面を
酸化されずにドープし、また窒化物や酸化物の禁制帯幅
中のダングリングボンドを減少させて、窒化物や炭化物
中で半導体材料を容易に量子井戸にした非線形光学特性
の良好な非線形光学材料と、その製造方法を提供するこ
とを目的とする。The present invention solves the above-mentioned drawbacks, dopes the surface of semiconductor particles without being oxidized, and reduces dangling bonds in the forbidden band of nitrides and oxides, thereby making semiconductors in nitrides and carbides. It is an object of the present invention to provide a nonlinear optical material with good nonlinear optical properties that can be easily made into a quantum well, and a method for manufacturing the same.
［課題を解決するための手段］
上記課題を解決するために本発明は、下記の構成を有す
るものである。[Means for Solving the Problems] In order to solve the above problems, the present invention has the following configuration.
（１）半導体微粒子か、前記半導体材料より大きな禁制
帯幅を有する水素を添加した窒化物あるいは炭化物の非
晶質薄膜中に分散されてなる非線形光学材料。(1) A nonlinear optical material comprising semiconductor fine particles or a nonlinear optical material dispersed in an amorphous thin film of hydrogen-doped nitride or carbide having a bandgap larger than that of the semiconductor material.
（２）水素を添加した窒化物あるいは炭化物中の前記水
素含有量が１〜４０原子％である前記１項に記載の非線
形光学材料。(2) The nonlinear optical material according to item 1, wherein the hydrogen content in the hydrogen-added nitride or carbide is 1 to 40 at%.
（３）半導体微粒子が前記半導体材料より大きな禁制帯
幅を有する水素を添加した窒化物あるいは炭化物の非晶
質薄膜中に分散されてなる非線形光学材料を製造する方
法において、ターゲットとして、前記半導体のターゲッ
トと、前記非晶質薄膜の構成成分のうち水素を除く構成
成分からなるターゲットとを設けて、スパッタリングガ
ス中に水素を含ませてスパッタリングすることを特徴と
する非線形光学材料の製造方法。(3) In a method for manufacturing a nonlinear optical material in which semiconductor fine particles are dispersed in an amorphous thin film of hydrogen-doped nitride or carbide having a larger bandgap than the semiconductor material, the semiconductor material is used as a target. A method for producing a nonlinear optical material, comprising providing a target and a target made of a constituent other than hydrogen among the constituents of the amorphous thin film, and performing sputtering with hydrogen included in a sputtering gas.
（４）半導体微粒子が前記半導体材料より大きな禁制帯
幅を有する水素を添加した窒化物からなる非晶質薄膜中
に分散されてなる非線形光学材料を製造する方法におい
て、ターゲットとして、前記半導体のターゲットと、前
記非晶質薄膜の構成成分のうち水素と窒素を除く構成成
分からなるターゲットとを設けて、スパッタリングガス
中に窒素と水素とを含ませるか、および／または窒素と
水素の化合物を含ませてスパッタリングすることを特徴
とする非線形光学材料の製造方法。(4) In a method for manufacturing a nonlinear optical material in which semiconductor fine particles are dispersed in an amorphous thin film made of a hydrogen-doped nitride having a bandgap larger than that of the semiconductor material, the semiconductor target is used as a target. and a target consisting of components other than hydrogen and nitrogen among the components of the amorphous thin film, so that the sputtering gas contains nitrogen and hydrogen and/or contains a compound of nitrogen and hydrogen. 1. A method for producing a nonlinear optical material, which comprises sputtering.
（５）半導体微粒子が前記半導体材料より大きな禁制帯
幅を有する水素を添加した炭化物からなる非晶質薄膜中
に分散されてなる非線形光学材料を製造する方法におい
て、ターゲットとして、前記半導体のターゲットと、前
記非晶質薄膜の構成成分のうち水素と炭素を除く構成成
分からなるターゲットとを設けて、スパッタリングガス
中に炭化水素と水素とを含ませてスパッタリングするこ
とを特徴とする非線形光学材料の製造方法。(5) In a method for manufacturing a nonlinear optical material in which semiconductor fine particles are dispersed in an amorphous thin film made of a hydrogen-doped carbide having a bandgap larger than that of the semiconductor material, the semiconductor target is used as a target. , a nonlinear optical material characterized in that sputtering is carried out with a sputtering gas containing hydrocarbons and hydrogen by providing a target consisting of components other than hydrogen and carbon among the components of the amorphous thin film. Production method.
［作用コ
本発明の非線形光学材料は半導体微粒子を半導体より大
きな禁制帯幅を有する水素を添加した窒化物あるいは炭
化物のうちいずれかの非晶質薄膜中にドープした構造を
有しているために、酸化物中に半導体微粒子をトープし
たものより、半導体材料の表面が酸化されることかない
。また、窒化物や炭化物の非晶質に水素を添加するので
、非晶質中のダングリングを水素で補償できる。すなわ
ち、非晶質中の多数の準位を水素によって減少させるこ
とができる。[Function] The nonlinear optical material of the present invention has a structure in which semiconductor fine particles are doped into an amorphous thin film of either hydrogen-doped nitride or carbide, which has a larger forbidden band width than a semiconductor. The surface of the semiconductor material is less likely to be oxidized than that of an oxide doped with semiconductor particles. Furthermore, since hydrogen is added to the amorphous nitride or carbide, dangling in the amorphous can be compensated for with hydrogen. That is, many levels in the amorphous state can be reduced by hydrogen.
また、第２番目の発明については、窒化物ないし炭化物
中の水素の含有量を１゛〜４０〜４０原子ので、これら
の非晶質薄膜の光学的禁制帯幅を太き（でき、また、薄
膜中に半導体材料をドープし、さらに均一な量子ドツト
を形成するために熱処理を行う場合にも安定であり好ま
しい。Regarding the second invention, since the hydrogen content in the nitride or carbide is 1~40~40 atoms, the optical forbidden band width of these amorphous thin films can be widened (also, It is also stable and preferred when a semiconductor material is doped into a thin film and heat treatment is performed to form uniform quantum dots.
第３〜５番目の発明については、スパッタリングガス中
に水素ないしはその化合物が含まれいる状態でスパッタ
リングを行うので、半導体微粒子を非晶質薄膜中に高濃
度で濃度分布が均一にドープした薄膜を作製することが
可能である。ゆえに半導体微粒子をドープした非晶質薄
膜からなる非線形光学材料を容易に得ることかできる。Regarding the third to fifth inventions, since sputtering is performed in a state where hydrogen or its compound is contained in the sputtering gas, a thin film in which semiconductor fine particles are doped at a high concentration and with a uniform concentration distribution in an amorphous thin film is formed. It is possible to create one. Therefore, a nonlinear optical material consisting of an amorphous thin film doped with semiconductor fine particles can be easily obtained.
また、非晶質を構成する材料が窒化物や炭化物と水素な
ので、半導体材料に大きく影響を与えることがない。さ
らに非線形光学材料を作製する場合、還元雰囲気となる
水素を用いるので、残留ガスの酸素による半導体材料の
酸化を防ぐことができる。Furthermore, since the materials forming the amorphous state are nitrides, carbides, and hydrogen, it does not significantly affect the semiconductor material. Furthermore, when producing a nonlinear optical material, since hydrogen is used as a reducing atmosphere, it is possible to prevent the semiconductor material from being oxidized by residual gas oxygen.
また、特に第４ならびに第５番目の発明については、水
素と窒素ないしはそれらの化合物あるいは水素と炭化水
素とをスパッタリングガス中に含めて水素を添加した窒
化物ないしは炭化物も同時に合成されるので、より良好
な理想的な品質の非晶質薄膜を同時に形成することが可
能となる。In addition, particularly in the fourth and fifth inventions, hydrogen and nitrogen or their compounds or hydrogen and hydrocarbons are included in the sputtering gas, and hydrogen-added nitrides or carbides are also synthesized at the same time. It becomes possible to simultaneously form an amorphous thin film of good ideal quality.
［実施例］
本発明の非晶質薄膜には水素を添加した窒化物あるいは
炭化物が用いられるが、ドープする半導体材料よりも大
きな禁制帯幅、好ましくは３ｅｖ以上の禁制帯幅を有す
る水素を添加した窒化物あるいは炭化物が好ましく、と
くに窒化ホウ素、窒化アルミニウム、窒化チタン、窒化
ケイ素、炭化ホウ素、炭化チタン、炭化ケイ素に水素を
添加した非晶質薄膜を用いると、半導体材料微粒子の分
散性が良好となり、より好ましい。[Example] Nitride or carbide doped with hydrogen is used for the amorphous thin film of the present invention, and hydrogen having a band gap larger than that of the semiconductor material to be doped, preferably 3ev or more is added. Preferred are nitrides or carbides, and in particular boron nitride, aluminum nitride, titanium nitride, silicon nitride, boron carbide, titanium carbide, and amorphous thin films made by adding hydrogen to silicon carbide provide good dispersibility of semiconductor material particles. Therefore, it is more preferable.
なお、水素を添加した窒化物ないしは炭化物中の水素の
含有量は１〜４０原そ％、特に１〜３０原子％が、これ
らの非晶質薄膜の光学的禁制帯幅を大きくでき、また、
薄膜中に半導体材料をドープし、さらに均一な量子ドツ
トを形成するために熱処理を行う場合にも安定であり好
ましい。The hydrogen content in the hydrogen-added nitride or carbide is 1 to 40 atomic %, particularly 1 to 30 atomic %, to increase the optical forbidden band width of these amorphous thin films, and
It is also stable and preferred when a semiconductor material is doped into a thin film and heat treatment is performed to form uniform quantum dots.
非晶質薄膜中に分散させる半導体微粒子には、ＣｕＣ１
などの金属塩化物、あるいは、ＣｄＳ。The semiconductor fine particles dispersed in the amorphous thin film include CuC1
metal chlorides such as CdS.
ＣｄＳｅ、ＣｄＴｅ、Ｚｎ５ｅ、ＺｎＯ，ＺｎＴｅ、Ｈ
ｇＴｅ、Ｃｄ５Ｓｅ、ＨｇＣｄＴｅなどの１ｌ−Ｖｌ族
化合物半導体、あるいはＧａＡｓ、ＧａＮ、ＧａＰ、Ｇ
ａＳｂ、ＩｎＡｓ、ＩｎＰ、ＩｎＳｂ、ＧａＡｌＡｓ、
ＩｎＡｌＡｓなどのＩＩＩ −Ｖ族化合物半導体、ある
いはＳｉ、Ｇｅなどの１ｖ族半導体が好ましい。CdSe, CdTe, Zn5e, ZnO, ZnTe, H
1l-Vl group compound semiconductors such as gTe, Cd5Se, HgCdTe, or GaAs, GaN, GaP, G
aSb, InAs, InP, InSb, GaAlAs,
III-V group compound semiconductors such as InAlAs, or 1V group semiconductors such as Si and Ge are preferred.
非晶質薄膜中に分散させる半導体微粒子の量は通常、０
，１〜３０重量％、特に０．１〜１０重量％が好ましい
。The amount of semiconductor fine particles dispersed in the amorphous thin film is usually 0.
, 1 to 30% by weight, particularly 0.1 to 10% by weight.
非線形光学特性を良好に発現させるためには、非晶質薄
膜中に分散した半導体微粒子の粒径は、用いる半導体の
種類によって異なるが、通常１゜ｎｍ〜０．５ｎｍ程度
か好ましく、特に、その半導体のボーア半径以上の大き
さであって、かつ、量子サイズ効果が現れる程度に小さ
いことが好ましい。In order to exhibit good nonlinear optical properties, the particle size of the semiconductor fine particles dispersed in the amorphous thin film varies depending on the type of semiconductor used, but is usually preferably about 1° nm to 0.5 nm. It is preferable that the size is equal to or larger than the Bohr radius of the semiconductor and small enough to cause a quantum size effect to appear.
また、スパッタリング条件としては、用いる材料の種類
やスパッタリング手法によって異なるので、−概に規定
しがたいが、例えば代表的なＲＦスパッタ法などの場合
には、１〜６００Ｐａの圧力で、常温〜４００℃の温度
などの範囲である。In addition, sputtering conditions vary depending on the type of material used and the sputtering method, so it is difficult to specify them generally, but for example, in the case of a typical RF sputtering method, the sputtering conditions are at a pressure of 1 to 600 Pa, at room temperature to 400 Pa. A range of temperatures such as degrees Celsius.
以下本発明の実施例について具体的に説明する。Examples of the present invention will be specifically described below.
実施例１ 本実施例で用いたスパッタ装置の構成を第１図に示す。Example 1 FIG. 1 shows the configuration of the sputtering apparatus used in this example.
第１図に示すように、半導体材料のターゲット１．窒化
物のターゲット２．基板３およびそれぞれのターゲット
に供給する高周波電源４゜５、絶縁物６ならびにガス供
給ロアによって、スパッタ装置８は構成されている。タ
ーゲット１に用いる半導体材料としては、金属塩化物の
ＣｕＣＩｔたはＩｆ−ｖ１半導体ノＣｄＳ Ｓｅ
（ｘ＝Ｏ。As shown in FIG. 1, a semiconductor material target 1. Nitride target 2. The sputtering apparatus 8 is constituted by a high frequency power source 4.5 supplied to the substrate 3 and each target, an insulator 6, and a gas supply lower. The semiconductor material used for the target 1 is CuCIt, which is a metal chloride, or CdSSe, which is an If-v1 semiconductor.
(x=O.
Ｋ Ｌｘ
１）、ターゲット２として用いる窒化物は窒化ケイ素、
基板３は石英ガラスを用いた。スパッタガスとしてはガ
ス供給ロアより水素とアルゴンの混合ガスを導入し、そ
れぞれを５Ｐａ、ＩＰａにした。K Lx 1), the nitride used as target 2 is silicon nitride,
The substrate 3 was made of quartz glass. As the sputtering gas, a mixed gas of hydrogen and argon was introduced from the gas supply lower, and the gas was set at 5 Pa and IPa, respectively.
ターゲットに供給した高周波電力は、ターゲット１に２
０Ｗ１ターゲツト２に２５０Ｗでスパッタリングを行な
い、膜厚３μｍの半導体ドープした非晶質薄膜を０．５
ｍｍ厚の石英ガラス上に形成した。The high frequency power supplied to the target is
Sputtering was performed on 0W1 target 2 at 250W to form a semiconductor-doped amorphous thin film with a thickness of 3 μm at 0.5 μm.
It was formed on quartz glass with a thickness of mm.
薄膜中のＣｕＣ１のドープ量は１０重量％であり、粒子
径は４〜６ｎｍであった。またＣｄＳ。The doping amount of CuC1 in the thin film was 10% by weight, and the particle size was 4 to 6 nm. Also CdS.
５ｅ１−１のドープ量は８重量％であり粒子径は５〜９
ｎｍであった。The doping amount of 5e1-1 is 8% by weight, and the particle size is 5-9.
It was nm.
上記の半導体をドープしない場合、水素添加の窒化ケイ
素薄膜の光学的禁制帯幅は５．２ｅＶであり、水素を添
加しない場合の窒化ケイ素薄膜の光学的禁制帯幅４．５
ｅＶに比べて、０．７ｅＶも大きくなった。水素添加の
窒化ケイ素薄膜の光学的禁制帯幅の値はバルクの値とほ
ぼ同じ値であり、この結果は、ダングリングボンドに起
因する禁制帯内の準位を水素によって補償したことがわ
かる。また、赤外線吸収スペクトルから水素添加の窒化
ケイ素薄膜中の水素含有量を求めると、１０原子％含ま
れていた。When the above semiconductor is not doped, the optical forbidden band width of a silicon nitride thin film with hydrogen addition is 5.2 eV, and the optical forbidden band width of a silicon nitride thin film without hydrogen addition is 4.5 eV.
eV, it became larger by 0.7 eV. The value of the optical forbidden band width of the hydrogen-doped silicon nitride thin film is almost the same as the value of the bulk, and this result shows that the levels within the forbidden band caused by dangling bonds were compensated by hydrogen. Further, when the hydrogen content in the hydrogenated silicon nitride thin film was determined from the infrared absorption spectrum, it was found to be 10 atomic %.
さらに、ＣｕＣ１、ＣｄＳ ５ｅ１−Ｘの半導体！
材料をドープした水素添加の窒化ケイ素非晶質薄膜の吸
収スペクトルから、得られた薄膜の禁制帯幅は、それぞ
れの材料のバルク値に比べ０．５゜０．４ｅＶブルーシ
フトしていることから、半導体材料が量子ドツトとなっ
ていることがわかった。Furthermore, CuC1, CdS 5e1-X semiconductors! From the absorption spectrum of a hydrogenated silicon nitride amorphous thin film doped with the material, the forbidden band width of the obtained thin film is blue-shifted by 0.5° 0.4 eV compared to the bulk value of each material. It was discovered that the semiconductor material is a quantum dot.
実施例２
実施例１と同様なスパッタ装置８を用いて、ケイ素のタ
ーゲット２と、窒素ガスと水素ガスの反応によって水素
を添加した窒化ケイ素の非晶質薄膜を形成しながら、半
導体ドープ非晶質薄膜を作成した。ガス供給ロアよりス
パッタガスとして窒素、水素、アルゴンを供給し、それ
ぞれ３Ｐａ。Example 2 Using the same sputtering device 8 as in Example 1, a semiconductor-doped amorphous film was formed while forming an amorphous thin film of silicon nitride to which hydrogen was added through a reaction between a silicon target 2 and nitrogen gas and hydrogen gas. A quality thin film was created. Nitrogen, hydrogen, and argon are supplied as sputtering gases from the gas supply lower, each at a pressure of 3 Pa.
０．５Ｐａ、２Ｐａにした。半導体のターゲット■は金
属塩化物のＣｕＣ１またはＩＩ−１１半導体のＣｄＳ
Ｓｅ （Ｘ＝０．１）にした。ターゲット１゜
ＬＸ
２に直流電力を供給し、ターゲット電圧はそれぞれ３０
０Ｖ、ＩＫＶにし、ターゲット電流密度は０．５ｍＡ／
Ｃｍ２にしてスパッタリングを行ない、膜厚２μｍの半
導体ドープ非晶質薄膜を基板（０，５ｍｍ）上に形成し
た。The pressure was set to 0.5 Pa and 2 Pa. Semiconductor target ■ is metal chloride CuC1 or II-11 semiconductor CdS
Se (X=0.1). DC power is supplied to target 1゜ LX 2, and the target voltage is 30
0V, IKV, target current density is 0.5mA/
Sputtering was performed at Cm2 to form a semiconductor-doped amorphous thin film with a thickness of 2 μm on a substrate (0.5 mm).
薄膜中のＣｕＣｌのドープ量は２０重量％であり粒子径
は４〜６ｎｍであった。また、ＣｄＳ工５ｅ１−Ｘのド
ープ量は１８重量％であり粒子径は５〜９ｎｍであった
。The amount of CuCl doped in the thin film was 20% by weight, and the particle size was 4 to 6 nm. Further, the doping amount of CdS 5e1-X was 18% by weight, and the particle size was 5 to 9 nm.
上記の半導体をドープしない場合、水素添加の窒化ケイ
素薄膜の光学的禁制帯幅は５．２ｅＶであり、水素を添
加しない場合の窒化ケイ素薄膜の光学的禁制帯幅４．８
ｅＶに比べて、０．４ｅＶも大きくなった。When the above semiconductor is not doped, the optical forbidden band width of a silicon nitride thin film with hydrogen addition is 5.2 eV, and the optical forbidden band width of a silicon nitride thin film without hydrogen addition is 4.8 eV.
eV, it became larger by 0.4 eV.
水素添加の窒化ケイ素薄膜の光学的禁制帯幅の値はバル
クの値とほぼ同じ値であり、この結果は、ダングリング
ボンドに起因する禁制帯内の準位を水素によって補償し
たことがわかる。また、赤外線吸収スペクトルから水素
添加の窒化ケイ素薄膜中の水素含有量を求めると、２０
原子％含まれていた。The value of the optical forbidden band width of the hydrogen-doped silicon nitride thin film is almost the same as the value of the bulk, and this result shows that the levels within the forbidden band caused by dangling bonds were compensated by hydrogen. Furthermore, when determining the hydrogen content in a hydrogenated silicon nitride thin film from the infrared absorption spectrum, it is found that 20
It contained atomic%.
上記２種の半導体材料をドープした窒化ケイ素非晶質薄
膜の吸収スペクトルから、得られた薄膜の禁制帯幅はそ
れぞれバルクの値に比べ０．４゜０．３５ｅＶブルーシ
フトしていることから半導体が量子ドツトとなっている
ことがわかった。From the absorption spectra of silicon nitride amorphous thin films doped with the above two types of semiconductor materials, the forbidden band widths of the obtained thin films are blue-shifted by 0.4° and 0.35 eV compared to the bulk values. was found to be a quantum dot.
なお、本実施例では半導体をドープした水素添加の窒化
ケイ素非晶質薄膜であったが、上記以外の窒化ホウ素、
窒化アルミニウム、窒化チタンについても半導体をドー
プするとブルーシフトを観察できた。In this example, a hydrogenated silicon nitride amorphous thin film doped with a semiconductor was used, but other materials such as boron nitride,
A blue shift was also observed when aluminum nitride and titanium nitride were doped with semiconductors.
本実施例では窒化ケイ素非晶質薄膜を作製する場合に窒
素ガスと水素ガスを用いたが、アンモニアガスのような
窒素と水素の化合物でもよいし、窒素化合物と水素化合
物の混合ガスを用いることもでき、第４番目の発明で言
う、窒素と水素の化合物とはこの両者を包含する意味で
ある。In this example, nitrogen gas and hydrogen gas were used when producing an amorphous silicon nitride thin film, but a compound of nitrogen and hydrogen such as ammonia gas may be used, or a mixed gas of a nitrogen compound and a hydrogen compound may be used. In the fourth invention, the term "compound of nitrogen and hydrogen" includes both of them.
実施例３
実施例１と同様なスパッタ装置８を用いて、ケイ素のタ
ーゲット２と炭化水素の反応によって炭化ケイ素の非晶
質薄膜を形成しなから、半導体トープ非晶質薄膜を作成
した。ガス供給ロアよりスパッタガスとしてメタンガス
（ＣＨ３）、水素ガス、アルゴンを供給し、それぞれ３
Ｐａ、ＩＰａ。Example 3 Using the same sputtering apparatus 8 as in Example 1, an amorphous thin film of silicon carbide was formed by a reaction between a silicon target 2 and a hydrocarbon, and then a semiconducting amorphous thin film was created. Methane gas (CH3), hydrogen gas, and argon are supplied as sputtering gases from the gas supply lower, and 3
Pa, IPa.
２Ｐａにした。半導体のターゲット１は、Ｉｌｌ ７Ｖ
半導体のＧａＡｓまたはＩＩ−Ｖｌ半導体のＣｄＴｅに
した。ターゲット１，２に供給した高周波電力はそれぞ
れ４０．２５０Ｗにしてスパッタリングを行ない、膜厚
５μｍの半導体ドープ非晶質薄膜を基板（０，５ｍｍ）
上に形成した後３００℃の電気炉中で１時間加熱しＧａ
ＡｓまたはＣｄＴｅの結晶を成長させた。I set it to 2Pa. Semiconductor target 1 is Ill 7V
The semiconductor GaAs or the II-Vl semiconductor CdTe was used. The high-frequency power supplied to targets 1 and 2 was set to 40.250 W, respectively, and sputtering was performed, and a semiconductor-doped amorphous thin film with a film thickness of 5 μm was deposited on a substrate (0.5 mm).
After forming the Ga
Crystals of As or CdTe were grown.
薄膜中のＧａＡｓのドープ量は１０重量％であり粒子径
は４〜６ｎｍであった。またＣｄＴｅのドープ量は１４
重量％であり粒子径は５〜９ｎｍであった。The amount of GaAs doped in the thin film was 10% by weight, and the particle size was 4 to 6 nm. Also, the doping amount of CdTe is 14
% by weight, and the particle size was 5 to 9 nm.
上記の半導体をドープしない場合の炭化ケイ素薄膜の吸
収スペクトルから薄膜の光学的禁制帯幅は２．５ｅＶで
あり、水素を添加しない場合の炭化ケイ素薄膜の光学的
禁制帯幅２．ＯｅＶに比べて、０．５ｅＶも大きくなっ
た。From the absorption spectrum of the silicon carbide thin film without doping with the semiconductor described above, the optical forbidden band width of the thin film is 2.5 eV, and the optical forbidden band width of the silicon carbide thin film without hydrogen addition is 2.5 eV. Compared to OeV, it became larger by 0.5 eV.
この値は、バルクの値とほぼ同じ値であり、この結果は
、ダングリングボンドに起因する禁制帯内の準位を水素
によって補償したことがわかる。This value is almost the same as the bulk value, and this result shows that the level in the forbidden band caused by dangling bonds was compensated by hydrogen.
また、赤外線吸収スペクトルから水素添加の炭化ケイ素
薄膜中の水素含有量を求めると、５原子％含まれていた
。Further, when the hydrogen content in the hydrogenated silicon carbide thin film was determined from the infrared absorption spectrum, it was found to be 5 at %.
上記２種の半導体材料をドープした炭化ケイ素非晶質薄
膜の吸収スペクトルから、得られた薄膜の禁制帯幅はそ
れぞれバルクの値に比べ０．５゜０．４ｅＶブルーシフ
トしていることがら半導体が量子ドツトとなっているこ
とがわかった。The absorption spectra of silicon carbide amorphous thin films doped with the above two semiconductor materials show that the forbidden band widths of the obtained thin films are blue-shifted by 0.5° and 0.4 eV compared to the bulk values. was found to be a quantum dot.
炭化ケイ素非晶質薄膜では上記半導体以外にＣｄＳｅ、
ＺｎＴｅ、ＨｇＴｅ、ＨｇＣｄＴｅなどのＩＩ−４１半
導体、Ｇａｒｂ、ＩｎＡｓ、ＩｎＰ。In the silicon carbide amorphous thin film, in addition to the above semiconductors, CdSe,
II-41 semiconductors such as ZnTe, HgTe, HgCdTe, Garb, InAs, InP.
ＩｎＳｂ、ＧａＡｌＡｓ、ｒｎＡＩＡｓなどのＩＩ１−
Ｖ族化合物半導体、あるいはＳｉ、Ｇｅなどの１ｖ族半
導体もドープすることができた。II1- such as InSb, GaAlAs, rnAIAs, etc.
Group V compound semiconductors or Group 1V semiconductors such as Si and Ge could also be doped.
なお、本実施例では半導体ドープ水素添加炭化ケイ素非
晶質薄膜であったが、上記以外の水素を添加した炭化ホ
ウ素、炭化チタンについても半導体をドープするとブル
ーシフトを観察できた。In this example, a semiconductor-doped hydrogenated silicon carbide amorphous thin film was used, but a blue shift could also be observed when hydrogen-doped boron carbide and titanium carbide other than those mentioned above were doped with a semiconductor.
本実施例では水素を添加した炭化ケイ素非晶質薄膜を作
製する場合にメタンガス（ＣＨ３）を用いたが、他の炭
化水素ガスでもよく、例えばエタンガス、プロパンガス
、エチレンガスなど、各種の炭化水素ガスを用いること
ができる。In this example, methane gas (CH3) was used to fabricate a silicon carbide amorphous thin film to which hydrogen was added, but other hydrocarbon gases may also be used. For example, various hydrocarbons such as ethane gas, propane gas, ethylene gas, etc. Gas can be used.
さらに、薄膜中の水素含有量も１〜４０原子％の範囲内
であり、良好な量子ドツトを形成する薄膜を得ることが
できた。Further, the hydrogen content in the thin film was within the range of 1 to 40 atomic %, and a thin film capable of forming good quantum dots could be obtained.
実施例４
実施例１，２に示した方法により作製したＣｕＣ１ドー
プおよびＣｄＳ Ｓｅ （Ｘ＝０．１）ドー
ｉＩ
プ窒化ケイ素非晶質薄膜を用い、光双安定素子を作製し
た。Example 4 CuC1-doped and CdS Se (X=0.1)-doped samples prepared by the method shown in Examples 1 and 2
An optical bistable device was fabricated using an amorphous silicon nitride thin film.
この素子の石英ガラス基板側から波長５３０ｎｍのレー
ザ光（Ｎ ２光励起色素レーザ光）をスポット径５μｍ
で入射した。A laser beam with a wavelength of 530 nm (N2 light excited dye laser beam) is emitted from the quartz glass substrate side of this element with a spot diameter of 5 μm.
The incident occurred at
次に入射光の強度と出射光の強度の関係を室温（２５℃
）にて測定したところ、第２図に示したような双安定特
性を示した。Next, we will calculate the relationship between the intensity of the incident light and the intensity of the emitted light at room temperature (25°C).
), it showed bistable characteristics as shown in Figure 2.
なお、実施例３に示した方法により作製したＧａＡｓド
ープおよびＣｄＴｅドープ炭化ケイ素非晶質薄膜の場合
も、光双安定素子を観察できた。Note that optical bistable elements could also be observed in the case of the GaAs-doped and CdTe-doped silicon carbide amorphous thin films produced by the method shown in Example 3.
［発明の効果コ
本発明の非線形光学材料は半導体微粒子を半導体より大
きな禁制帯幅を有する水素を添加した窒化物あるいは炭
化物のうちいずれかの非晶質薄膜中にドープした構造を
有しているために、酸化物中に半導体微粒子をドープし
たものより、半導体材料の表面が酸化されることがない
。また、窒化物や炭化物の非晶質に水素を添加するので
、非晶質中のダングリングを水素で補償でき非線形光学
特性の良好な非線形光学材料を提供できる。[Effects of the Invention] The nonlinear optical material of the present invention has a structure in which semiconductor fine particles are doped into an amorphous thin film of either hydrogen-doped nitride or carbide, which has a larger forbidden band width than a semiconductor. Therefore, the surface of the semiconductor material is less likely to be oxidized than when semiconductor particles are doped into an oxide. Furthermore, since hydrogen is added to the amorphous nitride or carbide, dangling in the amorphous can be compensated for by hydrogen, and a nonlinear optical material with good nonlinear optical properties can be provided.
また、第２番目の発明については、窒化物ないし炭化物
中の水素の含有量を１〜４０原子％としたので、これら
の非晶質薄膜の光学的禁制帯幅を大きくでき、また、さ
らに均一な量子ドツトを形成するために熱処理を行う場
合にも安定な非線形光学材料を提供できる。In addition, in the second invention, since the hydrogen content in the nitride or carbide is set to 1 to 40 at%, the optical bandgap width of these amorphous thin films can be increased, and the optical band width can be made even more uniform. A stable nonlinear optical material can be provided even when heat treatment is performed to form quantum dots.
第３〜５番目の発明については、上述の効果のほか、半
導体微粒子を非晶質薄膜中に高濃度で濃度分布が均一に
ドープした薄膜を作製することか可能であり、非線形光
学材料を容易に得ることができる。Regarding the third to fifth inventions, in addition to the above-mentioned effects, it is possible to fabricate a thin film in which semiconductor fine particles are doped in an amorphous thin film at a high concentration and with a uniform concentration distribution, and it is possible to easily produce nonlinear optical materials. can be obtained.
また、非晶質を構成する材料が窒化物や炭化物と水素な
ので、半導体材料に大きく影響を与えることがない。さ
らに非線形光学材料を作製する場合、還元雰囲気となる
水素を用いるので、残留ガスの酸素による半導体材料の
酸化を防ぐことができる。Furthermore, since the materials forming the amorphous state are nitrides, carbides, and hydrogen, it does not significantly affect the semiconductor material. Furthermore, when producing a nonlinear optical material, since hydrogen is used as a reducing atmosphere, it is possible to prevent the semiconductor material from being oxidized by residual gas oxygen.
特に第４ならびに第５番目の発明については、より良好
な品質の非晶質薄膜を同時に形成することが可能となる
。In particular, with the fourth and fifth inventions, it is possible to simultaneously form an amorphous thin film of better quality.
以上、本発明は、大きな非線形光学特性を有する薄膜を
得ることが可能で、その応用として光双安定素子などを
作製することができる。As described above, according to the present invention, it is possible to obtain a thin film having large nonlinear optical characteristics, and as an application thereof, an optical bistable device and the like can be manufactured.
第１図は本発明の実施例で用いたスバ・ツタ装置の概略
構成図、第２図は本発明の一実施例の半導体材料をドー
プした非晶質薄膜を用いた双安定素子の光双安定特性図
である。
１・・・半導体のターゲット、２・・・炭化物または窒
化物原料のターゲット、３・・・基板、４．５・・・高
周波電源、６・・・絶縁物、７・・・ガス供給口、８・
・・スｌ々ツタリング装置。Figure 1 is a schematic diagram of the Suba-Tuta device used in an embodiment of the present invention, and Figure 2 is an optical twin of a bistable device using an amorphous thin film doped with a semiconductor material according to an embodiment of the present invention. It is a stability characteristic diagram. DESCRIPTION OF SYMBOLS 1... Semiconductor target, 2... Target of carbide or nitride raw material, 3... Substrate, 4.5... High frequency power supply, 6... Insulator, 7... Gas supply port, 8・
...Slittering device.
Claims (5)
帯幅を有する水素を添加した窒化物あるいは炭化物の非
晶質薄膜中に分散されてなる非線形光学材料。(1) A nonlinear optical material in which semiconductor fine particles are dispersed in an amorphous thin film of hydrogen-doped nitride or carbide that has a larger forbidden band width than the semiconductor material.
素含有量が１〜４０原子％である請求項１に記載の非線
形光学材料。(2) The nonlinear optical material according to claim 1, wherein the hydrogen content in the hydrogen-added nitride or carbide is 1 to 40 at.%.
幅を有する水素を添加した窒化物あるいは炭化物の非晶
質薄膜中に分散されてなる非線形光学材料を製造する方
法において、ターゲットとして、前記半導体のターゲッ
トと、前記非晶質薄膜の構成成分のうち水素を除く構成
成分からなるターゲットとを設けて、スパッタリングガ
ス中に水素を含ませてスパッタリングすることを特徴と
する非線形光学材料の製造方法。(3) In a method for manufacturing a nonlinear optical material in which semiconductor fine particles are dispersed in an amorphous thin film of hydrogen-doped nitride or carbide having a larger bandgap than the semiconductor material, the semiconductor material is used as a target. A method for producing a nonlinear optical material, comprising providing a target and a target made of a constituent other than hydrogen among the constituents of the amorphous thin film, and performing sputtering with hydrogen included in a sputtering gas.
幅を有する水素を添加した窒化物からなる非晶質薄膜中
に分散されてなる非線形光学材料を製造する方法におい
て、ターゲットとして、前記半導体のターゲットと、前
記非晶質薄膜の構成成分のうち水素と窒素を除く構成成
分からなるターゲットとを設けて、スパッタリングガス
中に窒素と水素とを含ませるか、および／または窒素と
水素の化合物を含ませてスパッタリングすることを特徴
とする非線形光学材料の製造方法。(4) In a method for manufacturing a nonlinear optical material in which semiconductor fine particles are dispersed in an amorphous thin film made of a hydrogen-doped nitride having a bandgap larger than that of the semiconductor material, the semiconductor target is used as a target. and a target consisting of components other than hydrogen and nitrogen among the components of the amorphous thin film, so that the sputtering gas contains nitrogen and hydrogen and/or contains a compound of nitrogen and hydrogen. 1. A method for producing a nonlinear optical material, which comprises sputtering.
幅を有する水素を添加した炭化物からなる非晶質薄膜中
に分散されてなる非線形光学材料を製造する方法におい
て、ターゲットとして、前記半導体のターゲットと、前
記非晶質薄膜の構成成分のうち水素と炭素を除く構成成
分からなるターゲットとを設けて、スパッタリングガス
中に炭化水素と水素とを含ませてスパッタリングするこ
とを特徴とする非線形光学材料の製造方法。(5) In a method for manufacturing a nonlinear optical material in which semiconductor fine particles are dispersed in an amorphous thin film made of a hydrogen-doped carbide having a bandgap larger than that of the semiconductor material, the semiconductor target is used as a target. , a nonlinear optical material characterized in that sputtering is carried out with a sputtering gas containing hydrocarbons and hydrogen by providing a target consisting of components other than hydrogen and carbon among the components of the amorphous thin film. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33592190A JPH04204426A (en) | 1990-11-29 | 1990-11-29 | Nonlinear optical material and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33592190A JPH04204426A (en) | 1990-11-29 | 1990-11-29 | Nonlinear optical material and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04204426A true JPH04204426A (en) | 1992-07-24 |
Family
ID=18293853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33592190A Pending JPH04204426A (en) | 1990-11-29 | 1990-11-29 | Nonlinear optical material and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04204426A (en) |
-
1990
- 1990-11-29 JP JP33592190A patent/JPH04204426A/en active Pending
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