JPH04345137A - Production of nonlinear optical material - Google Patents
Production of nonlinear optical materialInfo
- Publication number
- JPH04345137A JPH04345137A JP11857491A JP11857491A JPH04345137A JP H04345137 A JPH04345137 A JP H04345137A JP 11857491 A JP11857491 A JP 11857491A JP 11857491 A JP11857491 A JP 11857491A JP H04345137 A JPH04345137 A JP H04345137A
- Authority
- JP
- Japan
- Prior art keywords
- nitride
- semiconductor
- target
- thin film
- 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
- 239000000463 material Substances 0.000 title claims abstract description 65
- 230000003287 optical effect Effects 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 239000004065 semiconductor Substances 0.000 claims abstract description 90
- 239000010409 thin film Substances 0.000 claims abstract description 50
- 150000004767 nitrides Chemical class 0.000 claims abstract description 44
- 239000000758 substrate Substances 0.000 claims abstract description 44
- 239000002245 particle Substances 0.000 claims abstract description 27
- 238000004544 sputter deposition Methods 0.000 claims abstract description 27
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 20
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 43
- 239000010419 fine particle Substances 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 15
- 229910052582 BN Inorganic materials 0.000 claims description 8
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 8
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 7
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000010408 film Substances 0.000 claims description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 abstract description 8
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 abstract description 8
- -1 silicon nitride Chemical class 0.000 abstract description 6
- 239000011521 glass Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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 5
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 229910001510 metal chloride Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- 229910005542 GaSb Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910004262 HgTe Inorganic materials 0.000 description 1
- 229910000673 Indium arsenide Inorganic materials 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- 229910000661 Mercury cadmium telluride Inorganic materials 0.000 description 1
- 229910007709 ZnTe Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 description 1
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 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
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は非線形光学効果を利用し
た光デバイスなどに有用な非線形光学材料の製造方法に
関するもので、とくにスパッタ法により半導体微粒子を
分散して非晶質薄膜を形成する非線形光学材料の製造方
法に関する。[Industrial Application Field] The present invention relates to a method for manufacturing nonlinear optical materials useful for optical devices that utilize nonlinear optical effects, and in particular, a nonlinear optical material that uses a sputtering method to disperse semiconductor particles to form an amorphous thin film. The present invention relates to a method for manufacturing optical materials.
【０００２】0002
【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 オプティカル ソサエティ
オブ アメリカ 第７３巻第６４７ 頁（Ｊｏｕｒ
ｎａｌ ｏｆ Ｏｐｔｉｃａｌ Ｓｏｃｉｅｔｙ ｏｆ
Ａｍｅｒｉｃａ ７３， ６４７（１９８３）） に
記載されているＣｄＳｘ Ｓｅ１−ｘ をホウケイ酸ガ
ラスにド−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ＣｄＳｘ Ｓｅ１−ｘ とホウケイ酸ガラス材料
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 Optical Society.
of America Vol. 73, p. 647 (Jour
nal of Optical Society of
America 73, 647 (1983)), a cut-off filter glass in which borosilicate glass is doped with CdSx Se1-x is used as a nonlinear optical material. This cut-off filter glass is produced by placing CdSx Se1-x and a borosilicate glass material in a platinum crucible and melting them at a high temperature of about 1600°C.
【０００３】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（Ｊｏ
ｕｒｎａｌ ｏｆ Ａｐｐｌｉｅｄ Ｐｈｙｓｉｃｓ
６３， ９５７（１９８８））に開示されているような
ＣｄＳ微粒子ド−プ薄膜ガラスがある。この薄膜ガラス
はタ−ゲットにコ−ニング社製“７０５９”ガラスと、
ＣｄＳとを用い高周波マグネトロンスパッタリング法に
より、“７０５９”ガラス中にＣｄＳを２〜４重量％分
散させたものである。[0003] Also, Journal of Applied Physics, Vol. 63, p. 957 (Jo
urnal of Applied Physics
63, 957 (1988)), there is a thin film glass doped with CdS particles. This thin film glass targets Corning's "7059" glass,
2 to 4% by weight of CdS is dispersed in "7059" glass by high-frequency magnetron sputtering using CdS.
【０００４】0004
【発明が解決しようとする課題】このような半導体微粒
子ド−プガラスの製造方法では、つぎのような２つの課
題があった。[Problems to be Solved by the Invention] This method of manufacturing glass doped with semiconductor fine particles has the following two problems.
【０００５】（１）溶融法を用いた場合：ＣｄＳｘ Ｓ
ｅ１−ｘ とホウケイ酸ガラスを１６００℃以上の高温
で溶融してカットオフフィルタガラスを作製するために
、ＣｄＳｘ Ｓｅ１−ｘ 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ＣｄＳｘ Ｓｅ１−ｘ 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
も困難である。(1) When using the melting method: CdSx S
In order to fabricate a cut-off filter glass by melting e1-x and borosilicate glass at a high temperature of 1600°C or higher, the surface of semiconductor fine particles such as CdSx Se1-x reacts with atmospheric gas and borosilicate glass, resulting in oxidation, etc. Causes chemical changes. This makes controlling the semiconductor composition extremely difficult. Furthermore, it is difficult to homogeneously disperse CdSx Se1-x in borosilicate glass in an amount of 2 to 4% by weight or more.
【０００６】（２）スパッタリング法を用いた場合：酸
化物であるガラス中に半導体微粒子を作製するので（１
）と同様に半導体表面が酸化され易くなる。また、ガラ
ス薄膜の形成に時間がかかり、とくに、スパッタリング
速度の小さなＳｉＯ２ ガラスの薄膜を形成する場合は
厚膜を形成するのが困難であり、例えば１μｍの膜厚に
するのに４〜５時間以上もかかる。(2) When using sputtering method: Since semiconductor fine particles are produced in glass, which is an oxide, (1
), the semiconductor surface becomes easily oxidized. In addition, it takes time to form a glass thin film, and it is difficult to form a thick film, especially when forming a thin film of SiO2 glass with a low sputtering rate. For example, it takes 4 to 5 hours to form a 1 μm thick film. It takes more than that.
【０００７】このような課題を解決するために、半導体
微粒子を窒化物の非晶質薄膜に分散させた材料が提案さ
れている。この場合、半導体表面が酸化されることはな
いが、半導体微粒子が窒素のためにアモルファス化され
非線形光学材料としての機能を失うおそれがある。In order to solve these problems, a material in which semiconductor fine particles are dispersed in an amorphous thin film of nitride has been proposed. In this case, although the semiconductor surface is not oxidized, the semiconductor particles may become amorphous due to nitrogen and lose their function as a nonlinear optical material.
【０００８】本発明は、このような課題を解決し、分散
された半導体微粒子の結晶性がよく、また半導体微粒子
の粒径分布が小さく、すぐれた非線形光学効果を有する
非線形光学材料の製造方法を提供することを目的とする
。The present invention solves these problems and provides a method for producing a nonlinear optical material that has excellent crystallinity of dispersed semiconductor particles, a small particle size distribution, and excellent nonlinear optical effects. The purpose is to provide.
【０００９】[0009]
【課題を解決するための手段】上記課題を解決するため
に本発明の第１の非線形光学材料の製造方法は、ターゲ
ットとして半導体材料のターゲットと前記半導体材料よ
り大きな禁制帯幅を有する窒化物のターゲットとを用い
てスパッタリングを行い、加熱された基板上に、半導体
微粒子を分散させた窒化物の非晶質薄膜を形成すること
からなる。[Means for Solving the Problems] In order to solve the above problems, the first method of manufacturing a nonlinear optical material of the present invention uses a semiconductor material target and a nitride material having a larger forbidden band width than the semiconductor material as targets. The method consists of performing sputtering using a target to form an amorphous thin film of nitride in which semiconductor fine particles are dispersed on a heated substrate.
【００１０】また、本発明の第２の非線形光学材料の製
造方法は、ターゲットとして半導体材料のターゲットと
前記半導体材料より大きな禁制帯幅を有する窒化物のタ
ーゲットとを用いてスパッタリングを行い、加熱された
基板上に半導体微粒子を分散させた窒化物の非晶質薄膜
を形成した後、前記基板の加熱温度より高い温度で熱処
理することからなる。[0010] Furthermore, in the second method of manufacturing a nonlinear optical material of the present invention, sputtering is performed using a semiconductor material target and a nitride target having a larger forbidden band width than the semiconductor material, and the sputtering is performed using a heated target. After forming an amorphous thin film of nitride in which semiconductor fine particles are dispersed on a substrate, heat treatment is performed at a temperature higher than the heating temperature of the substrate.
【００１１】また、本発明の第３の非線形光学材料の製
造方法は、ターゲットとして半導体材料のターゲットと
前記半導体材料より大きな禁制帯幅を有する窒化物の構
成成分のうち窒素を除く構成成分からなるターゲットと
を用いて、ガス中に窒素またはアンモニアのうち少なく
とも１種のガスを含ませてスパッタリングを行い、加熱
された基板上に、半導体微粒子を分散させた窒化物の非
晶質薄膜を形成することからなる。A third method of manufacturing a nonlinear optical material according to the present invention includes a target made of a semiconductor material and a nitride component having a larger forbidden band width than the semiconductor material, excluding nitrogen. Using a target, sputtering is performed using a gas containing at least one of nitrogen or ammonia to form an amorphous thin film of nitride in which semiconductor fine particles are dispersed on a heated substrate. Consists of things.
【００１２】また、本発明の第４の非線形光学材料の製
造方法は、ターゲットとして半導体材料のターゲットと
前記半導体材料より大きな禁制帯幅を有する窒化物の構
成成分のうち窒素を除く構成成分からなるターゲットと
を用いて、ガス中に窒素またはアンモニアのうち少なく
とも１種のガスを含ませてスパッタリングを行い、加熱
された基板上に、半導体微粒子を分散させた窒化物の非
晶質薄膜を形成した後、基板の加熱温度より高い温度で
熱処理することからなる。[0012] A fourth method of manufacturing a nonlinear optical material of the present invention includes a target made of a semiconductor material and a nitride component other than nitrogen, which has a larger forbidden band width than the semiconductor material. Using a target, sputtering was performed using a gas containing at least one of nitrogen or ammonia, and an amorphous thin film of nitride in which semiconductor fine particles were dispersed was formed on a heated substrate. After that, heat treatment is performed at a temperature higher than the heating temperature of the substrate.
【００１３】更に前記非線形光学材料の製造方法におい
ては、窒化物の非晶質薄膜が、窒化ホウ素、窒化アルミ
ニウム、窒化チタン、窒化珪素から選ばれた少なくとも
１種であることが好ましい。Furthermore, in the method for manufacturing a nonlinear optical material, the amorphous nitride thin film is preferably at least one selected from boron nitride, aluminum nitride, titanium nitride, and silicon nitride.
【００１４】[0014]
【作用】本発明の非線形光学材料の製造方法では、スパ
ッタリング法を適用することと窒化物の非晶質薄膜を用
いるために、半導体表面が酸化されることがない。また
加熱された基板上に半導体微粒子を分散させた窒化物の
非晶質薄膜を形成することにより、半導体微粒子がアモ
ルファスとならずに結晶化して窒化物の非晶質薄膜中に
分散される。[Operation] In the method of manufacturing a nonlinear optical material of the present invention, the semiconductor surface is not oxidized because the sputtering method is applied and an amorphous thin film of nitride is used. Furthermore, by forming an amorphous nitride thin film in which semiconductor fine particles are dispersed on a heated substrate, the semiconductor fine particles do not become amorphous but are crystallized and dispersed in the nitride amorphous thin film.
【００１５】本発明の第２の非線形光学材料の製造方法
では、さらに基板の加熱温度より高い温度で熱処理する
ことによって半導体微粒子の結晶性が向上する。また窒
化物の非晶質薄膜は緻密であるため、基板の加熱温度よ
り高い温度で熱処理しても半導体微粒子の結晶の成長は
ある程度で抑制されるため、基板の加熱温度より高い温
度で熱処理することによって粒径の均一化ができる。従
って、微細な半導体微粒子を窒化物の非晶質薄膜中に高
濃度で均一に分散させることが可能となり、すぐれた非
線形光学特性を有する非線形光学材料を容易に再現性よ
く得ることができる。In the second method of manufacturing a nonlinear optical material of the present invention, the crystallinity of the semiconductor fine particles is improved by further performing heat treatment at a temperature higher than the heating temperature of the substrate. In addition, since the amorphous thin film of nitride is dense, the growth of crystals of semiconductor particles is suppressed to a certain extent even if it is heat-treated at a temperature higher than the heating temperature of the substrate, so it is heat-treated at a temperature higher than the heating temperature of the substrate. This makes it possible to make the particle size uniform. Therefore, it becomes possible to uniformly disperse fine semiconductor particles at a high concentration in an amorphous thin film of nitride, and a nonlinear optical material having excellent nonlinear optical properties can be easily obtained with good reproducibility.
【００１６】また、本発明の第３の非線形光学材料の製
造方法においては、ターゲットとして半導体材料のター
ゲットと前記半導体材料より大きな禁制帯幅を有する窒
化物の構成成分のうち窒素を除く構成成分からなるター
ゲットとを用いて、ガス中に窒素またはアンモニアのう
ち少なくとも１種のガスを含ませてスパッタリングを行
い、加熱された基板上に、半導体微粒子を分散させた窒
化物の非晶質薄膜を形成するので前記本発明の製造方法
で説明した作用のほかに、窒素の取り込みを大きくでき
、窒化物中の窒素成分が逸散することなく安定した組成
の窒化物の非晶質薄膜の形成ができる。Further, in the third method of manufacturing a nonlinear optical material of the present invention, a semiconductor material target and a nitride component other than nitrogen, which has a larger forbidden band width than the semiconductor material, are used as a target. Sputtering is performed using a target containing at least one of nitrogen or ammonia in the gas to form an amorphous thin film of nitride in which semiconductor fine particles are dispersed on a heated substrate. Therefore, in addition to the effects described in the manufacturing method of the present invention, nitrogen uptake can be increased, and an amorphous thin film of nitride with a stable composition can be formed without the nitrogen component in the nitride escaping. .
【００１７】また、本発明の第４の非線形光学材料の製
造方法においては、前記第３の製造方法において、半導
体微粒子を分散させた窒化物の非晶質薄膜を形成した後
、更に基板の加熱温度より高い温度で熱処理するので、
前記本発明の第２と第３の製造方法で説明した作用が合
わせて発揮される。Further, in the fourth method of manufacturing a nonlinear optical material of the present invention, after forming the amorphous thin film of nitride in which semiconductor fine particles are dispersed in the third manufacturing method, the substrate is further heated. Since the heat treatment is performed at a temperature higher than the
The effects explained in the second and third manufacturing methods of the present invention are exhibited in combination.
【００１８】更に本発明の非線形光学材料の製造方法に
おいては、窒化物の非晶質薄膜が、窒化ホウ素、窒化ア
ルミニウム、窒化チタン、窒化珪素から選ばれた少なく
とも１種とすることにより、これらの窒化物は半導体微
粒子の分散性が良好であり、また光学的に大きな禁制帯
幅を有するので、非線形光学効果を大きくすることがで
き、好ましい。Furthermore, in the method for producing a nonlinear optical material of the present invention, the amorphous thin film of nitride is made of at least one selected from boron nitride, aluminum nitride, titanium nitride, and silicon nitride. Nitride is preferable because it has good dispersibility of semiconductor fine particles and has an optically large forbidden band width, so that the nonlinear optical effect can be increased.
【００１９】[0019]
【実施例】本発明に用いられる窒化物の非晶質薄膜とし
ては、半導体微粒子の分散性が良好である窒化ほう素，
窒化アルミニウム，窒化チタン，窒化珪素が好ましい。[Example] As the amorphous nitride thin film used in the present invention, boron nitride, which has good dispersibility of semiconductor particles,
Aluminum nitride, titanium nitride, and silicon nitride are preferred.
【００２０】窒化物の非晶質薄膜に分散させる半導体微
粒子としては、ＣｕＣｌなどの金属塩化物、あるいはＣ
ｄＳ，ＣｄＳｅ，ＣｄＯ，ＣｄＴｅ，ＺｎＳｅ，ＺｎＯ
，ＺｎＴｅ，ＨｇＴｅ，ＣｄＳＳｅ，ＨｇＣｄＴｅなど
のＩＩ−ＶＩ族化合物半導体、あるいはＧａＡｓ，Ｇａ
Ｎ，ＧａＰ，ＧａＳｂ，ＩｎＡｓ，ＩｎＰ，ＩｎＳｂ，
ＧａＡｌＡｓ，ＩｎＡｌＡｓなどのＩＩＩ −Ｖ族化合
物半導体、あるいはＳｉ、Ｇｅ等のＩＶ族半導体が好ま
しい。The semiconductor fine particles to be dispersed in the amorphous nitride film include metal chlorides such as CuCl, or C
dS, CdSe, CdO, CdTe, ZnSe, ZnO
, ZnTe, HgTe, CdSSe, HgCdTe, etc., or GaAs, Ga
N, GaP, GaSb, InAs, InP, InSb,
Group III-V compound semiconductors such as GaAlAs and InAlAs, or group IV semiconductors such as Si and Ge are preferred.
【００２１】スパッタリング条件は用いる材料などによ
って異なるので特に限定するものではないが、例えば通
常用いられるアルゴンガスやその他の不活性ガス等のス
パッタ用ガスを存在させて、また、ターゲットとして窒
化物の構成成分のうち窒素を除く構成成分からなるター
ゲットを用いる場合には、これらのガス中に更に窒素ま
たはアンモニアのうち少なくとも１種のガスを含ませて
、１０−３〜１０−１Ｔｏｒｒ程度の圧力で、基板温度
はおよそ１００〜５００℃、好ましくは１５０〜４００
℃程度の範囲で行うことが好ましい。The sputtering conditions are not particularly limited as they vary depending on the material used, but for example, sputtering gas such as commonly used argon gas or other inert gas is present, and a nitride composition is used as the target. When using a target consisting of components other than nitrogen, these gases further contain at least one gas among nitrogen or ammonia, and the target is heated at a pressure of about 10-3 to 10-1 Torr. The substrate temperature is approximately 100-500°C, preferably 150-400°C.
It is preferable to carry out the heating in a range of approximately ℃.
【００２２】また、半導体微粒子を分散させた窒化物の
非晶質薄膜を形成した後、基板の加熱温度より高い温度
で熱処理する場合の加熱温度についても半導体の種類な
どによって異なるので一概に規定しがたいが、例えば、
基板の加熱温度より高い温度であって且つ、およそ３０
０〜６００℃程度が好適である。[0022] Furthermore, after forming an amorphous thin film of nitride in which semiconductor fine particles are dispersed, the heating temperature when performing heat treatment at a temperature higher than the heating temperature of the substrate is not generally specified as it varies depending on the type of semiconductor. Although it is difficult, for example,
The temperature is higher than the heating temperature of the substrate and approximately 30
A temperature of about 0 to 600°C is suitable.
【００２３】以下、具体的実施例を挙げて更に詳細に説
明する。
実施例１
本実施例で用いた多元スパッタ装置の構成を図１に示す
。図１に示すように、多元スパッタ装置は、半導体材料
のターゲット１、非晶質窒化物用の原料ターゲット２、
基板３、基板加熱用ヒーター４、基板とそれぞれのター
ゲットの間に配置されたシャッター８、９およびそれぞ
れのターゲットに供給する高周波電源５、６、スパッタ
用ガス供給口７、真空室１０、真空ポンプ等に連結され
ている排気口１１から構成されている。半導体材料のタ
ーゲット１として金属塩化物のＣｕＣｌまたはＩＩ−Ｖ
Ｉ族半導体のＣｄＳｘ Ｓｅ１−ｘ （Ｘ＝０．１）、
非晶質窒化物用の原料ターゲット２として窒化珪素、基
板３として石英ガラスを用いた。スパッタ用ガスとして
アルゴンをスパッタ用ガス供給口７より真空室１０内に
供給し、圧力を５Ｐａにした。ターゲットに供給した高
周波電力はターゲット１には２０Ｗ、ターゲット２には
２５０ Ｗとした。[0023] Hereinafter, a more detailed explanation will be given with reference to specific examples. Example 1 The configuration of a multi-source sputtering apparatus used in this example is shown in FIG. As shown in FIG. 1, the multi-source sputtering apparatus includes a semiconductor material target 1, an amorphous nitride raw material target 2,
A substrate 3, a heater 4 for heating the substrate, shutters 8 and 9 arranged between the substrate and each target, high frequency power supplies 5 and 6 supplied to each target, a sputtering gas supply port 7, a vacuum chamber 10, and a vacuum pump. The exhaust port 11 is connected to the exhaust port 11, etc. Metal chloride CuCl or II-V as semiconductor material target 1
Group I semiconductor CdSx Se1-x (X=0.1),
Silicon nitride was used as the raw material target 2 for amorphous nitride, and quartz glass was used as the substrate 3. Argon was supplied as a sputtering gas into the vacuum chamber 10 from the sputtering gas supply port 7, and the pressure was set at 5 Pa. The high frequency power supplied to the targets was 20 W for target 1 and 250 W for target 2.
【００２４】まず基板加熱を行わないで半導体微粒子を
分散させた窒化珪素薄膜を作製したところ、半導体微粒
子は結晶化せずアモルファスであった。しかし、基板温
度を１００℃以上に設定することにより、半導体微粒子
はアモルファスとならずに結晶化した。このことより、
窒素のためにアモルファスとなった半導体微粒子は不安
定な物質であり、熱を加えることによって窒素が脱離し
て容易に結晶性の半導体微粒子に変化したと考えられる
。基板温度を高くすればするほど、半導体微粒子の結晶
性は向上するので好ましいが、基板温度を高くするにつ
れて半導体微粒子の堆積速度が減少するため、実用上基
板温度の上限は４００℃〜５００℃である。First, when a silicon nitride thin film in which semiconductor fine particles were dispersed was prepared without heating the substrate, the semiconductor fine particles were not crystallized and were amorphous. However, by setting the substrate temperature to 100° C. or higher, the semiconductor fine particles did not become amorphous but crystallized. From this,
Semiconductor particles that have become amorphous due to nitrogen are unstable substances, and it is thought that by applying heat, nitrogen is removed and easily changed to crystalline semiconductor particles. The higher the substrate temperature is, the better the crystallinity of the semiconductor particles is, so it is preferable, but as the substrate temperature is raised, the deposition rate of the semiconductor particles decreases, so the upper limit of the substrate temperature is practically 400°C to 500°C. be.
【００２５】基板温度を１５０℃に設定して、半導体と
窒化珪素を同時に基板３上に堆積させ、０．５ｍｍ 厚
の石英ガラス基板３上に、約３０μｍの半導体微粒子を
分散させた窒化珪素薄膜を形成した。この薄膜は光吸収
スペクトルではブルーシフトしており、量子サイズ効果
が確認できた。By setting the substrate temperature at 150° C., semiconductor and silicon nitride are simultaneously deposited on the substrate 3, and a silicon nitride thin film with approximately 30 μm semiconductor fine particles dispersed is formed on the 0.5 mm thick quartz glass substrate 3. was formed. The optical absorption spectrum of this thin film was blue-shifted, confirming the quantum size effect.
【００２６】再現性よく得るために、４００℃の電気炉
中で１時間加熱してＣｕＣｌまたはＣｄＳｘ Ｓｅ１−
ｘ の結晶を成長させた。このとき薄膜中の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ＣｄＳｘ Ｓｅ１−ｘ のドープ量は１８重量％で
あり粒子径は５〜７ｎｍであった。上記の半導体材料を
ドープしていない窒化ケイ素薄膜の吸収スペクトルから
窒化珪素薄膜の光学的禁制帯幅は４．５ｅＶ であり、
上記２種の半導体をド−プすることにより、光学的禁制
帯幅はそれぞれの材料のバルクの値３．２ ，２．４６
ｅＶ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ットとなっていること
がわかった。In order to obtain it with good reproducibility, CuCl or CdSx Se1- was heated in an electric furnace at 400°C for 1 hour.
A crystal of x was grown. At this time, 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 CdSx Se1-x was 18% by weight, and the particle size was 5 to 7 nm. From the absorption spectrum of the silicon nitride thin film not doped with the above semiconductor material, the optical forbidden band width of the silicon nitride thin film is 4.5 eV.
By doping the above two types of semiconductors, the optical forbidden band width is 3.2 and 2.46, which is the bulk value of each material.
The blue shift of 0.5 and 0.4 eV compared to eV indicates that the semiconductor material is a quantum dot.
【００２７】なお、本実施例では半導体微粒子を分散さ
せた窒化珪素薄膜について述べたが、上記以外の窒化ほ
う素，窒化アルミニウム，窒化チタンについても同様の
結果を得ることができた。In this example, a silicon nitride thin film in which semiconductor fine particles are dispersed was described, but similar results were obtained with boron nitride, aluminum nitride, and titanium nitride other than those mentioned above.
【００２８】実施例２
実施例１と同様な多元スパッタ装置を用いて、ターゲッ
ト１を金属塩化物のＣｕＣｌまたはＩＩ−ＶＩ族半導体
のＣｄＳｘ Ｓｅ１−ｘ （Ｘ＝０．１）、ターゲット
２を珪素とした。
本実施例ではターゲット２と窒素ガスの反応によって窒
化珪素の非晶質薄膜を形成しながら、半導体微粒子を分
散させた薄膜を試作した。基板３には石英ガラスを用い
た。スパッタ用ガスとして窒素及びアルゴンをスパッタ
用ガス供給口７より真空室１０内に供給し、それぞれ２
Ｐａ，３Ｐａにした。ターゲットに供給した高周波電力
はターゲット１には２０Ｗ、ターゲット２には２５０
Ｗとした。まず加熱されていない０．５ｍｍ 厚の石英
ガラス基板３上に半導体微粒子を分散させた膜厚３０μ
ｍの窒化珪素の薄膜を形成した。この薄膜の半導体微粒
子は結晶化しておらずアモルファスであった。しかし、
基板温度を１００℃以上に設定することにより、半導体
微粒子はアモルファスとならずに結晶化した。Example 2 Using a multi-component sputtering apparatus similar to Example 1, target 1 was CuCl of metal chloride or CdSx Se1-x (X=0.1) of II-VI group semiconductor, and target 2 was silicon. And so. In this example, an amorphous thin film of silicon nitride was formed by a reaction between the target 2 and nitrogen gas, and a thin film in which semiconductor fine particles were dispersed was prototyped. For the substrate 3, quartz glass was used. Nitrogen and argon are supplied as sputtering gases into the vacuum chamber 10 from the sputtering gas supply port 7.
The pressure was set to 3 Pa. The high frequency power supplied to the targets was 20W for target 1 and 250W for target 2.
It was set as W. First, a film with a thickness of 30 μm in which semiconductor fine particles are dispersed is formed on an unheated 0.5 mm thick quartz glass substrate 3.
A thin film of silicon nitride of m was formed. The semiconductor fine particles in this thin film were not crystallized and were amorphous. but,
By setting the substrate temperature to 100° C. or higher, the semiconductor fine particles were crystallized without becoming amorphous.
【００２９】このことより、窒素のためにアモルファス
となった半導体微粒子は不安定な物質であり、熱を加え
ることによって窒素が脱離して容易に結晶性の半導体微
粒子に変化したと考えられる。基板温度を高くすればす
るほど、半導体微粒子の結晶性は向上するので好ましい
が、基板温度を高くするにつれて半導体微粒子の堆積速
度が減少するため、実用上基板温度の上限は４００℃〜
５００℃である。From this, it is considered that the semiconductor fine particles which became amorphous due to nitrogen were unstable substances, and by applying heat, nitrogen was removed and easily changed into crystalline semiconductor fine particles. The higher the substrate temperature is, the better the crystallinity of the semiconductor particles is, so it is preferable, but as the substrate temperature is raised, the deposition rate of the semiconductor particles decreases, so in practice, the upper limit of the substrate temperature is 400 ° C.
The temperature is 500°C.
【００３０】基板温度を１５０℃に設定して、半導体微
粒子を分散させた窒化珪素薄膜を０．５ｍｍ 厚の石英
ガラス基板３上に約３０μｍ形成した。この薄膜は光吸
収スペクトルではブルーシフトしており、量子サイズ効
果が確認できた。The substrate temperature was set at 150° C., and a silicon nitride thin film having semiconductor particles dispersed therein was formed to a thickness of about 30 μm on a 0.5 mm thick quartz glass substrate 3. The optical absorption spectrum of this thin film was blue-shifted, confirming the quantum size effect.
【００３１】再現性よく得るために、４００℃の電気炉
中で１時間加熱してＣｕＣｌまたはＣｄＳｘ Ｓｅ１−
ｘ の結晶を成長させた。このとき薄膜中の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ＣｄＳｘ Ｓｅ１−ｘ のドープ量は１８重量％で
あり粒子径は５〜７ｎｍであった。In order to obtain it with good reproducibility, CuCl or CdSx Se1- was heated in an electric furnace at 400°C for 1 hour.
A crystal of x was grown. At this time, 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 CdSx Se1-x was 18% by weight, and the particle size was 5 to 7 nm.
【００３２】上記の半導体材料をドープしていない窒化
珪素薄膜の吸収スペクトルから窒化珪素薄膜の光学的禁
制帯幅は４．５ｅＶ であり、上記２種の半導体をド−
プすることにより、光学的禁制帯幅はそれぞれの材料の
バルクの値３．２ ，２．４６ｅＶに比べてそれぞれ０
．５ ，０．４ｅＶ ブルーシフトしていた。このこと
から、半導体微粒子が量子ドットとなっていることがわ
かった。From the absorption spectrum of the silicon nitride thin film not doped with the above semiconductor materials, the optical forbidden band width of the silicon nitride thin film is 4.5 eV.
By applying a
．． 5, 0.4 eV blue shift. This revealed that the semiconductor particles were quantum dots.
【００３３】なお、本実施例では半導体微粒子を分散さ
せた窒化珪素薄膜について述べたが、上記以外の窒化ほ
う素，窒化アルミニウム，窒化チタンについても同様の
結果を得ることができた。In this example, a silicon nitride thin film in which semiconductor fine particles are dispersed was described, but similar results were obtained with boron nitride, aluminum nitride, and titanium nitride other than those mentioned above.
【００３４】また、本実施例では窒化珪素薄膜を作製す
る場合に窒素ガス（Ｎ２ ）を用いたが、アンモニアガ
ス（ＮＨ３ ）でもよい。Further, in this embodiment, nitrogen gas (N2) was used when producing the silicon nitride thin film, but ammonia gas (NH3) may also be used.
【００３５】[0035]
【発明の効果】本発明における非線形光学材料の製造方
法では、窒化物の非晶質薄膜中に半導体微粒子がアモル
ファスとならずに結晶化して高濃度に分散させることが
でき、大きな非線形光学効果をもつ材料を得ることがで
きる。[Effects of the Invention] In the method for manufacturing a nonlinear optical material according to the present invention, semiconductor fine particles can be crystallized and dispersed in a high concentration in an amorphous nitride film without becoming amorphous, and a large nonlinear optical effect can be achieved. You can obtain materials that have
【００３６】本発明の第２の非線形光学材料の製造方法
では、さらに半導体微粒子の結晶性を向上させ、また粒
径の均一化ができる。従って、より非線形光学特性のす
ぐれた非線形光学材料を容易に再現性よく得ることがで
きる。In the second method of manufacturing a nonlinear optical material of the present invention, the crystallinity of semiconductor fine particles can be further improved and the particle size can be made uniform. Therefore, a nonlinear optical material with better nonlinear optical properties can be easily obtained with good reproducibility.
【００３７】また、本発明の第３の非線形光学材料の製
造方法では、前記本発明の効果のほかに、より安定した
組成の窒化物の非晶質薄膜の形成ができる。また、本発
明の第４の非線形光学材料の製造方法においては、さら
に半導体微粒子の結晶性を向上させ、また粒径の均一化
ができる。また、より安定した組成の窒化物の非晶質薄
膜の形成ができ、従って、より非線形光学特性のすぐれ
た非線形光学材料を容易に再現性よく得ることができる
。Furthermore, in the third method of manufacturing a nonlinear optical material of the present invention, in addition to the effects of the present invention described above, an amorphous thin film of nitride having a more stable composition can be formed. Furthermore, in the fourth method of manufacturing a nonlinear optical material of the present invention, the crystallinity of the semiconductor fine particles can be further improved and the particle size can be made uniform. Furthermore, it is possible to form an amorphous thin film of nitride with a more stable composition, and therefore, a nonlinear optical material with more excellent nonlinear optical properties can be easily obtained with good reproducibility.
【００３８】更に本発明の非線形光学材料の製造方法に
おいては、窒化物の非晶質薄膜が、窒化ホウ素、窒化ア
ルミニウム、窒化チタン、窒化珪素から選ばれた少なく
とも１種とすることにより、非線形光学効果を大きくす
ることができる。Furthermore, in the method for producing a nonlinear optical material of the present invention, the amorphous thin film of nitride is made of at least one selected from boron nitride, aluminum nitride, titanium nitride, and silicon nitride. The effect can be increased.
【図１】 本発明の一実施例で用いたスパッタ装置の
概略構成図。FIG. 1 is a schematic configuration diagram of a sputtering apparatus used in an embodiment of the present invention.
１ 半導体材料のターゲット ２ 非晶質窒化物用の原料ターゲット３ 基板 ４ 基板加熱用ヒーター ５，６ 高周波電源 ７ スパッタ用ガス供給口 ８，９ シャッター １０ 真空室 １１ 排気口 1. Semiconductor material target 2 Raw material target for amorphous nitride 3 Substrate 4 Heater for heating the substrate 5, 6 High frequency power supply 7 Gas supply port for sputtering 8,9 Shutter 10 Vacuum chamber 11 Exhaust port
Claims (5)
ットと前記半導体材料より大きな禁制帯幅を有する窒化
物のターゲットとを用いてスパッタリングを行い、加熱
された基板上に、半導体微粒子を分散させた窒化物の非
晶質薄膜を形成することからなる非線形光学材料の製造
方法。1. Sputtering is performed using a semiconductor material target and a nitride target having a larger forbidden band width than the semiconductor material, and a nitride film in which semiconductor fine particles are dispersed is sputtered onto a heated substrate. A method for producing a nonlinear optical material comprising forming an amorphous thin film.
ットと前記半導体材料より大きな禁制帯幅を有する窒化
物のターゲットとを用いてスパッタリングを行い、加熱
された基板上に半導体微粒子を分散させた窒化物の非晶
質薄膜を形成した後、前記基板の加熱温度より高い温度
で熱処理することからなる非線形光学材料の製造方法。2. Sputtering is performed using a semiconductor material target and a nitride target having a larger forbidden band width than the semiconductor material, and a nitride non-woven material with semiconductor fine particles dispersed on a heated substrate is sputtered. A method for manufacturing a nonlinear optical material, which comprises forming a crystalline thin film and then performing heat treatment at a temperature higher than the heating temperature of the substrate.
ットと前記半導体材料より大きな禁制帯幅を有する窒化
物の構成成分のうち窒素を除く構成成分からなるターゲ
ットとを用いて、ガス中に窒素またはアンモニアのうち
少なくとも１種のガスを含ませてスパッタリングを行い
、加熱された基板上に、半導体微粒子を分散させた窒化
物の非晶質薄膜を形成することからなる非線形光学材料
の製造方法。3. Using a target made of a semiconductor material as a target and a target made of a nitride component other than nitrogen, which has a larger forbidden band width than the semiconductor material, nitrogen or ammonia is added to the gas. A method for manufacturing a nonlinear optical material, which comprises performing sputtering with at least one type of gas included to form an amorphous thin film of nitride in which semiconductor fine particles are dispersed on a heated substrate.
ットと前記半導体材料より大きな禁制帯幅を有する窒化
物の構成成分のうち窒素を除く構成成分からなるターゲ
ットとを用いて、ガス中に窒素またはアンモニアのうち
少なくとも１種のガスを含ませてスパッタリングを行い
、加熱された基板上に、半導体微粒子を分散させた窒化
物の非晶質薄膜を形成した後、基板の加熱温度より高い
温度で熱処理することからなる非線形光学材料の製造方
法。4. Using a target made of a semiconductor material as a target and a target made of a nitride component other than nitrogen, which has a larger forbidden band width than the semiconductor material, nitrogen or ammonia is added to the gas. Sputtering is performed with at least one type of gas impregnated to form an amorphous thin film of nitride in which semiconductor particles are dispersed on a heated substrate, and then heat treatment is performed at a temperature higher than the heating temperature of the substrate. A method for producing a nonlinear optical material.
窒化アルミニウム、窒化チタン、窒化珪素から選ばれた
少なくとも１種である請求項１、２、３または４のいず
れかに記載の非線形光学材料の製造方法。5. The amorphous nitride thin film comprises boron nitride, boron nitride,
5. The method for manufacturing a nonlinear optical material according to claim 1, wherein the material is at least one selected from aluminum nitride, titanium nitride, and silicon nitride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11857491A JPH04345137A (en) | 1991-05-23 | 1991-05-23 | Production of nonlinear optical material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11857491A JPH04345137A (en) | 1991-05-23 | 1991-05-23 | Production of nonlinear optical material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04345137A true JPH04345137A (en) | 1992-12-01 |
Family
ID=14739967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11857491A Pending JPH04345137A (en) | 1991-05-23 | 1991-05-23 | Production of nonlinear optical material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04345137A (en) |
-
1991
- 1991-05-23 JP JP11857491A patent/JPH04345137A/en active Pending
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