JPH0297497A - Production of cadmium sulfide thin film - Google Patents
Production of cadmium sulfide thin filmInfo
- Publication number
- JPH0297497A JPH0297497A JP24920588A JP24920588A JPH0297497A JP H0297497 A JPH0297497 A JP H0297497A JP 24920588 A JP24920588 A JP 24920588A JP 24920588 A JP24920588 A JP 24920588A JP H0297497 A JPH0297497 A JP H0297497A
- Authority
- JP
- Japan
- Prior art keywords
- cadmium
- sulfur
- molecular beam
- thin film
- cadmium sulfide
- 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
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 19
- 239000010409 thin film Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 20
- 239000011593 sulfur Substances 0.000 claims abstract description 20
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 17
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 15
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 10
- 230000001678 irradiating effect Effects 0.000 claims abstract 2
- 239000013078 crystal Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 5
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 claims description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 claims description 2
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims 1
- 238000005979 thermal decomposition reaction Methods 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 4
- 238000001451 molecular beam epitaxy Methods 0.000 abstract description 3
- 230000008016 vaporization Effects 0.000 abstract description 2
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 238000009834 vaporization Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- YRDGEBQKBARXFW-UHFFFAOYSA-N (dimethyl-$l^{3}-sulfanyl)methane Chemical compound C[S](C)C YRDGEBQKBARXFW-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241001333909 Soter Species 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は発光ダイオードなどの発光素子やイメージセン
サなどの受光素子に用いられる半導体薄膜月利の製造方
法に関し、特に緑色領域で良好な↑４ｒ性を示す硫化カ
ドミウム薄膜の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for manufacturing a semiconductor thin film used for light emitting elements such as light emitting diodes and light receiving elements such as image sensors, and relates to a method for manufacturing a semiconductor thin film used for light emitting elements such as light emitting diodes and light receiving elements such as image sensors. The present invention relates to a method for producing a cadmium sulfide thin film shown in the figure.
従来の技術
従来、硫化カドミウム薄膜を製造する方法として、第２
図に示すような真空蒸着装置を用い、真空容器１内でル
ツボ３内に装填した硫化カドミウム原料３ａを加熱蒸発
させ、基板４の表面に硫化カドミウム薄膜５を形成する
ものが知られている。Conventional technology Conventionally, as a method for producing a cadmium sulfide thin film, the second
It is known that a vacuum evaporation apparatus as shown in the figure is used to heat and evaporate a cadmium sulfide raw material 3a loaded in a crucible 3 in a vacuum vessel 1 to form a cadmium sulfide thin film 5 on the surface of a substrate 4.
２は真空ポンプ、６は基板ホルダ、７はヒーターである
。2 is a vacuum pump, 6 is a substrate holder, and 7 is a heater.
発明が解決しようとする課題
しかしながら上述のような従来の方法では、カドミウム
と硫黄の原子または分子が同時に基板面に飛来するため
、膜形成の初期において、基板而上の結晶成長の起こり
やすい位置に集中して結晶が成長し、いわゆる島状成長
の杖態となる。この場合、得られた膜は結晶粒の集合体
となるため、結晶粒界に格子欠陥が多数発生し、発光・
受光素子材料として充分な特性が得られないという点が
課題であった。またこの場合、膜面の凹凸や膜厚分布が
大きくなるという点も課題であった。Problems to be Solved by the Invention However, in the conventional method as described above, cadmium and sulfur atoms or molecules simultaneously fly onto the substrate surface, so in the early stage of film formation, they are placed on the substrate at a position where crystal growth is likely to occur. The crystals grow in a concentrated manner, forming what is called a cane of island-like growth. In this case, the obtained film becomes an aggregate of crystal grains, and many lattice defects occur at the grain boundaries, causing light emission and
The problem was that sufficient characteristics could not be obtained as a light-receiving element material. In this case, another problem was that the unevenness of the film surface and the film thickness distribution became large.
課題を解決するための手段
本発明は上記課題を解決するため、金属カドミウムを加
熱蒸発させて得たカドミウム分子線と、硫黄を含む化合
物のガスを熱分解させて得た硫黄分子線を交互に基板に
照射するものである。Means for Solving the Problems In order to solve the above problems, the present invention alternately uses cadmium molecular beams obtained by heating and vaporizing metal cadmium and sulfur molecular beams obtained by thermally decomposing a gas of a sulfur-containing compound. It irradiates the substrate.
作用
本発明は上記の手段により、カドミウムと硫黄の原子層
を一層ずつ交互に形成し、その結果、膜形成の初期より
均一な二次元的な結晶成長が生じるという作用に基づく
ものである。Effect The present invention is based on the effect that atomic layers of cadmium and sulfur are alternately formed one by one by the above-described means, and as a result, uniform two-dimensional crystal growth occurs from the initial stage of film formation.
実施例 以下、本発明を実施例により詳細に説明する。Example Hereinafter, the present invention will be explained in detail with reference to Examples.
第１図は本発明の製造方法の一実施例で用いられる分子
線エピタキ／−装置の構造を示す概略図である。同図に
おいて、９は通常の蒸発用ルツボで原料となる金属カド
ミウム９ａを装填しておき、ヒーター７により加熱蒸発
させてカドミウム分子線９ ｂを得る。また１０はガス
分解セルで、硫化水素ガス容器１１から導入されたガス
をヒーター８により加熱分解させて、硫黄分子線１０ｂ
を得る。ここで硫黄分子線の原料に硫化水素ガスを用い
る理由は、単体の硫７１ｔ（固体）は室温でもかなり高
い蒸気圧を有するため、高真空を得るのに不可欠なｈ’
Ｌ空容：（（１の加熱脱ガス処理の過程で蒸発してしま
うので実用的でないことによる。FIG. 1 is a schematic diagram showing the structure of a molecular beam epitaxy apparatus used in an embodiment of the manufacturing method of the present invention. In the figure, reference numeral 9 denotes an ordinary evaporation crucible loaded with metal cadmium 9a as a raw material, which is heated and evaporated by a heater 7 to obtain a cadmium molecular beam 9b. Further, 10 is a gas decomposition cell, which heats and decomposes the gas introduced from the hydrogen sulfide gas container 11 with a heater 8 to produce a sulfur molecular beam 10b.
get. The reason for using hydrogen sulfide gas as the raw material for the sulfur molecular beam is that 71t of sulfur (solid) has a fairly high vapor pressure even at room temperature, so h' is essential for obtaining a high vacuum.
L empty volume: ((This is because it is not practical because it evaporates during the heating and degassing process in step 1.
実際の薄膜成長は次のような手順で行なう。まず表面を
ｌｉ’ｆ 抑にした基板４を基板ホルダ６に装着する。Actual thin film growth is performed in the following steps. First, the substrate 4 whose surface is li'f suppressed is mounted on the substrate holder 6.
基板材料としては硫化カドミウムそのものの単結晶や、
硫化カドミウムに近い格子定数を持つインジウム燐の単
結晶などが好適である。次に真空容器１を１（１”Ｔｏ
ｒｒ以下程度の超高真空までυｒ気する。その後、ルツ
ボ９を例えば４００℃程度に加熱し、適切な強度のカド
ミウム分子線９ｂが得られるようにする。またガス分解
セル１０を加熱するとともに、流量調節弁１２を開いて
硫化水素ガスを流し、適切な強度の硫黄分子線１０ｂが
得られるようにする。ガス分解セルの温度は、７００′
Ｃ以上あれば硫化水素ガスをほぼ完全に分解することが
できる。The substrate material is single crystal of cadmium sulfide itself,
A single crystal of indium phosphorus having a lattice constant close to that of cadmium sulfide is suitable. Next, vacuum container 1 is
It is possible to reach an ultra-high vacuum below rr. Thereafter, the crucible 9 is heated to, for example, about 400° C. to obtain a cadmium molecular beam 9b of appropriate strength. In addition, while heating the gas decomposition cell 10, the flow control valve 12 is opened to allow hydrogen sulfide gas to flow, so that a sulfur molecular beam 10b of appropriate strength can be obtained. The temperature of the gas decomposition cell is 700'
C or higher, hydrogen sulfide gas can be almost completely decomposed.
次に基板４を約６００℃に加熱して表面をさらに清浄化
する。その後、基板を結晶成長に適切な温度まで下げる
。この場合には例えば３００℃とする。この後、シャッ
ター１３および１４を交互に開き、結晶成長を行なう。Next, the substrate 4 is heated to about 600° C. to further clean the surface. The substrate is then lowered to a temperature suitable for crystal growth. In this case, the temperature is, for example, 300°C. After this, the shutters 13 and 14 are opened alternately to perform crystal growth.
すなわち、例えばまずンヤソター１３を開いてカドミウ
ム分子線９ｂを基板に照射するとカドミウム原子層が一
層だけ形成される。その後シャッター１３を閉じ、シャ
ッター１４を開いて、硫黄分子線１０ｂを照射すると、
硫黄原子層が一層だけ形成される。この操作を繰り返す
と、シャッターの開閉回数に比例した膜厚の硫化カドミ
ウム均一に形成することができる。シャッターを開いて
お（時間は、一原子層が形成されるのに充分な時間以上
であれば特に制限はない。これはカドミウムおよび硫黄
の蒸気圧が」二連の基板温反では充分に高いため、原子
層が一層形成されると同種原子はそれ以上堆積せず、再
蒸発するためである。That is, for example, when the soter soter 13 is first opened and the substrate is irradiated with the cadmium molecular beam 9b, only one cadmium atomic layer is formed. After that, the shutter 13 is closed, the shutter 14 is opened, and the sulfur molecular beam 10b is irradiated.
Only one layer of sulfur atoms is formed. By repeating this operation, it is possible to form a uniform cadmium sulfide film with a thickness proportional to the number of times the shutter is opened and closed. Open the shutter (there is no particular restriction on the time as long as it is at least enough time for a single atomic layer to form. This means that the vapor pressures of cadmium and sulfur are sufficiently high for double substrate heating. Therefore, once an atomic layer is formed, the same kind of atoms are no longer deposited and are re-evaporated.
以上のような方法で形成した硫化カドミウム薄膜は、成
長初期より二次元的で均一な結晶成長をするため、極め
て格子欠陥の少ない良質な単結晶膜となり、優れた電気
的・光学的性質を示す。The cadmium sulfide thin film formed by the above method undergoes two-dimensional and uniform crystal growth from the initial stage of growth, resulting in a high-quality single crystal film with extremely few lattice defects and exhibiting excellent electrical and optical properties. .
なお上述の実施例では硫黄分子線の原料として硫化水素
を用いたが、この他ツメチル硫黄やジエチル硫黄などの
硫黄を含む打機化合物ガスを用いても同様の効果が得ら
れる。Although hydrogen sulfide was used as the raw material for the sulfur molecular beam in the above-described embodiments, similar effects can be obtained by using other sulfur-containing batter compound gases such as trimethyl sulfur and diethyl sulfur.
また、薄膜形成中の基板温度は、２００℃以上５００℃
以下が好適である。２００℃以下では各原子が正確な格
子位置に安定せず、また５００℃以上では原子の再蒸発
が過剰になり原子の空孔が生じるので、何れの場合も完
全な結晶が得られなくなるためである。In addition, the substrate temperature during thin film formation is 200°C or more and 500°C.
The following are preferred. Below 200°C, each atom is not stabilized in its correct lattice position, and above 500°C, atoms re-evaporate excessively and create atomic vacancies, making it impossible to obtain a perfect crystal in either case. be.
発明の効果
以上述べてきたように、本発明によれば、格子欠陥の少
ない良質な硫化カドミウム薄膜を均一に形成することが
できる。その結果、高効率の発光ダイオードや高感度の
イメージセンサなどが実現でき実用的に極めて有用であ
る。Effects of the Invention As described above, according to the present invention, a high quality cadmium sulfide thin film with few lattice defects can be uniformly formed. As a result, highly efficient light emitting diodes and highly sensitive image sensors can be realized, which are extremely useful in practice.
第１図は本発明の一実施例で用いられる分子線エピタキ
ンー装置の＋ｆｉ造を示す概略図、第２図は従来例で用
いられる蒸着装置の構造を示す（概略図である。
１・・や真空容器、２φ壷・真空ポンプ、４・・・基板
、５ｅ令φ硫化カドミウム薄膜、６ｍ−・基板ホルダ、
７，８・・・ヒーター ９・６６ルツボ、９ ａＩ 嗜
・カドミウム、９ｂ・・Φカドミウム分子線、１０番−
０ガス分解セル、１０ｂ・・・硫黄分子線、１１・・・
硫化水素ガス容器、１２・・・流量調節弁、１３．１４
−・・シャッター
代理人の氏名 弁理士 栗野重孝 はか１名１３／４
シマ・・クーFig. 1 is a schematic diagram showing a +fi structure of a molecular beam epitaxy apparatus used in an embodiment of the present invention, and Fig. 2 is a schematic diagram showing the structure of a vapor deposition apparatus used in a conventional example. Vacuum container, 2φ jar/vacuum pump, 4...substrate, 5e φ cadmium sulfide thin film, 6m-・substrate holder,
7, 8... Heater 9/66 crucible, 9 aI cadmium, 9b... Φ cadmium molecular beam, No. 10-
0 gas decomposition cell, 10b... sulfur molecular beam, 11...
Hydrogen sulfide gas container, 12...Flow rate control valve, 13.14
- Name of Shutter agent Patent attorney Shigetaka Kurino Haka 1 person 13/4 Shima Koo
Claims (5)
む化合物の気体を熱分解して得た硫黄分子線を交互に基
板表面に照射することを特徴とする硫化カドミウム薄膜
の製造方法。(1) A method for producing a cadmium sulfide thin film, which comprises alternately irradiating a substrate surface with a cadmium molecular beam and a sulfur molecular beam obtained by thermally decomposing a gas of a sulfur-containing compound in a vacuum.
またはジエチル硫黄とした特許請求の範囲第１項記載の
硫化カドミウム薄膜の製造方法。(2) The method for producing a cadmium sulfide thin film according to claim 1, wherein the sulfur-containing compound is hydrogen sulfide, dimethyl sulfur, or diethyl sulfur.
７００℃以上とした特許請求の範囲第１項記載の硫化カ
ドミウム薄膜の製造方法。(3) The method for producing a cadmium sulfide thin film according to claim 1, wherein the sulfur-containing compound is hydrogen sulfide, and the thermal decomposition temperature is 700°C or higher.
で構成した特許請求の範囲第１項から第３項までのいず
れかに記載の硫化カドミウム薄膜の製造方法。(4) A method for producing a cadmium sulfide thin film according to any one of claims 1 to 3, comprising a cadmium sulfide single crystal or an indium phosphorus single crystal.
請求の範囲第１項から第４項までの何れかに記載の硫化
カドミウム薄膜の製造方法。(5) The method for producing a cadmium sulfide thin film according to any one of claims 1 to 4, wherein the substrate temperature is 250°C or more and 500°C or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24920588A JPH0297497A (en) | 1988-10-03 | 1988-10-03 | Production of cadmium sulfide thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24920588A JPH0297497A (en) | 1988-10-03 | 1988-10-03 | Production of cadmium sulfide thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0297497A true JPH0297497A (en) | 1990-04-10 |
Family
ID=17189477
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24920588A Pending JPH0297497A (en) | 1988-10-03 | 1988-10-03 | Production of cadmium sulfide thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0297497A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62141717A (en) * | 1985-12-16 | 1987-06-25 | Fujitsu Ltd | Growing method for atomic layer level zincblende-type crystal and its device |
| JPS62229846A (en) * | 1986-03-30 | 1987-10-08 | Nippon Seiki Co Ltd | Manufacture of ii-vi compound semiconductor element |
-
1988
- 1988-10-03 JP JP24920588A patent/JPH0297497A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62141717A (en) * | 1985-12-16 | 1987-06-25 | Fujitsu Ltd | Growing method for atomic layer level zincblende-type crystal and its device |
| JPS62229846A (en) * | 1986-03-30 | 1987-10-08 | Nippon Seiki Co Ltd | Manufacture of ii-vi compound semiconductor element |
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