JPS5934628A - Manufacture of semiconductor thin-film - Google Patents

Manufacture of semiconductor thin-film

Info

Publication number
JPS5934628A
JPS5934628A JP14465082A JP14465082A JPS5934628A JP S5934628 A JPS5934628 A JP S5934628A JP 14465082 A JP14465082 A JP 14465082A JP 14465082 A JP14465082 A JP 14465082A JP S5934628 A JPS5934628 A JP S5934628A
Authority
JP
Japan
Prior art keywords
semiconductor thin
adduct
group
substrates
substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP14465082A
Other languages
Japanese (ja)
Other versions
JPS639742B2 (en
Inventor
Naoki Kobayashi
直樹 小林
Takashi Fukui
孝志 福井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Telegraph and Telephone Corp
Original Assignee
Nippon Telegraph and Telephone Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Telegraph and Telephone Corp filed Critical Nippon Telegraph and Telephone Corp
Priority to JP14465082A priority Critical patent/JPS5934628A/en
Publication of JPS5934628A publication Critical patent/JPS5934628A/en
Publication of JPS639742B2 publication Critical patent/JPS639742B2/ja
Granted legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02422—Non-crystalline insulating materials, e.g. glass, polymers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/301—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02538—Group 13/15 materials
    • H01L21/02546—Arsenides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Recrystallisation Techniques (AREA)

Abstract

PURPOSE:To form the semiconductor thin-film in a large area through easy operation by using a safety and low-cost device by applying an organic metallic adduct of a III group organic metallic compound and a V group organic metallic compound or a II group organic metallic compound and a VI group organic metallic compound on a substrate and heating and treating the substrate in a hydrogen atmosphere. CONSTITUTION:A device for manufacturing the semiconductor thin-film is constituted by a reaction pipe 1, the substrates 2, an inert-gas bomb 3 for nitrogen gas, etc., a bomb 4 in which the organic metallic adduct is entered, a hydrogen bomb 5, sprays 6 for applying the organic metallc adduct, a susceptor 7 for supporting the substrates, a heater 8 for heating the substrates, a hydrogen purifier 50, etc. The organic metallic adduct (CH3)3Ga.As(CH3)3 is applied on the substrates 2 by the sprays 6. The substrates 2 are heated at 450 deg.C while flowing hydrogen, the organic metallic adduct applied is decomposed by the heating, and the GaAs III V group semiconductor thin-film is formed. Said substrates are replaced with glass substrates, and the GaAs semiconductor thin-film can be formed on the glass substrate through quite the same treatment operation.

Description

【発明の詳細な説明】 本発明は、有機金属化合物を原料として用いる半導体薄
膜製造法に関するものにして、特に、簡単な装置で、容
易な操作で、安全に、短時間に、大面積の半導体薄膜を
製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing semiconductor thin films using organometallic compounds as raw materials. The present invention relates to a method of manufacturing a thin film.

従来、有機金属化合物を用いる半導体薄膜製造法は気相
成長によるものであった。ＧａＡｓ基板」ニにＧａ　Ａ
ｓを成長させる場合を例にとって説明すると次の通シで
ある。Conventionally, semiconductor thin film manufacturing methods using organometallic compounds have been based on vapor phase growth. GaAs substrate
Taking the case of growing s as an example, the following is the explanation.

従来の気相エピタキシャル成長装置の構成を第１図に示
す。第１図を参照して、加熱用ＲＴ”コイル１０、基板
支持用サセプタ１１を備えた反応管１中に原料化合物等
を導入するだめの導入管１２を設け、この導入管１２に
水素化物用ボンベ１３、原料化合物用ボンベ１４を、そ
れぞれ、バルブ６０．４０を介して接続するとともに、
原料化合物を搬送するだめのキャリアガスボンベ１５を
キャリアガス純化装置５０および水素化物用ボンベ１６
、原料化合物用ボンベ１４よりのそれぞれのガスｌ：　
反応管１へ搬送するように、マスフローコントローラ６
１．４１を介して導入管１２に接続しである。ＧａＡｓ
を成長させる場合、アルシンＡ　ｓ　Ｉ（３の入ってい
るボンベ１６およびトリメチルガリウムＧａ（ＣＨ３）
３の入っているボンベ１４の、ツレぞれのパルプ６０．
４０を開き、導入管１２を介して原料ガスをＲＦコイル
１０によシ加熱された基板支持用サセプタ１１の入った
反応管１に導入する。The configuration of a conventional vapor phase epitaxial growth apparatus is shown in FIG. Referring to FIG. 1, an introduction pipe 12 for introducing raw material compounds, etc. is provided in the reaction tube 1 equipped with a heating RT'' coil 10 and a susceptor 11 for substrate support. The cylinder 13 and the raw material compound cylinder 14 are connected through valves 60 and 40, respectively, and
The carrier gas cylinder 15 for transporting the raw material compound is connected to the carrier gas purifier 50 and the hydride cylinder 16.
, each gas l from the raw material compound cylinder 14:
A mass flow controller 6 is used to transport the fluid to the reaction tube 1.
1.41 to the inlet pipe 12. GaAs
When growing arsine A s I (3) and trimethylgallium Ga (CH3)
60. of pulp from cylinder 14 containing 3.
40 is opened, and raw material gas is introduced through the introduction pipe 12 into the reaction tube 1 containing the substrate supporting susceptor 11 heated by the RF coil 10.

この方法は、原料供給系が複雑であり、装置が高価であ
ること、用いる有機金属化合物の蒸気圧が高く、引火性
が強いこと、アルシンＡ−ｓ　Ｉ（３などの■族水素化
物の許容濃度が低く、毒性が著しく強いため、装置の取
り扱い保守に細心の注意が必要であることなど、大量生
産用としては欠点が多い方法であった。This method requires a complicated raw material supply system, expensive equipment, high vapor pressure and strong flammability of the organometallic compound used, and tolerance of group I hydrides such as arsine A-s I (3). This method had many drawbacks for mass production, such as the low concentration and extremely high toxicity, which required careful handling and maintenance of the equipment.

本発明の目的は、上記の従来技術におけるような欠点の
ない半導体薄膜製造法を提供することにある。さらに詳
細には、簡単な装置で、容易な操作で、安全に、短時間
に大面積の薄膜を製造する方法を提供することにある。An object of the present invention is to provide a method for manufacturing semiconductor thin films that does not have the drawbacks of the prior art described above. More specifically, it is an object of the present invention to provide a method for safely producing a large-area thin film in a short time using a simple device, easy operation, and safety.

上記の目的の本発明の半導体薄膜製造法の特徴とすると
ころは、半導体薄膜の製造において、原料化合物として
、■族有機金属化合物と■族有機金属化合物との付加物
、あるいは、■族有機金属化合物と■族有機金属化合物
との伺加物を用い、前記の有機金属付加物を基板に塗布
し、水素雰囲気中で加熱処理して、基板上にｌＩＶ族化
合物、あるいはＩＩＶＩ族化合物の半導体薄膜を形成す
ることにある。The feature of the method for producing a semiconductor thin film of the present invention for the above purpose is that in the production of a semiconductor thin film, an adduct of a group (III) organometallic compound and a group (III) organometallic compound or a group (III) organometallic compound is used as a raw material compound. Using an admixture of a compound and a group II organometallic compound, the organometallic adduct is applied to a substrate, and heat treated in a hydrogen atmosphere to form a semiconductor thin film of a group IIV compound or a group IIIVI compound on the substrate. The goal is to form a

本発明を、さらに具体的に、Ｇａ　Ａｓの場合を例にと
って説明すれば、次の通りである。The present invention will be explained in more detail by taking the case of GaAs as an example.

原料化合物として、トリメチルガリウム（Ｃｌ−１３）
６Ｑａと、トリメチルアルシ／（ＣＩＩ乙）３ＡＳトノ
付加物である（　Ｃｌ−１３）３Ｇａ　−Ａｓ　（ＣＦ
Ｉ３）３、寸たは、ジメチルガリウムクロライド（ＣＨ
３）　２　ＣｌＧ　ａとトリメチルアルシン（ＣＨ３）
　３　Ａ　ｓ　　との付加物である（　ＣＨ３）２　ｃ
ｚ　Ｇａ　−Ａｓ　（Ｃｌ−Ｈ６）　６　　などを用い
る。Trimethylgallium (Cl-13) as a raw material compound
6Qa and (Cl-13)3Ga-As (CF
I3) 3, or dimethyl gallium chloride (CH
3) 2ClGa and trimethylarsine (CH3)
(CH3)2 c which is an adduct with 3 A s
zGa-As(Cl-H6)6 etc. are used.

これらの有機金属付加物は、分子が太きいために室温付
近で蒸気圧の低い液体であり、従来技術における蒸気圧
の高く引火性の強いトリメチルガリウム（ＣＨ３）３Ｇ
ａに比べ引火する危険性は少なく取り扱いやすい物質で
ある。また、成長時に、従来技術におけるような、毒性
の著しく強いアルシンＡ　ｓ　Ｔ（３を流す必要もなく
、安全性の点でも優れている。These organometallic adducts are liquids with low vapor pressure near room temperature due to their large molecules, and are different from trimethylgallium (CH3) 3G, which has a high vapor pressure and is highly flammable in the prior art.
It is a substance that is easier to handle and has less risk of igniting than a. Furthermore, there is no need to flush extremely toxic arsine A s T (3) during growth, unlike in the prior art, and it is also excellent in terms of safety.

本発明においては、これらの有機金属付加物をＧａＡｓ
単結晶基板、ガラス基板上に、スプレーなどによって塗
布し、次に、水素雰囲気中で加熱処理する。加熱処理に
よって、有機金属付加物のメチル基、すなわちＣ患基は
付加物から解離し、水素と反応してメタンガスＣｌ−１
４、もしくはメチル基どうし反応してエタンガスとなり
系外に排出される。そのあとに、ＧａＡｓの薄膜が残る
ことになる。In the present invention, these organometallic adducts are
It is applied onto a single crystal substrate or a glass substrate by spraying or the like, and then heat-treated in a hydrogen atmosphere. By heat treatment, the methyl group of the organometallic adduct, that is, the C group, is dissociated from the adduct and reacts with hydrogen to produce methane gas Cl-1.
4, or methyl groups react with each other to form ethane gas, which is discharged from the system. After that, a thin film of GaAs will remain.

このように、本発明の方法は、従来の通常の有機金属化
合物を用いる気相成長法に比べ、装置が簡単で安価であ
シ、短時間に大面積の基板上に薄膜を形成できるという
大きな利点のあることは明らかである。As described above, the method of the present invention has the advantage that the equipment is simpler and cheaper than the conventional vapor phase growth method using a normal organometallic compound, and a thin film can be formed on a large area substrate in a short time. The benefits are clear.

以下に、本発明を実施例につき、装置を示す図面を参照
して説明する。In the following, the invention will be explained by way of example and with reference to the drawings showing the apparatus.

実施例　１ 第２図は、本実施例における半導体薄膜製造用の装置の
概略説明図である。Example 1 FIG. 2 is a schematic explanatory diagram of an apparatus for manufacturing a semiconductor thin film in this example.

第２図において、符号１は反応管、２は基板、６は窒素
ガスなどの不活性ガスボンベ、４は有機金属化合物゛の
入ったボンベ、５は水素ボンベ、６は有機金属付加物塗
布用のスプレー、７は基板支持用サセプタ、８は基板加
熱用ヒータ、５０は水素純化装置である。In Fig. 2, numeral 1 is a reaction tube, 2 is a substrate, 6 is an inert gas cylinder such as nitrogen gas, 4 is a cylinder containing an organometallic compound, 5 is a hydrogen cylinder, and 6 is a cylinder for applying an organometallic adduct. 7 is a susceptor for supporting the substrate, 8 is a heater for heating the substrate, and 50 is a hydrogen purification device.

この装置を用い、ＧａＡｓ基板上にＩＴＩＶ族半導体で
あるＧａＡｓ薄膜を成長させた。その操作は下記の通シ
である。Using this apparatus, a GaAs thin film, which is an ITIV group semiconductor, was grown on a GaAs substrate. The operation is as follows.

まず、基板２上に、スプレー乙により、有機金属付加物
（ＣＨ３）３　Ｇａ　−Ａｓ　（ＣＨ６）　３を塗布し
た。First, an organic metal adduct (CH3)3Ga-As(CH6)3 was applied onto the substrate 2 by spraying.

次に、水素を流しながら、基板２を４５０℃に加熱した
。この加熱により、塗布された有機金属付加物は分解し
、ＧａＡｓのＩＩＩ　Ｖ族半導体薄膜が形成された。Next, the substrate 2 was heated to 450° C. while flowing hydrogen. By this heating, the applied organometallic adduct was decomposed, and a GaAs III-V semiconductor thin film was formed.

上記における基板を、ガラス基板に換えて、全く同様の
処理操作を行い、ガラス基板上にＧａＡｓの半導体薄膜
を形成することができた。By replacing the substrate in the above with a glass substrate and performing exactly the same processing operations, it was possible to form a GaAs semiconductor thin film on the glass substrate.

実施例　２ 実施例１における有機金属付加物を換えた以外は、全く
同一の処理操作を行った。Example 2 The same treatment operations as in Example 1 were performed except that the organometallic adduct was changed.

この場合、有機金属付加物に（ＣＨ３）２Ｃｚ　Ｑａ・
Ａｓ　（Ｃｌ−Ｈ３）　３　を用いたδその結果、Ｇａ
Ａｓ基板上、およびガラス基板上に、それぞれ、ＧａＡ
ｓの半導体薄膜を形成すること・ができた。In this case, (CH3)2Cz Qa・
δ using As (Cl-H3) 3 As a result, Ga
GaA on the As substrate and on the glass substrate, respectively.
It was possible to form a semiconductor thin film of s.

実施例　に の実施例は、ＩＩＶＩ族半導体薄膜製造の例である。Example The example is an example of Group III semiconductor thin film production.

実施例１におけるＧａＡｓ基板をＺｎ８基板に換え、有
機金属付加物を（Ｃ１−Ｉ３）　２Ｚｎ・５（ＣＩ−Ｉ
３）２に換えた以外は、全く同一の処理操作を行った。The GaAs substrate in Example 1 was replaced with a Zn8 substrate, and the organometallic adduct was (C1-I3)2Zn.5(CI-I
3) Exactly the same processing operation was performed except for changing to 2.

その結果、ＺｎＳおよびガラス基板上に、それぞれ、Ｚ
ｎ８半導体薄膜を形成することができだ。As a result, Z
It is possible to form an n8 semiconductor thin film.

実施例　４ この実施例は、実施例６と同様、ＩＩ　ＶＩ族半導体薄
膜の製造例である。Example 4 This example, like Example 6, is an example of manufacturing a group II VI semiconductor thin film.

実施例６におけるＺｎＳ基板をＣｄＳ基板に換え、有機
金属付加物を（Ｃｌ５）２Ｃｄ　、　Ｓ　（ＣＩ−Ｔ３
）２に換えだ以外は、実施例６と同様の処理操作を行っ
た。The ZnS substrate in Example 6 was replaced with a CdS substrate, and the organometallic adduct was (Cl5)2Cd,S (CI-T3
) The same processing operations as in Example 6 were performed except that 2 was used instead.

その結果、ＣｄＳおよびガラス基板上に、それぞれＣｄ
Ｓ半導体薄膜を形成することができた。As a result, CdS and glass substrates were deposited, respectively.
A S semiconductor thin film could be formed.

以上説明したように、本発明は、室温で蒸気圧の低い液
体の有機金属付加物を用い、それを基板上に塗布し、水
素雰囲気中で加熱処理することによるものであり、従来
の有機金属化合物を用いる気相成長法に比べ、安全かつ
安価な装置を用い、容易な操作により、大面積に半導体
薄膜を形成できるという大きな利点がある。As explained above, the present invention uses a liquid organometallic adduct with a low vapor pressure at room temperature, coats it on a substrate, and heat-treats it in a hydrogen atmosphere. Compared to vapor phase growth methods using compounds, this method has the great advantage of being able to form semiconductor thin films over large areas using safe and inexpensive equipment and with easy operations.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図は従来の有機金属化合物を用いる気相エピタキシ
ャル成長装置の概略説明図である。 第２図は本発明実施例の半導体薄膜製造用の装置の概略
説明図である。 １・・・反応管　　　　　　２・・・基板６・・・窒素
ガスなどの不活性ガスボンベ４・・・有機金属付加物の
入ったボンベ５“゛水素ボンベ　　　　６・・・スプレ
ー７・・・サセプタ　　　　　８・・・ヒータ５０・・
・水素純化装置 特許出願人　　日本電信電話公社 代理人弁理士　　中村純之助FIG. 1 is a schematic explanatory diagram of a conventional vapor phase epitaxial growth apparatus using an organometallic compound. FIG. 2 is a schematic explanatory diagram of an apparatus for manufacturing a semiconductor thin film according to an embodiment of the present invention. 1...Reaction tube 2...Substrate 6...Inert gas cylinder such as nitrogen gas 4...Cylinder containing organometallic additive 5''Hydrogen cylinder 6...Spray 7...Susceptor 8 ...Heater 50...
・Hydrogen purification device patent applicant Junnosuke Nakamura, patent attorney representing Nippon Telegraph and Telephone Public Corporation

Claims (1)

【特許請求の範囲】[Claims] 半導体薄膜の製造において、原料化合物として、ＩＪＴ
族有機金属化合物と■族有機金属化合物との付加物、あ
るいは、■族有機金属化合物と■族有機金属化合物との
付加物を用い、前記の有機金属付加物を基板に塗布し、
水素雰囲気中で加熱処理して、基板上にｎＩＶ族化合物
、あるいはＩＩＶＴ族化合物の半導体薄膜を形成するこ
とを特徴とする半導体薄膜製造法。In the production of semiconductor thin films, IJT is used as a raw material compound.
Using an adduct of a group organometallic compound and a group Ⅰ organometallic compound, or an adduct of a group Ⅰ organometallic compound and a group Ⅰ organometallic compound, applying the organometallic adduct to a substrate,
1. A method for manufacturing a semiconductor thin film, which comprises forming a semiconductor thin film of an nIV group compound or a group IIVT compound on a substrate by heat treatment in a hydrogen atmosphere.
JP14465082A 1982-08-23 1982-08-23 Manufacture of semiconductor thin-film Granted JPS5934628A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP14465082A JPS5934628A (en) 1982-08-23 1982-08-23 Manufacture of semiconductor thin-film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP14465082A JPS5934628A (en) 1982-08-23 1982-08-23 Manufacture of semiconductor thin-film

Publications (2)

Publication Number Publication Date
JPS5934628A true JPS5934628A (en) 1984-02-25
JPS639742B2 JPS639742B2 (en) 1988-03-01

Family

ID=15367010

Family Applications (1)

Application Number Title Priority Date Filing Date
JP14465082A Granted JPS5934628A (en) 1982-08-23 1982-08-23 Manufacture of semiconductor thin-film

Country Status (1)

Country Link
JP (1) JPS5934628A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0198219A (en) * 1987-10-09 1989-04-17 Matsushita Electric Works Ltd Manufacture of compound semiconductor thin-film
JPH0445065A (en) * 1990-06-08 1992-02-14 Teijin Seiki Co Ltd Winding method for cross winding cop

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0198219A (en) * 1987-10-09 1989-04-17 Matsushita Electric Works Ltd Manufacture of compound semiconductor thin-film
JPH0445065A (en) * 1990-06-08 1992-02-14 Teijin Seiki Co Ltd Winding method for cross winding cop

Also Published As

Publication number Publication date
JPS639742B2 (en) 1988-03-01

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