JPS60142579A - Manufacture of light conducting film - Google Patents

Manufacture of light conducting film

Info

Publication number
JPS60142579A
JPS60142579A JP58250819A JP25081983A JPS60142579A JP S60142579 A JPS60142579 A JP S60142579A JP 58250819 A JP58250819 A JP 58250819A JP 25081983 A JP25081983 A JP 25081983A JP S60142579 A JPS60142579 A JP S60142579A
Authority
JP
Japan
Prior art keywords
cadmium
thin film
vapor pressure
cadmium chloride
chloride
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
Application number
JP58250819A
Other languages
Japanese (ja)
Inventor
Kosuke Ikeda
光佑 池田
Hiroko Wada
裕子 和田
Yoichi Harada
洋一 原田
Noboru Yoshigami
由上 登
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.)
Panasonic Holdings Corp
Original Assignee
Matsushita Electric Industrial Co Ltd
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 Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
Priority to JP58250819A priority Critical patent/JPS60142579A/en
Publication of JPS60142579A publication Critical patent/JPS60142579A/en
Pending legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264Inorganic materials
    • H01L31/0296Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1828Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Light Receiving Elements (AREA)

Abstract

PURPOSE:To increase the responding speed of a light conducting film which is mainly composed of solid solution of cadmium sulfide-cadmium selenide by a method wherein the vapor pressure of cadmium chloride is made low than the saturated vapor pressure at the activate temperature. CONSTITUTION:The vapor pressure of cadmium chloride is made under 50% of the saturated vapor pressure, when a film composed of mainly solid solution of cadmium sulfied-cadmium selenide formed on a base plate, and containing a small amount of copper, is crystal grown in the atmosphere of the cadmium chloride vapor and is activated to give the light conductivity. The vapor pressure of cadmium chloride is made low than the saturated vapor pressure, cadmium sulfide or cadmium selenide or the mixture of these materials being placed between the evapolating source of cadmium chloride and the film and a part of or the most part of the cadmium chloride vapor being absorbed. It is preferable that the amount of absorbents are 10-30 times of the weight of cadmium chloride in the evapolating source, and the amount of cupper in the solid solution film are 0.005-0.1mol% and the activate temperature is 450-580 deg.C.

Description

【発明の詳細な説明】 産業上の利用分野 本発明は硫化カドミウム−セレン化カドミウム固溶体を
主体とする光導電性薄膜すなわち光センサ薄膜の製造方
法に関するものである。
DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing a photoconductive thin film, that is, a photosensor thin film, mainly composed of a cadmium sulfide-cadmium selenide solid solution.

従来例の構成とその問題点 従来より硫化カドミウム−セレン化カドミウム固溶体を
主体として、これに少量の銅を含有した薄膜を基板上に
形成し、これを500〜600”Cの高温度下で塩化カ
ドミウムの飽和蒸気中で加熱し、結晶成長と共に光導電
性を伺与する活性化のプロセスによって光導電性薄膜す
なわち光センサを作製できることはよく知られている。
Conventional Structure and Problems Conventionally, a thin film mainly composed of cadmium sulfide-cadmium selenide solid solution containing a small amount of copper is formed on a substrate, and this is chlorinated at a high temperature of 500 to 600"C. It is well known that photoconductive thin films, or optical sensors, can be fabricated by heating in saturated cadmium vapor and an activation process that imparts photoconductivity along with crystal growth.

このような材料と製法で得られる光導電性薄膜は、セレ
ン化カドミウムの固溶濃度を適当に選べば、可視全域の
光によく感応させることができ、また銅濃度を適当に選
べば、光電流と暗電流との比いわゆる明暗比を十分大き
くすることができる。
Photoconductive thin films obtained using such materials and manufacturing methods can be made sensitive to light in the visible range by appropriately selecting the solid solution concentration of cadmium selenide, and can be made sensitive to light in the visible range by appropriately selecting the copper concentration. The ratio between current and dark current, so-called brightness ratio, can be made sufficiently large.

しかしながら、比較的弱い光に対しての応答特性、すな
わち光を照射して後の電流の立上シや光を切って後の電
流の立下りが遅いという欠点がある。
However, there is a drawback in that the response characteristics to relatively weak light are slow, that is, the rise of the current after irradiation with light is slow, and the fall of the current after turning off light is slow.

上記の製法で得られる応答特性は、たとえばセレン化カ
ドミウムの分量が40モモル係銅の分量が0.01モモ
ル係、膜厚が4000人、活性化温度が520”Cの光
導電性薄膜で30ルツクスの光(波長6″65nmのL
ED単色光)を照射した場合、光電流の立上シ、立下り
時間は共に26ミリ秒であった。なお上記光電流の立土
シ時間とは、光を照射し始めて後電流が飽和値の90%
に達する迄の時間、立下り時間とは、光を切って後電流
が飽和値の10%に減少するまでの時間を意味する。
The response characteristics obtained by the above manufacturing method are, for example, 30% for a photoconductive thin film in which the amount of cadmium selenide is 40 mmol, the amount of copper oxide is 0.01 mmol, the film thickness is 4000 mm, and the activation temperature is 520''C. Lux light (wavelength 6″65nm L)
When irradiated with ED monochromatic light, both the rise and fall times of the photocurrent were 26 milliseconds. The above-mentioned photocurrent standing time is the time when the current after starting to irradiate light is 90% of the saturation value.
The fall time means the time it takes for the current to decrease to 10% of the saturation value after the light is turned off.

上記応答上の欠点は固溶体中セレン化カドミウムの分量
を増やすことによって除くことができるが、この場合に
は応答が早くなる代シに短い波長の光に感応しなくなり
、カラー用として使い難くなるなどの欠点が生じる。
The above-mentioned drawbacks in response can be eliminated by increasing the amount of cadmium selenide in the solid solution, but in this case, the response becomes faster, but it becomes less sensitive to short wavelength light, making it difficult to use for color applications. disadvantages arise.

発明の目的 本発明は、感光波長域がそのまますなわち固溶体中のセ
レン化カドミウムの分量が同じもので通常の製法で得ら
れる光導電性薄膜に比べて、応答特性の優れた薄膜を得
る製法を提供することを目的とする。
Purpose of the Invention The present invention provides a manufacturing method for obtaining a photoconductive thin film with excellent response characteristics compared to a photoconductive thin film obtained by a conventional manufacturing method in which the photoconductive wavelength range is the same, that is, the amount of cadmium selenide in the solid solution is the same. The purpose is to

発明の構成 本発明は、基板上に形成した硫化カドミウム−セレン化
カドミウム固溶体を主体とし、これに少量の銅を含有し
た薄膜を、半密閉容器に入れ、高温度で塩化カドミウム
蒸気の雰囲気中にて結晶成長させ光導電性を付与する活
性化に際して、塩化カドミウムの蒸気圧が前記高温度で
の飽和蒸気圧の50%以下であるようにコントロールし
て作製することを特徴としている。
Structure of the Invention The present invention consists of a thin film mainly consisting of a cadmium sulfide-cadmium selenide solid solution formed on a substrate and containing a small amount of copper, placed in a semi-closed container, and exposed to an atmosphere of cadmium chloride vapor at high temperature. During activation to grow crystals and impart photoconductivity, the vapor pressure of cadmium chloride is controlled to be 50% or less of the saturated vapor pressure at the high temperature.

実施例の説明 活性化温度での塩化カドミウムの蒸気圧を飽和蒸気圧の
60%以下としたのは、50%を越えては活性化を抑制
してその結果応答速度を早めるという効果が小さいから
である。半密閉容器中で塩化カドミウムの蒸気圧を飽和
蒸気圧より低くする有効な方法は、塩化カドミウムの蒸
発源と薄膜との中間に硫化カドミウムやセレン化カドミ
ウムあるいはこれらの混合物をおき塩化カドミウム蒸気
の一部分または大部分を吸収して薄膜部分での有効蒸気
圧を減らすことである。活性化に必要な塩化カドミウム
の分量は100X10−3〜1ji/1で、吸収剤とし
ての硫化カドミウム、セレン化カドミウムあるいはこれ
らの混合物の分量は蒸発源塩化カドミウムの10〜30
重量倍程度が好ましい。塩化カドミウムの分量が上記範
囲よシ少ながったシ、硫化カドミウムなどの吸収剤の分
量が上記範囲よシ多い場合には活性化不足が生じ結晶成
長が不十分で光電流が小さくなシ、また塩化カドミウム
の分量が上記範囲より多かったり、吸収剤の分量が上記
範囲より少ない場合には活性化過剰となり結晶が成長し
過ぎてピンホールを生じ、そのために光電流が小さくな
ってしまう。
Description of Examples The reason why the vapor pressure of cadmium chloride at the activation temperature was set to be 60% or less of the saturated vapor pressure is because if it exceeds 50%, the effect of suppressing activation and speeding up the response speed will be small. It is. An effective method for lowering the vapor pressure of cadmium chloride below the saturated vapor pressure in a semi-closed container is to place cadmium sulfide, cadmium selenide, or a mixture thereof between the cadmium chloride evaporation source and the thin film, and to absorb a portion of the cadmium chloride vapor. Alternatively, the effective vapor pressure in the thin film region may be reduced by absorbing most of the vapor. The amount of cadmium chloride required for activation is 100X10-3 to 1ji/1, and the amount of cadmium sulfide, cadmium selenide, or a mixture thereof as an absorbent is 10 to 30 times the amount of cadmium chloride as the evaporation source.
It is preferably about twice the weight. If the amount of cadmium chloride is less than the above range, or if the amount of absorbent such as cadmium sulfide is more than the above range, activation will be insufficient, crystal growth will be insufficient, and photocurrent will be small. Furthermore, if the amount of cadmium chloride is greater than the above range, or if the amount of absorbent is less than the above range, the activation will be excessive and crystals will grow too much, resulting in pinholes, which will reduce the photocurrent.

固溶体薄膜中の銅の分量は0.005〜0.1モル饅が
好ましい。0.005モル係よシ少ないと暗電流が大き
く、したがって光電流の立下りが大きくなり、また0、
1モル係より多いと光電流そのものが小さくなってしま
うからである。薄膜の膜厚は2000〜8o0〇八であ
ることが好ましい。
The amount of copper in the solid solution thin film is preferably 0.005 to 0.1 mol. When the amount is less than 0.005 molar, the dark current becomes large, and therefore the fall of the photocurrent becomes large.
This is because if the amount is more than 1 molar, the photocurrent itself becomes small. The thickness of the thin film is preferably 2000 to 8008.

2000人よシ薄いと光電流が小さくなってしまい、5
ooo人よシ厚いと光電流の立下シが長くなる傾向があ
る。また活性化温度は、450〜580 ”Cが好まし
い。450 ”Cより低いと活性化が不十分で光電流が
小さく、580“°Cより高いと逆に活性化が過剰で膜
中にピンホールを生じてそのため光電流が小さくなって
し丑うからである。
If it is thinner than 2,000 people, the photocurrent will be small, and 5
ooo If the wire is thicker, the fall of the photocurrent tends to be longer. The activation temperature is preferably 450 to 580"C. If it is lower than 450"C, the activation will be insufficient and the photocurrent will be small; if it is higher than 580"C, the activation will be excessive and pinholes will occur in the film. This is because the photocurrent becomes smaller.

以上のような条件下で塩化カドミウムの蒸気圧を減少さ
せて作った光導性薄膜は、飽和蒸気圧下で作った薄膜に
比べて光電流の大きさ、分光感度、温度特性などが変ら
ないま\で光電流の立下りが数分の1と短くすることが
できる。
A photoconductive thin film made by reducing the vapor pressure of cadmium chloride under the above conditions has the same photocurrent magnitude, spectral sensitivity, temperature characteristics, etc. as compared to a thin film made under saturated vapor pressure. With this, the fall of the photocurrent can be reduced to a fraction of the time.

以下、本発明を一実施例により説起する。The present invention will be explained below by way of an example.

実施例 ガラス基板(コーニング社7059)上に硫化カドミウ
ム、セレン化カドミウム、それに銅を含有する固溶体(
セレン化カドミウム40モル係、銅0.01モル%)の
薄膜を真空蒸着法にて形成した。膜厚は約4000八で
あった。この蒸着膜を半密閉容器中に入れ、4oOrn
g/l(容器)の塩化カドミウムを底部に置き、蒸着膜
と塩化第2銅との間に5胴ギヤツプ、20關長の狭あい
部分を設け、この部分に塩化カドミウム4ootngに
対して8gの硫化カドミウムを敷き、容器を500”Q
で約50分間加熱した。このようにして活性化した薄膜
に、幅とギャップの比が2対1である様にAIの対向電
極を蒸着形成した。この光導電性薄膜に655nm、3
0ルツクスの光を照射したら光電流は12μA5その立
上り、立下り時間はそれぞれ20ミリ秒、10ミリ秒で
あった。活性化温度が650“°Cの場合には光電流は
1oμAでその立上り、立下り時間はそれぞれ26ミリ
秒、7ミリ秒であった。
Example A solid solution containing cadmium sulfide, cadmium selenide, and copper was deposited on a glass substrate (Corning Corporation 7059).
A thin film of 40 mol % of cadmium selenide and 0.01 mol % of copper was formed by vacuum evaporation. The film thickness was approximately 4,000. This vapor-deposited film was placed in a semi-closed container, and
g/l (container) of cadmium chloride is placed at the bottom, a 5-body gap and a narrow part of 20 gap length is provided between the vapor deposited film and cupric chloride, and 8 g of cadmium chloride is placed in this part for 4 ootng of cadmium chloride. Lay cadmium sulfide and set the container to 500”Q.
It was heated for about 50 minutes. A counter electrode of AI was formed on the thus activated thin film by vapor deposition so that the width to gap ratio was 2:1. This photoconductive thin film was coated with 655 nm, 3
When irradiated with 0 lux light, the photocurrent was 12 μA5, and its rise and fall times were 20 milliseconds and 10 milliseconds, respectively. When the activation temperature was 650"°C, the photocurrent had a rise time of 1 μA and a fall time of 26 milliseconds and a fall time of 7 milliseconds, respectively.

比較のため同じ様に蒸着薄膜を準備して、硫化カドミウ
ムを敷かない標準製法で活性化した試料を準備した。同
じ条件下で特性を測定したら500“C活性化の場合に
光電流は14 It A、その立上り、立下り時間はそ
れぞれ25ミリ秒、20ミリ秒であった。560“′C
の場合には光電流は12μAでその立上り、立下り時間
はそれぞれ30ミリ秒、2oミリ秒であった◇ 発明の効果 上記実施例から明らかな様に本発明の製法で得られる光
導電性薄膜は従来の製法で得られるものに比べてその光
電流の立下り時間が172〜1/4に旬縮される。
For comparison, a sample was prepared in which a vapor-deposited thin film was prepared in the same way and activated using the standard manufacturing method without cadmium sulfide. When the characteristics were measured under the same conditions, in the case of activation at 500"C, the photocurrent was 14 It A, and its rise and fall times were 25 ms and 20 ms, respectively. 560"'C
In the case of , the photocurrent was 12 μA, and the rise and fall times were 30 milliseconds and 20 milliseconds, respectively. ◇ Effects of the Invention As is clear from the above examples, the photoconductive thin film obtained by the production method of the present invention The fall time of the photocurrent is shortened to 172 to 1/4 compared to that obtained by conventional manufacturing methods.

Claims (5)

【特許請求の範囲】[Claims] (1)硫化カドミウムとセレン化カドミウムとの固溶体
を主体とし、銅を添加含有させた薄膜を基板上に形成し
、この薄膜を半密閉容器に入れ、高温度にて塩化カドミ
ウムの蒸気に暴露して結晶成長させ、光導電性を付与す
る活性化に際して、前記塩化カドミウムの蒸気圧が前記
高温度での飽和蒸気圧の60%以下であることを特徴と
する光導電性薄膜の製造方法。
(1) A thin film mainly consisting of a solid solution of cadmium sulfide and cadmium selenide with added copper is formed on a substrate, and this thin film is placed in a semi-closed container and exposed to cadmium chloride vapor at high temperature. A method for producing a photoconductive thin film, characterized in that the vapor pressure of the cadmium chloride is 60% or less of the saturated vapor pressure at the high temperature during activation for imparting photoconductivity.
(2)銅の分量が固溶体全量中0.005〜0.1モル
チ、薄膜の膜厚が2000〜5ooo人、活性化温度が
460〜680℃であることを特徴とする特許請求の範
囲第1項記載の光導電性薄膜の製造方法。
(2) Claim 1, characterized in that the amount of copper is 0.005 to 0.1 molty in the total amount of the solid solution, the thickness of the thin film is 2000 to 500 mm, and the activation temperature is 460 to 680°C. A method for producing a photoconductive thin film as described in .
(3)塩化カドミウムの蒸発源と薄膜との間に硫化カド
ミウムかセレン化カドミウムあるいはそれらの混合物を
置き、薄膜の置かれた場所での塩化カドミウムの蒸気圧
を減少させることを特徴とする特許請求の範囲第2項記
載の光導電性薄膜の製造方法。
(3) A patent claim characterized in that cadmium sulfide, cadmium selenide, or a mixture thereof is placed between the cadmium chloride evaporation source and the thin film to reduce the vapor pressure of cadmium chloride at the location where the thin film is placed. A method for producing a photoconductive thin film according to item 2.
(4)塩化カドミウムの分量が半密閉容器中100X1
0−5〜1g ” l %硫化カドミウムかセレン化カ
ドミウムあるいはそれらの混合物の分量が塩化カドミウ
ム1gに対して10〜409であることを特徴とする特
許請求の範囲第3項記載の光導電性薄膜の製造方法。
(4) The amount of cadmium chloride is 100x1 in a semi-closed container.
The photoconductive thin film according to claim 3, characterized in that the amount of cadmium sulfide, cadmium selenide, or a mixture thereof is 10 to 409% per gram of cadmium chloride. manufacturing method.
(5)蒸着薄膜と塩化カドミウムの蒸発源との間のすき
間を5〜10+a、長さを10〜20 mmにして、こ
の部分に硫化カドミウムかセレン化カドミウムあるいは
それらの混合物をおいて高温度で薄膜に到達する塩化カ
ドミウムの蒸気圧を減少させることを特徴とする特許請
求の範囲第4項記載の光導電性薄膜の製造方法。
(5) Set the gap between the deposited thin film and the cadmium chloride evaporation source to 5 to 10+ a and the length to 10 to 20 mm, and place cadmium sulfide, cadmium selenide, or a mixture thereof in this part and heat it at high temperature. 5. A method for producing a photoconductive thin film according to claim 4, characterized in that the vapor pressure of cadmium chloride reaching the thin film is reduced.
JP58250819A 1983-12-28 1983-12-28 Manufacture of light conducting film Pending JPS60142579A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP58250819A JPS60142579A (en) 1983-12-28 1983-12-28 Manufacture of light conducting film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP58250819A JPS60142579A (en) 1983-12-28 1983-12-28 Manufacture of light conducting film

Publications (1)

Publication Number Publication Date
JPS60142579A true JPS60142579A (en) 1985-07-27

Family

ID=17213504

Family Applications (1)

Application Number Title Priority Date Filing Date
JP58250819A Pending JPS60142579A (en) 1983-12-28 1983-12-28 Manufacture of light conducting film

Country Status (1)

Country Link
JP (1) JPS60142579A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0198271A (en) * 1987-10-12 1989-04-17 Matsushita Electric Ind Co Ltd Manufacture of photosensor
JPH0198267A (en) * 1987-10-12 1989-04-17 Matsushita Electric Ind Co Ltd Manufacture of photosensor

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0198271A (en) * 1987-10-12 1989-04-17 Matsushita Electric Ind Co Ltd Manufacture of photosensor
JPH0198267A (en) * 1987-10-12 1989-04-17 Matsushita Electric Ind Co Ltd Manufacture of photosensor

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