JPH0476513B2 - - Google Patents
Info
- Publication number
- JPH0476513B2 JPH0476513B2 JP60218631A JP21863185A JPH0476513B2 JP H0476513 B2 JPH0476513 B2 JP H0476513B2 JP 60218631 A JP60218631 A JP 60218631A JP 21863185 A JP21863185 A JP 21863185A JP H0476513 B2 JPH0476513 B2 JP H0476513B2
- Authority
- JP
- Japan
- Prior art keywords
- cdse
- photoelectric conversion
- conversion element
- film
- cds
- 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.)
- Expired - Lifetime
Links
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 13
- 238000004381 surface treatment Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 150000004820 halides Chemical class 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 description 16
- 230000003595 spectral effect Effects 0.000 description 15
- 239000000758 substrate Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000006104 solid solution Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- 229940088601 alpha-terpineol Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
Landscapes
- Light Receiving Elements (AREA)
Description
【発明の詳細な説明】
＜産業上の利用分野＞
本発明は、フアクシミリや文字画像の読取り入
力装置に用いて好適な光電変換素子の製造方法に
関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method of manufacturing a photoelectric conversion element suitable for use in facsimiles and character image reading/input devices.
＜従来の技術＞
従来、画像読取り用の密着型イメージセンサの
光導電膜にはCdSとCdSeを任意の割合で固溶さ
せたCdSSe膜が用いられ、この割合によつて主に
分光感度特性、光応答速度が変化する。固溶の割
合がCdSeに近づくにつれて光応答が速くなるが、
分光感度のピークは520nｍから720nｍへと可視
領域中心からずれてくる。<Conventional technology> Conventionally, a CdSSe film in which CdS and CdSe are dissolved in a solid solution in an arbitrary ratio is used as a photoconductive film in a contact-type image sensor for image reading, and this ratio mainly determines the spectral sensitivity characteristics, Light response speed changes. As the solid solution ratio approaches CdSe, the photoresponse becomes faster;
The peak of spectral sensitivity shifts from the center of the visible region from 520 nm to 720 nm.
第５図は固溶の各割合に対する分光感度特性を
示す図である。この第５図よりも明らかなように
純粋なCdSeでは分光感度のピークが725nｍ付近
にあり、赤色光付近に主な感度を持つている。従
つて赤色文字画像を読取る必要性のある場合に
は、好適な光電変換素子とは言えなくなる。これ
に対し純粋なCdSでは赤色文字画像の読取りに関
しては好適であるが、光応答速度がCdSeと比べ
て遅いという欠点を持つている。 FIG. 5 is a diagram showing spectral sensitivity characteristics for each ratio of solid solution. As is clear from Figure 5, pure CdSe has a spectral sensitivity peak around 725 nm, with its main sensitivity around red light. Therefore, it cannot be said to be a suitable photoelectric conversion element when it is necessary to read a red character image. On the other hand, although pure CdS is suitable for reading red character images, it has the disadvantage that its optical response speed is slower than that of CdSe.
＜発明が解決しようとする問題点＞
以上のように、光応答速度と分光感度特性とは
相反する傾向にあり、固溶の割合を適当に行なつ
ても両方の中間的特性を持つた光電変換素子しか
作れないという問題点があつた。<Problems to be solved by the invention> As described above, the photoresponse speed and the spectral sensitivity characteristics tend to contradict each other, and even if the proportion of solid solution is appropriately adjusted, it is difficult to obtain a photoelectron with intermediate characteristics between the two. The problem was that only conversion elements could be made.
本発明は上記の事情に鑑みて創案されたもの
で、純粋なCdSeと同等の光応答速度を持ち、か
つ、分光感度特性の優れた光電変換素子の製造方
法を提供するものである。 The present invention was devised in view of the above circumstances, and provides a method for manufacturing a photoelectric conversion element that has a photoresponse speed equivalent to that of pure CdSe and has excellent spectral sensitivity characteristics.
＜問題点を解決するための手段＞
上記の目的を達成するため、本発明の光電変換
素子の製造方法は、CdSeを主成分とする光導電
膜の光入射側の表面を、CdSとその融剤である
Cdのハロゲン化物の混合物を焼成したときの蒸
気によつて表面処理して光電変換素子を作製する
ように構成している。<Means for Solving the Problems> In order to achieve the above object, the method for manufacturing a photoelectric conversion element of the present invention uses CdS and its fused surface on the light incident side of a photoconductive film containing CdSe as a main component. agent
The structure is such that a photoelectric conversion element is fabricated by surface-treating the surface of the Cd halide mixture using the steam produced when it is fired.
＜作用＞
上記のような構成により、CdSeを主成分とす
る光導電膜の光入射側の表面を、CdSとその融剤
であるCdのハロゲン化物の混合物を焼成したと
きの蒸気によつて表面処理して、CdSe膜表面に
極めて薄層のCdS層を形成し、CdSe膜と同等の
光応答速度のまま分光感度を短波長側まで延ばす
ことができる。<Function> With the above configuration, the light incident side surface of the photoconductive film containing CdSe as a main component is heated by the vapor produced when a mixture of CdS and Cd halide, which is its fluxing agent, is fired. By processing, an extremely thin CdS layer is formed on the surface of the CdSe film, making it possible to extend the spectral sensitivity to shorter wavelengths while maintaining the same optical response speed as the CdSe film.
＜実施例＞
以下、図面を参照して本発明の一実施例を詳細
に説明する。<Example> Hereinafter, an example of the present invention will be described in detail with reference to the drawings.
第１図は本発明の光電変換素子の製造方法の一
実施例の表面処理法を説明するための基板配置図
である。第１図において、１は光電変換素子側の
基板、２はこの基板１上に形成されたCdSe膜、
３は表面処理用混合物側の基板、４は表面処理用
混合物側の基板３上に形成されたCdSとその融剤
であるCdのハロゲン化物の混合膜である。 FIG. 1 is a substrate layout diagram for explaining a surface treatment method in an embodiment of the method for manufacturing a photoelectric conversion element of the present invention. In FIG. 1, 1 is a substrate on the photoelectric conversion element side, 2 is a CdSe film formed on this substrate 1,
3 is a substrate on the surface treatment mixture side, and 4 is a mixed film of CdS and Cd halide, which is a fluxing agent, formed on the substrate 3 on the surface treatment mixture side.
上記CdSe膜２は、あらかじめ活性化熱処理を
施した平均粒径0.5μｍのCdSe粉体と、その融剤
であるCdのハロゲン化物（例えばCdCl2）を4.5
モル％と、ガラス転移温度が400℃の低融点ガラ
スフリツト10重量％と、少量のエチルセルロース
を含んだα−テルピネオール適量とを混合し十分
分散した塗膜用ペーストをガラス基板１上にスク
リーン印刷法にて塗膜した後、N2ガス雰囲気中
で100℃で30分乾燥することにより作製する。ま
た、同様にして、上記混合膜４はCdS粉体と、そ
の融剤であるCdのハロゲン化物適量と、少量の
エチルセルロースを含んだα−テルピオネール適
量とを混合して十分分散した塗膜用ペーストをガ
ラス基板３上にスクリーン印刷法にて塗膜した
後、N2ガス雰囲気中で100℃で30分乾燥すること
により作製する。以上のようにして作製した
CdSe膜３とCdS膜４を第１図に示すように近接
して（例えば0.4mm〜0.8mm）対向させ、この状態
で300℃で30分、500℃で１時間熱処理する。 The CdSe film 2 is made of CdSe powder with an average particle size of 0.5 μm that has been heat-treated for activation, and a Cd halide (for example, CdCl 2 ) as a fluxing agent of 4.5 μm.
mol%, 10% by weight of a low-melting glass frit with a glass transition temperature of 400°C, and an appropriate amount of α-terpineol containing a small amount of ethyl cellulose are mixed and sufficiently dispersed, and a coating paste is applied onto a glass substrate 1 by screen printing. After coating the film, it is dried at 100°C for 30 minutes in an N 2 gas atmosphere. Similarly, the above-mentioned mixed film 4 is a coating film prepared by mixing CdS powder, an appropriate amount of Cd halide as a fluxing agent, and an appropriate amount of α-terpionelle containing a small amount of ethyl cellulose and sufficiently dispersing the mixture. The paste is produced by coating the glass substrate 3 with a screen printing method and then drying it at 100° C. for 30 minutes in an N 2 gas atmosphere. Made as above
The CdSe film 3 and the CdS film 4 are placed close to each other (for example, 0.4 mm to 0.8 mm) as shown in FIG.
この熱処理の過程で、CdCl2が融剤として働
き、CdSe粒子同志が表皮で溶けあいながら粒成
長を遂げ、最終的には、平均粒径２〜3μｍの粒
の集合によつて形成される熱処理膜２が完成す
る。また、この熱処理の過程で光導電膜として用
いるCdSe膜２の表面に極めて薄層（例えば数千
Å）のCdS層を活性化処理と同時に形成する。 During this heat treatment process, CdCl 2 acts as a flux, and the CdSe particles undergo grain growth while melting together on the skin, and finally, the heat treatment forms a collection of grains with an average grain size of 2 to 3 μm. Membrane 2 is completed. In addition, during this heat treatment process, an extremely thin CdS layer (for example, several thousand Å) is formed on the surface of the CdSe film 2 used as a photoconductive film at the same time as the activation process.
上記のようにして作製した光導電膜に、第２図
に示すように、電極間隔50μｍ、電極幅60μｍ、
電極ピツチ125μｍのプレーナ型電極５をリフト
オフ法により形成し、光電変換素子を作製する。 As shown in FIG.
Planar electrodes 5 with an electrode pitch of 125 μm are formed by a lift-off method to produce a photoelectric conversion element.
このようにして作製した光電変換素子の分光感
度特性を第３図に示す。 The spectral sensitivity characteristics of the photoelectric conversion element thus produced are shown in FIG.
第３図において、点線が従来のCdSe膜の分光
感度特性であり、実線が本発明の表面処理を施し
たCdSe膜の分光感度特性である。 In FIG. 3, the dotted line is the spectral sensitivity characteristic of the conventional CdSe film, and the solid line is the spectral sensitivity characteristic of the CdSe film subjected to the surface treatment of the present invention.
この第３図より明らかなように表面処理を施し
たCdSe膜は非常に優れた分光感度特性であるこ
とがわかる。 As is clear from FIG. 3, the surface-treated CdSe film has extremely excellent spectral sensitivity characteristics.
第４図に表面処理を施したCdSe膜の光応答時
間と照射光強度の関係を示す。ここでは、光応答
時間は光電変換素子に光が照射されて定常光電流
の50％値に達するまでの立上り時間τrと、光電変
換素子に照射されていた光を遮断してから定常電
流の50％値に減衰するまでの立下り時間τdとで表
わす。表面処理を施したCdSe膜と未処理のCdSe
膜の応答時間の差異はなく、表面処理をすること
では光応答時間に悪影響を及ぼさず、第４図に示
すように光電変換素子として十分満足のゆく光応
答時間を示すことがわかる。 Figure 4 shows the relationship between the photoresponse time and the irradiation light intensity of the surface-treated CdSe film. Here, the photoresponse time is defined as the rise time τ r from when the photoelectric conversion element is irradiated with light until it reaches 50% of the steady-state photocurrent, and the rise time τ r from when the photoelectric conversion element is irradiated with light until it reaches 50% of the steady-state photocurrent. It is expressed as the falling time τ d until it decays to the 50% value. CdSe film with surface treatment and untreated CdSe
It can be seen that there is no difference in the response time of the films, and that the surface treatment has no adverse effect on the photoresponse time, and as shown in FIG. 4, the photoresponse time is sufficiently satisfactory as a photoelectric conversion element.
＜発明の効果＞
以上のように本発明の光電変換素子の作製法
は、光電変換素子の光応答速度を遅くすることな
く分光感度を短波長側まで延ばすことができ非常
に優れた分光感度特性を持たせることができる。<Effects of the Invention> As described above, the method for manufacturing a photoelectric conversion element of the present invention can extend the spectral sensitivity to the short wavelength side without slowing down the photoresponse speed of the photoelectric conversion element, resulting in extremely excellent spectral sensitivity characteristics. can have.
第１図は本発明の光電変換素子製造方法の一実
施例の表面処理法を説明するための基板配置図、
第２図は本発明により作製された光電変換素子の
構造例を示す図、第３図は本発明の光電変換素子
の分光感度特性を示す図、第４図は本発明の光電
変換素子の光応答時間と照射光強度の関係を示す
図、第５図はCdSとCdSeの各固溶割合に対する
分光感度特性である。
１……光電変換素子側の基板、２……CdSe膜、
３……表面処理用混合物側の基板、４……CdS
膜、５……電極、６……光入射を示す矢印。
FIG. 1 is a substrate layout diagram for explaining a surface treatment method in an embodiment of the photoelectric conversion element manufacturing method of the present invention;
FIG. 2 is a diagram showing a structural example of a photoelectric conversion element manufactured according to the present invention, FIG. 3 is a diagram showing spectral sensitivity characteristics of the photoelectric conversion element of the present invention, and FIG. Figure 5, a diagram showing the relationship between response time and irradiation light intensity, shows spectral sensitivity characteristics for each solid solution ratio of CdS and CdSe. 1... Substrate on the photoelectric conversion element side, 2... CdSe film,
3... Substrate on the surface treatment mixture side, 4... CdS
Film, 5...electrode, 6...arrow indicating light incidence.
Claims (1)
表面を、CdSとCdのハロゲン化物の混合物の焼
成時蒸気によつて表面処理する工程を含んでなる
ことを特徴とした光電変換素子の製造方法。 ２ 前記CdSeを主成分とする光導電膜の光入射
側の表面と、CdSとCdのハロゲン化物の混合物
よりなる膜を対向配置せしめて熱処理することに
より、上記光導電膜の表面処理を行なうようにな
したことを特徴とする特許請求の範囲第１項記載
の光電変換素子の製造方法。[Claims] 1. A method comprising the step of treating the light incident side surface of a photoconductive film containing CdSe as a main component with steam during firing of a mixture of CdS and Cd halides. A method for manufacturing a photoelectric conversion element. 2. The light incident side surface of the photoconductive film containing CdSe as a main component and a film made of a mixture of CdS and Cd halides are placed facing each other and heat treated to perform surface treatment of the photoconductive film. A method for manufacturing a photoelectric conversion element according to claim 1, which is characterized in that:
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60218631A JPS6278885A (en) | 1985-09-30 | 1985-09-30 | Manufacture of photoelectric conversion element |
| DE19863632210 DE3632210A1 (en) | 1985-09-25 | 1986-09-23 | METHOD FOR PRODUCING A PHOTOELECTRIC CONVERSION FILM |
| US06/910,875 US4759951A (en) | 1985-09-25 | 1986-09-23 | Heat-treating Cd-containing photoelectric conversion film in the presence of a cadmium halide |
| GB8622999A GB2183089B (en) | 1985-09-25 | 1986-09-24 | Process for producing photoelectric conversion film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60218631A JPS6278885A (en) | 1985-09-30 | 1985-09-30 | Manufacture of photoelectric conversion element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6278885A JPS6278885A (en) | 1987-04-11 |
| JPH0476513B2 true JPH0476513B2 (en) | 1992-12-03 |
Family
ID=16722975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60218631A Granted JPS6278885A (en) | 1985-09-25 | 1985-09-30 | Manufacture of photoelectric conversion element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6278885A (en) |
-
1985
- 1985-09-30 JP JP60218631A patent/JPS6278885A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6278885A (en) | 1987-04-11 |
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