JPS59198464A - Visible and near infrared light sensitive photoconductive material - Google Patents
Visible and near infrared light sensitive photoconductive materialInfo
- Publication number
- JPS59198464A JPS59198464A JP58073404A JP7340483A JPS59198464A JP S59198464 A JPS59198464 A JP S59198464A JP 58073404 A JP58073404 A JP 58073404A JP 7340483 A JP7340483 A JP 7340483A JP S59198464 A JPS59198464 A JP S59198464A
- Authority
- JP
- Japan
- Prior art keywords
- visible
- photoconductive material
- photoconductive
- light
- sb2se3
- 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
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
Abstract
Description
【発明の詳細な説明】
〔技術分野〕
本発明は光４電材料に関し、特に４００〜１１０００ｎ
の波長の可視域から近赤外域の光に対してすぐれた感度
を有する光導電性材料に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to photovoltaic materials, particularly 400 to 11000 nm.
The present invention relates to a photoconductive material that has excellent sensitivity to light in the visible to near-infrared wavelength range.
従来、可視域から近赤外域（４００〜１０００ ｎｍ
）の光に対して感度を有する光導′亀材料は極めて少な
い。一方、半導体レーザー技術の発展にともない、フォ
トセンサー、光通信などに使用し得るこの近赤外域にす
ぐれた感度を有する光導電材料に対する要望がとみに高
まってきている。Conventionally, from the visible region to the near-infrared region (400 to 1000 nm
) There are very few light guide materials that are sensitive to light. On the other hand, with the development of semiconductor laser technology, there is a growing demand for photoconductive materials that have excellent sensitivity in the near-infrared region and can be used in photo sensors, optical communications, and the like.
ところで、現有の代表的な半導体レーザーとしての（Ｇ
ａ 、 ＡＩ）−Ａｓ系は、その遷移の関係から、レー
ザーダイオードとしての機能を満足するためにはＡＩの
含有割合が必然的に決定され、このため、発振波長の短
波化には限界がある。したがって、このような半導体レ
ーザーを光源とするフォトセンサーなどに適用し得る光
導電材料としては、可視域から近赤外域、特に７００
ｎｍ−１１０００ｎの波長域にすぐれた感度を有するも
のが必要となる。By the way, (G
a, AI)-As system, due to its transition relationship, the content ratio of AI is inevitably determined in order to satisfy the function as a laser diode, and for this reason, there is a limit to shortening the oscillation wavelength. . Therefore, photoconductive materials that can be applied to photosensors using such semiconductor lasers as light sources are suitable for use in the visible to near-infrared range, especially in the 700 nm range.
A material having excellent sensitivity in the wavelength range of nm-11000n is required.
しかし、現在のところこの領域に感度を有する材料は、
その種類が８１ 、 ＣｄＴｌなどごくわずかのものに
限られ、かつそれらは大面積状に成形して使用すること
が困難であるという問題がある。However, currently the only materials sensitive to this region are
There are problems in that the types are limited to only a few, such as 81 and CdTl, and it is difficult to mold and use them in a large area.
本発明は上述の点に鑑みてなされたものであり、可視域
から近赤外域、特に４００ ｎｍ 〜１０００ ｎ＋１
１の波長域の光に対してすぐれた光導電特性を有する光
導電材料を提供することを目的とする。The present invention has been made in view of the above-mentioned points, and has been made in the visible range to the near-infrared range, particularly from 400 nm to 1000 n+1.
An object of the present invention is to provide a photoconductive material having excellent photoconductive properties for light in one wavelength range.
上記目的を達成するため、本発明の可視・近赤外域用光
導電材料は、Ｃｄ５−８ｂ２Ｓ３・Ｓｂ２Ｓｅ３系化合
物を主成分として構成されており、このＣｄＳ・Ｓｂ２
Ｓ３・Ｓｂ２Ｓｅ３系化合物は、酒石酸アンチモニルカ
リウム、三塩化アンチモンおよびカドミウム塩を含有す
る酸性水溶液に硫化水素ガスおよびセレン化水素ガスを
通気させることにより調製される。In order to achieve the above object, the photoconductive material for visible and near-infrared regions of the present invention is composed of a Cd5-8b2S3/Sb2Se3-based compound as a main component, and this CdS/Sb2
The S3.Sb2Se3-based compound is prepared by passing hydrogen sulfide gas and hydrogen selenide gas through an acidic aqueous solution containing potassium antimonyl tartrate, antimony trichloride, and a cadmium salt.
このようにして得られるＣｄ５−８ｂ２Ｓ３・Ｓｂ２Ｓ
ｅ３系化合物は粉末形態である。したがって、これを焼
結膜として厚膜の形で使用することも、またノ々イング
ーとともに用いて塗布することも、さらに−また加圧成
形して蒸着源あるいはスノξツタ用ターゲットとして用
いて薄膜形にすることもできる。Cd5-8b2S3・Sb2S obtained in this way
The e3-based compound is in powder form. Therefore, it can be used in the form of a thick film as a sintered film, or it can be applied with a non-ingu, or it can be pressed into a thin film form and used as a vapor deposition source or a target for snow ivy. It can also be done.
また、光感Ｉｆをさらに高めるため、必要に応じて、Ｃ
ｕ、ＧａなどのＩｂ族元素、■ｂ族元素などの活性成分
を添加して熱拡散させることもできる。In addition, in order to further increase the photosensitivity If, C
It is also possible to add active ingredients such as Ib group elements such as u and Ga, and b group elements to effect thermal diffusion.
ＣｄＳ’５ｂ２Ｓ３− Ｓｂ２Ｓｅ３系の光導′亀材料
は、ＣｄＳが主として６００ ｎｍ〜８００ｎｍの波長
域の光に対して感度を示し、さらにＳｂ２Ｓｅ３が８０
０〜１１０００ｎの波長域の光に対して感度を有するこ
とから、可視・近赤外領域の広範の光に対して感度を有
するのであろうと考えられる。CdS'5b2S3-Sb2Se3-based light guiding material has CdS showing sensitivity mainly to light in the wavelength range of 600 nm to 800 nm, and Sb2Se3 showing sensitivity to light in the wavelength range of 80 nm to 800 nm.
Since it is sensitive to light in the wavelength range of 0 to 11,000 nm, it is thought that it is sensitive to a wide range of light in the visible and near-infrared regions.
以下本発明の光導電材料を、実施例に基づいて説明する
。The photoconductive material of the present invention will be explained below based on Examples.
実施例１
酒石酸アンチモニルカリウムＫ〔５ｂ（Ｃ４Ｈ２０６）
（ＯＨ２） ］ ０．３ｍｏｌ、三塩化アンチモン５ｂ
Ｃ１３０，３ｍｏｌおよび塩化カドミウムＣｄ Ｃｌ
２０− Ｊ ｍ ｏ １を各々秤量し、これを２Ｎの硫
酸水溶液に溶解させたのち、これを５０°ＣＫ調温した
。Example 1 Potassium antimonyl tartrate K [5b (C4H206)
(OH2) ] 0.3 mol, antimony trichloride 5b
C130,3 mol and cadmium chloride Cd Cl
20-J m o 1 was weighed and dissolved in a 2N sulfuric acid aqueous solution, and then the temperature was adjusted to 50°C.
との水溶液に、硫化水素０．６１／ｍｉｎおよびセレン
化水素０．３ ｌ〆ｍｌｎの割合で、硫化水素およびセ
レン化水素を各々３０分間通気し、（０，３ＣｄＳ）・
（０，３８ｂ２Ｓ３）・（０，３Ｓｂ２Ｓ８３）と推定
される沈殿物を得た。(0,3CdS).
A precipitate estimated to be (0,38b2S3)/(0,3Sb2S83) was obtained.
この沈殿物を純水でよく洗浄したのち、脱水し、５０℃
の温度下で４８時間乾燥させた。乾燥後、これをよく粉
砕し、次いで石英ルツボに充填し、Ｎ２雰囲気下４００
℃で６０分間熱処理を行った。熱処理後、これをよく洗
浄し、十分乾燥した。得られた粉体を、プレスによって
、直径５ｍｒｒ＋、厚さ１．０ｍｍの大きさに成形し、
これを蒸着源として表面清浄なガラス基板（２０ｍｍ
Ｘ ２０ ｍｍ Ｘ １ ｒｎｍ）上に膜厚２μｍの薄
膜ケ形ｆＥシた。この時の蒸着は、基板温度３２０°Ｃ
１酸素分圧５ Ｘ １０＝ Ｔｏｒｒの真空条件下で行
い、膜厚モニターはエビワーズ社製ＦＴＭ−３を用いた
。After thoroughly washing this precipitate with pure water, it was dehydrated and heated to 50°C.
It was dried for 48 hours at a temperature of . After drying, it was thoroughly crushed, then filled into a quartz crucible, and heated for 400 minutes under an N2 atmosphere.
Heat treatment was performed at ℃ for 60 minutes. After the heat treatment, this was thoroughly washed and thoroughly dried. The obtained powder was molded into a size with a diameter of 5 mrr+ and a thickness of 1.0 mm using a press,
Using this as an evaporation source, a glass substrate with a clean surface (20 mm
A thin film with a thickness of 2 μm was deposited on the substrate (20 mm x 1 rnm). At this time, the deposition temperature was 320°C.
The coating was carried out under a vacuum condition of 1 oxygen partial pressure of 5 x 10 Torr, and the film thickness was monitored using FTM-3 manufactured by Eviewars.
さらにこの蒸着ｊ模をＮ２′４囲気下、１５０℃の温度
で２０分＋ｔｌアニールを行ったのち、この薄膜上に、
マスク音用いて蒸着によりり／型状の金−俵を設け、分
光光電流５ｆ：測定した。Furthermore, after performing annealing of this evaporated pattern at a temperature of 150° C. for 20 minutes in an N2'4 atmosphere, on this thin film,
A mold-shaped gold bale was provided by vapor deposition using a mask sound, and a spectroscopic photocurrent of 5f was measured.
測定は、ハロゲンランプを光源とし、ブレーズ波長７５
０ ｎｍのグレーティング（格子刻線６００本／ｍｍ）
をイイするモノクロメータにコンＧ−２５０型）を使用
した。波長による光エネルギーの変動を防止するため、
モノクロメータを通過した光を一部フオドマルチシライ
ヤー（光電増倍管）に受光させ、これを回転型連続ＮＤ
フィルターにフィートノ々ツクさせることにより、試料
に照射される光エネルギーが一定になるようにした。The measurement uses a halogen lamp as the light source, and the blaze wavelength is 75.
0 nm grating (600 grating lines/mm)
A monochromator (Con G-250 model) was used. To prevent fluctuations in light energy due to wavelength,
A portion of the light that has passed through the monochromator is received by a photomultiplier (photomultiplier tube), which is then transferred to a rotating continuous ND.
By striking the filter, the light energy irradiated onto the sample was made constant.
第１図に測定結果を示す。図中ａは本発明の光導電材料
の分光特性曲線、ｂは比較用の８１の分光特性曲線であ
る。この測定結果がら明らがなように、本発明で得られ
た光導電材料は、４０（）−１０００ｎｍの可視・近赤
外域用の光導電素子として使用するに十分な特性を有す
ることが確−ｅされた。Figure 1 shows the measurement results. In the figure, a is a spectral characteristic curve of the photoconductive material of the present invention, and b is a spectral characteristic curve of 81 for comparison. As is clear from these measurement results, it is confirmed that the photoconductive material obtained in the present invention has sufficient characteristics to be used as a photoconductive element for the visible and near-infrared region of 40()-1000 nm. -e was made.
実施例２
上記実施例１と同様にして、（０，３Ｃｄ５）・（０，
３Ｓｂ２Ｓ３）−（０，３Ｓｂ２Ｓｅ３）と推定される
沈殿物を洗浄乾燥したのち、この化１投物に対してＣｕ
３０ ｐｐｍ、 Ｇａ ６０ ｐｐｍを添加した。次い
でこ扛を石英ルツボ中に充填し、実施例１と同一条件で
熱処理して蒸着源用材料を作成した。さらに実施例１と
同様にして、試料を作成し、分光光′６流を測定した。Example 2 In the same manner as in Example 1 above, (0,3Cd5)・(0,
After washing and drying the precipitate estimated to be 3Sb2S3)-(0,3Sb2Se3), Cu
30 ppm and 60 ppm of Ga were added. Next, this material was filled into a quartz crucible and heat treated under the same conditions as in Example 1 to produce a material for a vapor deposition source. Furthermore, a sample was prepared in the same manner as in Example 1, and the spectroscopic light '6 flow was measured.
測定結果を第２図に示す。図中ａは本発明の光６１国材
料の分光特性曲線であり、ｂは実施例１と同様の比較用
の８１ の分光特性曲線である。第２図のから明らかな
ように、可視域４００〜６００ ｎｍにおいて光電流が
増加していることが認められる。The measurement results are shown in Figure 2. In the figure, a is the spectral characteristic curve of the optical 61 material of the present invention, and b is the spectral characteristic curve of 81 for comparison, which is the same as in Example 1. As is clear from FIG. 2, it is recognized that the photocurrent increases in the visible range of 400 to 600 nm.
これは、添加した不純物がＣｄＳに対して増感中心とし
て働いているためであると考えられるう〔効果〕
上記実施例から明らかなように、本発明の光導′ｉＬ利
料は、可視領域ならびに近赤外頭載の光に対してすぐれ
た感度を有し、さらに成形性にもすぐれている。したが
って、本冗明の光導電材料は、可視近赤外域用の受光素
子、フォトセンサー、レーデ−ダイオードの用いられる
プリンター、光通信などへの適用が’Ｔ能である。This is thought to be because the added impurity acts as a sensitizing center for CdS. [Effect] As is clear from the above examples, the light guide iL of the present invention can be used in both the visible region and It has excellent sensitivity to near-infrared overhead light and also has excellent moldability. Therefore, the photoconductive material of the present invention can be applied to light-receiving elements for visible and near-infrared regions, photosensors, printers using radar diodes, optical communications, and the like.
第１図および第２図は本発明の光導亀拐料の分光特性曲
線すグラフである。
ａ・・・本発明の光４電材料の分光特性曲線。
ｂ・・・Ｓｔの分光特性曲線（比較）。FIGS. 1 and 2 are graphs of the spectral characteristic curves of the light guiding material of the present invention. a... Spectral characteristic curve of the photovoltaic material of the present invention. b... Spectral characteristic curve of St (comparison).
Claims (1)
びカドミウム塩を含有する酸性水溶液に硫化水素ガスお
よびセレン化水素ガスを通気することにより得られるＣ
ｄ５−８ｂ２Ｓ３・Ｓｂ２Ｓｅ３系化合物を主成分とす
ることを特徴とする、可視・近赤外域用光導電材料。Tartar [C obtained by bubbling hydrogen sulfide gas and hydrogen selenide gas into an acidic aqueous solution containing potassium 17-temonyl, antimony trichloride and cadmium salt.
A photoconductive material for visible and near-infrared regions, characterized by containing a d5-8b2S3/Sb2Se3-based compound as a main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58073404A JPS59198464A (en) | 1983-04-26 | 1983-04-26 | Visible and near infrared light sensitive photoconductive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58073404A JPS59198464A (en) | 1983-04-26 | 1983-04-26 | Visible and near infrared light sensitive photoconductive material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS59198464A true JPS59198464A (en) | 1984-11-10 |
Family
ID=13517219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58073404A Pending JPS59198464A (en) | 1983-04-26 | 1983-04-26 | Visible and near infrared light sensitive photoconductive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59198464A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583272A (en) * | 2012-01-21 | 2012-07-18 | 哈尔滨工业大学 | Vermicular Sb2Se3 hydrogen storage material and preparation method thereof |
| CN102583271A (en) * | 2012-01-21 | 2012-07-18 | 哈尔滨工业大学 | Spine-like SbSe3 semiconductor hydrogen storage material and preparation method thereof |
-
1983
- 1983-04-26 JP JP58073404A patent/JPS59198464A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583272A (en) * | 2012-01-21 | 2012-07-18 | 哈尔滨工业大学 | Vermicular Sb2Se3 hydrogen storage material and preparation method thereof |
| CN102583271A (en) * | 2012-01-21 | 2012-07-18 | 哈尔滨工业大学 | Spine-like SbSe3 semiconductor hydrogen storage material and preparation method thereof |
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