JPS6327870B2 - - Google Patents
Info
- Publication number
- JPS6327870B2 JPS6327870B2 JP54106373A JP10637379A JPS6327870B2 JP S6327870 B2 JPS6327870 B2 JP S6327870B2 JP 54106373 A JP54106373 A JP 54106373A JP 10637379 A JP10637379 A JP 10637379A JP S6327870 B2 JPS6327870 B2 JP S6327870B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- cdte
- crucible
- evaporation source
- znte
- 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
Links
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F71/00—Manufacture or treatment of devices covered by this subclass
- H10F71/125—The active layers comprising only Group II-VI materials, e.g. CdS, ZnS or CdTe
- H10F71/1253—The active layers comprising only Group II-VI materials, e.g. CdS, ZnS or CdTe comprising at least three elements, e.g. HgCdTe
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
- H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
- H10P14/29—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials characterised by the substrates
- H10P14/2901—Materials
- H10P14/2922—Materials being non-crystalline insulating materials, e.g. glass or polymers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
- H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
- H10P14/34—Deposited materials, e.g. layers
- H10P14/3402—Deposited materials, e.g. layers characterised by the chemical composition
- H10P14/3424—Deposited materials, e.g. layers characterised by the chemical composition being Group IIB-VIA materials
- H10P14/3428—Sulfides
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
- H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
- H10P14/34—Deposited materials, e.g. layers
- H10P14/3402—Deposited materials, e.g. layers characterised by the chemical composition
- H10P14/3424—Deposited materials, e.g. layers characterised by the chemical composition being Group IIB-VIA materials
- H10P14/3431—Selenides
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
- H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
- H10P14/34—Deposited materials, e.g. layers
- H10P14/3402—Deposited materials, e.g. layers characterised by the chemical composition
- H10P14/3424—Deposited materials, e.g. layers characterised by the chemical composition being Group IIB-VIA materials
- H10P14/3432—Tellurides
Landscapes
- Light Receiving Elements (AREA)
Description
【発明の詳細な説明】
本発明は、ZnSxSe1-x（ただし０Ｘ１）ま
たはZnSeを第１層とし、（ZnyCd1-yTe）z
（In2Te3）1-z（ただし０Ｙ，Ｚ１）を第２層
とする複合光導電膜を備えた光導電素子の製造方
法に関する。[Detailed description of the invention] The present invention uses ZnS x Se 1-x (0X1) or ZnSe as the first layer, and (Zn y Cd 1-y Te) z
The present invention relates to a method for manufacturing a photoconductive element having a composite photoconductive film having (In 2 Te 3 ) 1-z (0Y, Z1) as a second layer.
ZnSxSe1-xを第１層とし、（ZnyCd1-yTe）z
（In2Te3）1-zを第２層とする複合光導電膜を備え
た撮像管は、ニユービコンの商品名で市販されて
おり、また、かかる複合光導電膜を製造する方法
は、特公昭52−4406号公報等により知られてい
る。ところで、既知の製造方法、とくに前記公報
に記載の一蒸発源蒸着法によつてかかる複合光導
電膜を製造する場合、長波長側の限界波長を決定
するCdTe量を、第２層用蒸発源物質（ZnyCd1-y
Te）z（In2Te3）1-z中のCdTeの量で制御せざるを
得ない。なぜなら、第２層用蒸発源物質中の
CdTeと、ZnTeまたはIn2Te3との間にはかなり
の蒸気圧差が存在するため、第２層の蒸着時にそ
の蒸発源温度や蒸着時間を調整して最良の光電特
性を得ることは困難であるからである。 ZnS x Se 1-x is the first layer, (Zn y Cd 1-y Te) z
An image pickup tube equipped with a composite photoconductive film having (In 2 Te 3 ) 1-z as the second layer is commercially available under the trade name Nubicon, and a method for manufacturing such a composite photoconductive film is known. It is known from Publication No. 52-4406. By the way, when manufacturing such a composite photoconductive film by a known manufacturing method, particularly the single evaporation source evaporation method described in the above-mentioned publication, the amount of CdTe that determines the critical wavelength on the long wavelength side is determined by the evaporation source for the second layer. Substance (Zn y Cd 1-y
It must be controlled by the amount of CdTe in Te) z (In 2 Te 3 ) 1-z . This is because the evaporation source material for the second layer
Because there is a significant vapor pressure difference between CdTe and ZnTe or In 2 Te 3 , it is difficult to adjust the evaporation source temperature and deposition time to obtain the best photoelectric properties when depositing the second layer. Because there is.
本発明の光導電素子の製造方法においては、第
２層の形成時に、（ZnyCd1-yTe）z（In2Te3）1-zの
うちの少なくともCdTeとZnTeとを別々のるつ
ぼから蒸発させるとともに、各るつぼの上方に設
けたシヤツタを選択的に開閉制御して、CdTeお
よびZnTeの各蒸着量を個別に制御せしめるので
あり、以下本発明の光導電素子の製造方法を、図
面に示した実施例とともに説明する。 In the method for manufacturing a photoconductive element of the present invention, at least CdTe and ZnTe of (Zn y Cd 1-y Te) z (In 2 Te 3 ) 1-z are placed in separate crucibles when forming the second layer. At the same time, shutters provided above each crucible are selectively controlled to open and close to individually control the amount of CdTe and ZnTe deposited. This will be explained together with the embodiment shown in .
第１図においてベルジヤ１内に設けられた円形
の回転板２は、その軸３を軸として１〜30r.p.m.
の速度で回転し、回転板２の周面に沿つて設けら
れた多数の透孔４内には、撮像管のフエイスプレ
ートとなるガラス基板５がとり外し自在にとりつ
けられている。また、回転板２の上方にはガラス
基板加熱用の加熱器６が設けられており、回転板
２の下方には第１ないし第３の蒸発源加熱用ルツ
ボ７，８，９が、透孔４の配列円周に対応した円
周上に散設されている。さらに、図示を省略した
が、各ルツボの上方には、蒸着タイミングおよび
蒸着所要時間を規正するための開閉自在なシヤツ
タが設けられており、各ガラス基板５の下面には
透明導電膜がスパツタまたは蒸着により付設され
ており、各ルツボの外周面には絶縁被覆付き加熱
繊条が設けられている。 In FIG. 1, a circular rotary plate 2 provided in a bell gear 1 has a rotation speed of 1 to 30 rpm with its shaft 3 as an axis.
A glass substrate 5, which serves as a face plate of the image pickup tube, is removably mounted in a large number of through holes 4 provided along the circumferential surface of the rotating plate 2. Further, a heater 6 for heating the glass substrate is provided above the rotating plate 2, and first to third crucibles 7, 8, 9 for heating the evaporation source are provided below the rotating plate 2 with through holes. They are scattered on the circumference corresponding to the array circumference of No. 4. Further, although not shown, a shutter that can be opened and closed is provided above each crucible to regulate the vapor deposition timing and the required vapor deposition time, and a transparent conductive film is sputtered or closed on the lower surface of each glass substrate 5. It is attached by vapor deposition, and heating fibers with an insulating coating are provided on the outer peripheral surface of each crucible.
第１の蒸発源加熱用ルツボ７内には、第１層光
導電材料としてのZnSxSe1-xまたはZnSeが充填さ
れ、第２の蒸発源加熱用ルツボ８内には、たとえ
ば（CdTe）0.99（In2Te3）0.11が、そして、第３の
蒸発源加熱用ルツボ９内には、たとえば（ZnTe）
0.98（In2Te3）0.02がそれぞれ充填される。 The first evaporation source heating crucible 7 is filled with ZnS x Se 1-x or ZnSe as the first layer photoconductive material, and the second evaporation source heating crucible 8 is filled with (CdTe), for example. 0.99 (In 2 Te 3 ) 0.11 , and in the third evaporation source heating crucible 9, for example (ZnTe)
0.98 (In 2 Te 3 ) 0.02 are filled respectively.
第１層の形成にさいしては、ベルジヤ１内を１
×10-5Torr以上の真空に保持し、回転板２を回
転させてガラス基板５を周回移動させる。そし
て、加熱器６に通電してガラス基板５を150℃〜
350℃の温度に保持させるとともに、第１の蒸発
源加熱用ルツボ７を800℃〜980℃に加熱し、この
ルツボ７の上方のシヤツタを開く。これによつ
て、ルツボ７内の光導電物質が、ベルジヤ１内を
周回移動するガラス基板５の透明導電膜上に蒸着
されるから、蒸着層厚が900Å〜1500Åに達した
時点で前記シヤツタを閉じ、ルツボ７の加熱を止
める。 When forming the first layer, the inside of the bell gear 1 is
A vacuum of ×10 -5 Torr or more is maintained, and the rotating plate 2 is rotated to move the glass substrate 5 around. Then, the heater 6 is energized to heat the glass substrate 5 to 150℃~
While keeping the temperature at 350°C, the first evaporation source heating crucible 7 is heated to 800°C to 980°C, and the shutter above the crucible 7 is opened. As a result, the photoconductive material in the crucible 7 is deposited on the transparent conductive film of the glass substrate 5 that moves around in the bell jar 1, so the shutter is closed when the deposited layer thickness reaches 900 Å to 1500 Å. Close and stop heating the crucible 7.
このようにして第１層を形成したのち、ガラス
基板５の温度を250℃に保ち、第２および第３の
蒸発源加熱用ルツボ８，９を加熱するのである
が、（ZnTe）0.98（In2Te3）0.02を充填した第３の蒸
発源加熱用ルツボ９に対する加熱は２段階に分け
て行なうのがよく、その１例は第２図に示す。す
なわち、ガラス基板５を約250℃の温度に保ち、
第２および第３の蒸発源加熱用ルツボ８，９をほ
ぼ同時に加熱する。そして時刻t1において両ルツ
ボ８，９のシヤツタを開き、両ルツボ８，９内の
光導電物質を、周回移動中の第１層上に蒸着させ
るのであり、時刻t2において第３の蒸発源加熱用
ルツボ９を750℃から800℃に昇温させる。この場
合、第２の蒸発源加熱用ルツボ８内の（CdTe）0.9
９（In2Te3）0.01の加熱は、必要な長波長側感度が
光導電膜に得られる時点まで続行せ得るので、
CdTeを多く含んだ第２層をうることができる。 After forming the first layer in this way, the temperature of the glass substrate 5 is maintained at 250°C, and the second and third evaporation source heating crucibles 8 and 9 are heated. The third evaporation source heating crucible 9 filled with 2 Te 3 ) 0.02 is preferably heated in two stages, one example of which is shown in FIG. That is, the glass substrate 5 is maintained at a temperature of about 250°C,
The second and third evaporation source heating crucibles 8 and 9 are heated almost simultaneously. Then, at time t 1 , the shutters of both crucibles 8 and 9 are opened, and the photoconductive material in both crucibles 8 and 9 is evaporated onto the first layer that is moving in a circular motion. The heating crucible 9 is heated from 750°C to 800°C. In this case, (CdTe) in the second evaporation source heating crucible 8 is 0.9
9 (In 2 Te 3 ) 0.01 can be continued until the photoconductive film has the required sensitivity on the long wavelength side, so
A second layer containing a large amount of CdTe can be obtained.
第２層形成の他の方法として、第２の蒸発源加
熱用ルツボ８内の（CdTe）0.99（In2Te3）0.01を時
刻t1に蒸発させ、時刻t3に第３の蒸発源加熱用ル
ツボ９内の（ZnTe）0.98（In2Te3）0.02を蒸着させ
ることができる。この場合、最初に蒸着形成した
（CdTe）0.99（In2Te3）0.01層の層厚を、長波長側感
度をみながら調整できるから、この２例のうちの
いずれを選んでも、CdTe量の制御が容易にで
き、しかもこの制御はシヤツタの開閉という簡単
な操作によつて高精度に行なうことができる。 As another method for forming the second layer, (CdTe) 0.99 (In 2 Te 3 ) 0.01 in the second evaporation source heating crucible 8 is evaporated at time t 1 , and the third evaporation source is heated at time t 3 . (ZnTe) 0.98 (In 2 Te 3 ) 0.02 in the crucible 9 can be vapor-deposited. In this case, the layer thickness of the first (CdTe) 0.99 (In 2 Te 3 ) 0.01 layer formed by vapor deposition can be adjusted while looking at the sensitivity on the long wavelength side, so no matter which of these two examples is selected, the amount of CdTe can be adjusted. Control is easy, and this control can be performed with high precision by a simple operation of opening and closing the shutter.
他の実施例として、第２の蒸発源加熱用ルツボ
８内にCdTeを、第３の蒸発源加熱用ルツボ９内
にZnTeをそれぞれ充填し、かつ、追加した第４
の蒸発源加熱用ルツボ（図示せず）内にIn2Te3
を充填することができる。この場合、第３図に示
すような昇温特性で３つのルツボ内の材料を蒸発
させ、第２層を形成するのであるが、CdTeの蒸
着時間は、長波長側の感度をみながら決定する。 As another example, the second evaporation source heating crucible 8 is filled with CdTe, the third evaporation source heating crucible 9 is filled with ZnTe, and a fourth evaporation source heating crucible 9 is filled with ZnTe.
In 2 Te 3 in a crucible (not shown) for heating the evaporation source.
can be filled. In this case, the materials in the three crucibles are evaporated using the heating characteristics shown in Figure 3 to form the second layer, but the CdTe deposition time is determined by looking at the sensitivity on the long wavelength side. .
このようにして得られた複合光導電膜は、その
後、約600℃の温度下で約20分間の熱処理を受け
るが、完成した光導電膜は第４図に示すような分
光感度特性を示す。なお、本発明の製造方法は、
第２層上に第１層と同様のZnSxSe1-x（ただし０
ｘ１）の層を第３層として形成した３層構造
の光導電素子の製造にも適用できるのは勿論であ
る。 The composite photoconductive film thus obtained is then subjected to heat treatment at a temperature of about 600° C. for about 20 minutes, and the completed photoconductive film exhibits spectral sensitivity characteristics as shown in FIG. 4. In addition, the manufacturing method of the present invention is as follows:
ZnSxSe 1-x (but 0
Of course, the present invention can also be applied to the manufacture of a photoconductive element having a three-layer structure in which the layer x1) is formed as the third layer.
以上のように、本発明の光導電素子の製造方法
は、一方の面上に透明導電膜を備えたガラス基板
を周回移動させつつ前記透明導電膜上に
ZnSxSe1-xからなる第１層を蒸着形成し、しかる
のち（ZnyCd1-yTe）z（In2Te3）1-zからなる第２層
を周回移動中の前記第１層の面上に蒸着形成する
にさいし、前記（ZnyCd1-yTe）z（In2Te3）1-zのう
ちの少なくともCdTeとZnTeとを別々のるつぼ
から蒸発させるとともに、各るつぼの上方に設け
たシヤツタを選択的に開閉制御して、CdTeおよ
びZnTeの各蒸着量を個別に制御せしめるのであ
り、膜厚方向における材料分布を高い精度で制御
でき、とくにCdTe量の制御によつて長波長側感
度を最適値に設定できる利点がある。また、被蒸
着物をベルジヤ内に周回移動させるので、蒸発源
が複数であるにもかかわらず均一な特性の光導電
膜をむらなく形成することができる。 As described above, in the method for manufacturing a photoconductive element of the present invention, a glass substrate having a transparent conductive film on one surface is moved around and a glass substrate is placed on the transparent conductive film.
A first layer consisting of ZnSxSe 1-x is formed by vapor deposition, and then the first layer is moved around a second layer consisting of (Zn y Cd 1-y Te) z (In 2 Te 3 ) 1-z . During vapor deposition on the surface, at least CdTe and ZnTe of the above (Zn y Cd 1-y Te) z (In 2 Te 3 ) 1-z are evaporated from separate crucibles, and the upper part of each crucible is The amount of CdTe and ZnTe deposited can be controlled individually by selectively controlling the opening and closing of the shutter provided in the film.The material distribution in the film thickness direction can be controlled with high precision, and in particular, by controlling the amount of CdTe, the amount of CdTe and ZnTe deposited can be controlled individually. This has the advantage that the wavelength side sensitivity can be set to an optimal value. Further, since the material to be evaporated is moved around inside the bell gear, a photoconductive film with uniform characteristics can be uniformly formed even though there are a plurality of evaporation sources.
第１図は本発明の光導電素子の製造方法におい
て用いられる蒸着装置の一部破断斜視図、第２図
および第３図はそれぞれ同製造方法における昇温
特性図、第４図は同製造方法によつて製造された
光導電素子の分光感度特性図である。
１……ベルジヤ、２……回転板、５……ガラス
基板、６……加熱器、７，８，９……蒸発源加熱
用ルツボ。
FIG. 1 is a partially cutaway perspective view of a vapor deposition apparatus used in the method for manufacturing a photoconductive element of the present invention, FIGS. 2 and 3 are temperature rise characteristics diagrams for the same manufacturing method, and FIG. 4 is a diagram for the same manufacturing method. FIG. 2 is a spectral sensitivity characteristic diagram of a photoconductive element manufactured by. 1... Belgear, 2... Rotating plate, 5... Glass substrate, 6... Heater, 7, 8, 9... Crucible for heating the evaporation source.
Claims (1)
を周回移動させつつ前記透明導電膜上にZnSx
Se1-x（ただし０≦ｘ≦１）またはZnSeからなる
第１層を蒸着形成し、しかるのち（ZnyCd1-yTe）
z（In2Te3）1-z（ただし０≦ｙ，ｚ≦１）からな
る第２層を周回移動中の前記第１層の面上に蒸着
形成するにさいし、前記（ZnyCd1-yTe）z
（In2Te3）1-zのうちの少なくともCdTeとZnTeと
を別々のるつぼから蒸発させるとともに、各るつ
ぼの上方に設けたシヤツタを選択的に開閉制御し
て、CdTeおよびZnTeの各蒸着量を個別に制御
することを特徴とする光導電素子の製造方法。1 While rotating a glass substrate with a transparent conductive film on one surface, ZnS x
A first layer consisting of Se 1-x (0≦x≦1) or ZnSe is formed by vapor deposition, and then (Zn y Cd 1-y Te)
When forming the second layer consisting of z (In 2 Te 3 ) 1-z (0≦y, z≦1) on the surface of the first layer while it is moving around, the above (Zn y Cd 1 -yTe ） z
(In 2 Te 3 ) At least CdTe and ZnTe of 1-z are evaporated from separate crucibles, and shutters provided above each crucible are selectively controlled to open and close to control the amount of CdTe and ZnTe deposited. 1. A method for manufacturing a photoconductive element, characterized by individually controlling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10637379A JPS5630772A (en) | 1979-08-20 | 1979-08-20 | Manufacture of photoconductive element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10637379A JPS5630772A (en) | 1979-08-20 | 1979-08-20 | Manufacture of photoconductive element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5630772A JPS5630772A (en) | 1981-03-27 |
| JPS6327870B2 true JPS6327870B2 (en) | 1988-06-06 |
Family
ID=14431910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10637379A Granted JPS5630772A (en) | 1979-08-20 | 1979-08-20 | Manufacture of photoconductive element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5630772A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2723227B2 (en) * | 1986-09-26 | 1998-03-09 | 株式会社東芝 | Method for manufacturing semiconductor light emitting device |
-
1979
- 1979-08-20 JP JP10637379A patent/JPS5630772A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5630772A (en) | 1981-03-27 |
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