JPH0693432B2 - <II>-<VI> Group compound thin film forming apparatus - Google Patents
<II>-<VI> Group compound thin film forming apparatusInfo
- Publication number
- JPH0693432B2 JPH0693432B2 JP14519686A JP14519686A JPH0693432B2 JP H0693432 B2 JPH0693432 B2 JP H0693432B2 JP 14519686 A JP14519686 A JP 14519686A JP 14519686 A JP14519686 A JP 14519686A JP H0693432 B2 JPH0693432 B2 JP H0693432B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- substrate
- group compound
- compound thin
- evaporation source
- 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
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Description
【発明の詳細な説明】 産業上の利用分野 本発明は、絶縁性非晶質基板上に結晶のすぐれたII−VI
族化合物薄膜を形成するために用いられる。Description: INDUSTRIAL APPLICABILITY The present invention relates to excellent crystalline II-VI on an insulating amorphous substrate.
It is used to form a thin film of a group compound.
従来の技術 II−VI族化合物等のように構成元素の蒸気圧が著しく異
なる場合に有効な薄膜形成法としてホット・ウォールデ
ポジション法（以下HWD法と略す）がある。この方法に
ついては、A.Lopez−OteroがThin Solid Films（シン
ソリッド フィルムス）49（1978）P3〜に詳しく解説し
ている。その方法による形成装置の概略図の一例を第２
図に示した。基板１上への薄膜の堆積は、真空容器15内
を真空に排気しながらII−VI族化合物蒸発源11、壁面12
及び基板１をそれぞれ蒸発源温度制御部10、壁面温度制
御部７及び基板温度制御部４によって加熱温度制御した
状態で行なわれる。以上の様に加熱された壁面12を設け
ることによって、基板表面においては単なる真空蒸着法
に比べて熱平衡状態に近い状態が実現し、堆積されるII
−VI族化合物薄膜もストイキオメトリーを保ったまま基
板面に析出する。また、ドーピングに関しては、壁面12
と基板１で囲われた空間が反応室となり、真空容器15の
外部よりｎ型ドーパントガス13やＰ型ドーパントガスを
その反応室内に適当量導入しながら薄膜堆積を行えばで
きる。ドーパントガスとしては、ｎ型及びＰ型の不純物
をドープするために、それぞれIII族及びＶ族の元素を
結合させた有機化合物たとえば、III族のものとして(C2
H5)3In,(C2H5)3Al,(C2H5)3Ga、Ｖ族のものとして(C2H5)
3P,(CH3)3As,(CH3)3Sb等を用いる場合が多い。2. Description of the Related Art The hot wall deposition method (hereinafter abbreviated as HWD method) is a thin film forming method that is effective when the vapor pressures of constituent elements such as II-VI compounds are significantly different. For this method, see A. Lopez-Otero in Thin Solid Films.
Solid Films) 49 (1978) P3 onwards. Second example of schematic view of forming apparatus by the method
As shown in the figure. The deposition of the thin film on the substrate 1 is performed by evacuating the inside of the vacuum container 15 to a vacuum, and the II-VI group compound evaporation source 11 and the wall 12
The substrate 1 and the substrate 1 are heated under temperature control by the evaporation source temperature controller 10, the wall surface temperature controller 7, and the substrate temperature controller 4, respectively. By providing the heated wall surface 12 as described above, a state closer to a thermal equilibrium state is realized on the substrate surface as compared with a simple vacuum deposition method, and the substrate is deposited II
-Group VI compound thin film also deposits on the substrate surface while maintaining stoichiometry. Regarding doping, the wall surface 12
The space surrounded by the substrate 1 serves as a reaction chamber, and thin film deposition can be performed while introducing an appropriate amount of n-type dopant gas 13 or P-type dopant gas from the outside of the vacuum chamber 15 into the reaction chamber. As the dopant gas, an organic compound in which a group III element and a group V element are combined to dope n-type and P-type impurities, for example, as a group III (C 2
H 5) 3 I n, ( C 2 H 5) 3 Al, (C 2 H 5) 3 G a, as Group V (C 2 H 5)
3 P, (CH 3 ) 3 As, (CH 3 ) 3 Sb etc. are often used.
第２図に示した様な方法でII−VI族化合物薄膜を形成し
かつ同時に気相反応によってドーピングをする場合、先
に述べた導入される有機化合物が熱分解しかつII−VI族
化合物薄膜中に活性な状態で取り込まれる必要があり、
そのためには、壁面及び基板の温度が適切である必要が
ある。用いる有機化合物のドーパントガスによって多少
熱分解の温度が異なるし、また熱分解された後のIII族,
V族の元素が、活性な状態でII−VI族化合物にドーピン
グされるための適切な温度も多少異なるが、一般的には
300℃以上の温度が必要である。しかし、HWD法によるII
−VI族化合物薄膜の絶縁性非晶質基板上における結晶性
は、多結晶の配向性の観点からすれば、壁面温度及び基
板温度が300℃を越えたあたりから配向性が弱まり、結
晶性が悪くなる傾向にある。したがって、HWD法によっ
て絶縁性非晶質基板上にドーピングしたII−VI族化合物
を形成する際には、薄膜多結晶の配向性を犠牲にしてド
ーピングせざるを得ないという問題点がある。When the II-VI group compound thin film is formed by the method as shown in FIG. 2 and is simultaneously doped by the vapor phase reaction, the introduced organic compound is thermally decomposed and the II-VI group compound thin film is introduced. Needs to be taken in in the active state,
For that purpose, it is necessary that the temperatures of the wall surface and the substrate are appropriate. The temperature of the thermal decomposition differs somewhat depending on the dopant gas of the organic compound used, and the group III after the thermal decomposition,
Suitable temperatures for doping Group II-VI compounds with Group V elements in the active state are slightly different, but generally
A temperature of 300 ° C or higher is required. However, by the HWD method II
From the viewpoint of the orientation of polycrystals, the crystallinity of the group VI compound thin film on the insulating amorphous substrate becomes weaker when the wall temperature and the substrate temperature exceed 300 ° C. It tends to get worse. Therefore, when the doped II-VI group compound is formed on the insulating amorphous substrate by the HWD method, there is a problem that the orientation of the thin film polycrystal must be sacrificed for doping.
問題点を解決するための手段 上記に述べたような問題点は、II−VI族化合物薄膜形成
用の基板を保持する基板ホルダーと、前記基板を加熱し
温度制御する手段と、II−VI族化合物薄膜形成用の蒸発
源と、前記蒸発源を保持する蒸発源保持部と前記蒸発源
保持部を加熱し温度制御する手段と、前記基板ホルダー
と前記蒸発源保持部の両者を結合するように設けられた
壁面部と、前記壁面部を加熱し温度制御する手段と、前
記蒸発源保持部と前記壁面部とで囲われた空間内を真空
に引く手段と、前記基板ホルダー部に保持されている基
板に光を照射できる手段を有することを特徴とするII−
VI族化合物薄膜形成装置を用いて、II−VI族化合物薄膜
を形成することによって解決できる。Means for Solving Problems The problems as described above include a substrate holder for holding a substrate for forming a II-VI compound thin film, a means for heating and controlling the temperature of the substrate, and a II-VI group. An evaporation source for forming a compound thin film, an evaporation source holding unit for holding the evaporation source, a unit for heating and controlling the temperature of the evaporation source holding unit, and the substrate holder and the evaporation source holding unit are connected together. A wall surface portion provided, a means for heating and controlling the temperature of the wall surface portion, a means for drawing a vacuum in a space surrounded by the evaporation source holding portion and the wall surface portion, and a means for being held by the substrate holder portion. II-, characterized by having means for irradiating the existing substrate with light
This can be solved by forming a II-VI compound thin film using a VI compound thin film forming apparatus.
作用 この構成により、従来の装置を用いてドーピングされた
II−VI族化合物薄膜を形成する場合、壁面及び基板温度
を300℃以上に設定してその配向性を犠牲にしていた
が、本発明の装置を用いて形成されたII−VI族化合物薄
膜は、壁面及び基板温度を300℃以上400℃以下に設定し
ておけば、II−VI族化合物薄膜の配向性を保持しつつ、
不純物のドーピングも可能となる。By this configuration, it was doped using conventional equipment.
When forming the II-VI group compound thin film, the wall surface and the substrate temperature were set to 300 ° C. or higher to sacrifice the orientation, but the II-VI group compound thin film formed using the apparatus of the present invention If the wall surface and the substrate temperature are set to 300 ° C. or higher and 400 ° C. or lower, while maintaining the orientation of the II-VI group compound thin film,
It is possible to dope impurities.
実施例 本発明の一実施例を従来の場合と比較して以下に述べ
る。第２図に示した装置を用い、5NのCdSの粉末を蒸発
源として、HWD法によってCdS薄膜をガラス基板上に堆積
すると、その薄膜の配向性の基板温度依存性は、第３図
のようになった。なお、この実験においては、第２図の
熱電対９は、840℃に制御しており、壁面温度と基板温
度は第２図の熱電対６及び３が同じ温度を示すように制
御して行ない、配向性の評価としてＸ線の回析パターン
を用いた。この結果から、従来のHWD法によるCdS薄膜の
場合、300℃を越えると六方晶系のＣ軸配向性を示す（0
00.2）面の回析が弱くなってその配向性が低下している
ことがわかる。対して、光照射を用いる第１図に示した
本発明の装置を用いて同様にCdS薄膜をガラス基板上に
堆積するとその薄膜の配向性の基板温度依存性は、第４
図のようになった。なお、この実験においても配向性の
評価としてＸ線の回析パターンを用い、光照射は、超高
圧水銀ランプを用いた。第４図で得られた結果は、本発
明の装置によって形成されたCdS薄膜が、基板温度が400
℃まで強いＣ軸の配向性を保持していることを示してい
る。実際この効果を利用して、壁面及び基板温度を400
℃とし、蒸発源温度840℃として、第１図に示したよう
な方法でIII族元素やＶ族元素をCdS薄膜中に制御性良
く、しかもCdS薄膜の強いＣ軸配向性を保持したままド
ーピングできることを確認している。また、本発明の装
置において、CdS薄膜形成の際に、基板１の上に、CdS薄
膜数μｍからなるフィルターを設置し、基板１にはCdS
のバンドギャップに相当する光の波長より長波長のもの
のみの透過させて同様な実験を行うと、そのCdS薄膜の
配向性は従来の装置を用いて形成した場合と同様な第３
図に示したような結果を得た。このことは本発明による
CdS薄膜形成時に、CdSのバンドギャップに相当する波長
より長波長の光の照射は、何の効果も及ぼさないことを
示している。EXAMPLE One example of the present invention will be described below in comparison with the conventional case. When the CdS thin film was deposited on the glass substrate by the HWD method using the apparatus shown in FIG. 2 with 5N CdS powder as the evaporation source, the substrate temperature dependence of the orientation of the thin film was as shown in FIG. Became. In this experiment, the thermocouple 9 in FIG. 2 was controlled at 840 ° C., and the wall surface temperature and the substrate temperature were controlled so that the thermocouples 6 and 3 in FIG. 2 showed the same temperature. The X-ray diffraction pattern was used to evaluate the orientation. From these results, in the case of CdS thin film prepared by the conventional HWD method, hexagonal C-axis orientation is exhibited at temperatures above 300 ° C (0
It can be seen that the diffraction of the (00.2) plane is weakened and its orientation is lowered. On the other hand, when a CdS thin film is similarly deposited on a glass substrate using the apparatus of the present invention shown in FIG. 1 using light irradiation, the substrate temperature dependence of the orientation of the thin film is
It became like the figure. Also in this experiment, the X-ray diffraction pattern was used as the evaluation of the orientation, and the light irradiation was performed by using the ultra-high pressure mercury lamp. The results obtained in FIG. 4 show that the CdS thin film formed by the device of the present invention has a substrate temperature of 400
It is shown that the orientation of the C axis is strong up to ° C. In fact, by utilizing this effect, the wall and substrate temperatures can be increased to 400
C. and the evaporation source temperature 840.degree. C. By the method shown in FIG. 1, doping of group III element or group V element into the CdS thin film with good controllability and maintaining the strong C-axis orientation of the CdS thin film. I have confirmed that I can do it. In addition, in the apparatus of the present invention, when forming a CdS thin film, a filter having a thickness of several μm of the CdS thin film is installed on the substrate 1, and
When a similar experiment is carried out by transmitting only those having a wavelength longer than the wavelength of light corresponding to the band gap of the CdS thin film, the orientation of the CdS thin film is similar to that of the case where it is formed by using the conventional device.
The results shown in the figure were obtained. This is according to the invention
It is shown that irradiation with light having a wavelength longer than the wavelength corresponding to the band gap of CdS has no effect when the CdS thin film is formed.
また、以上の実施例に述べた効果はCdS薄膜に限るもの
ではない。The effects described in the above embodiments are not limited to the CdS thin film.
発明の効果 本発明によって、絶縁非晶質基板上にすぐれた結晶性の
II−VI族化合物が形成でき、かつその結晶性を損うこと
なく不純物をドーピングできるようになった。EFFECTS OF THE INVENTION According to the present invention, it is possible to obtain excellent crystallinity on an insulating amorphous substrate.
A II-VI group compound can be formed and impurities can be doped without impairing its crystallinity.
第１図は本発明におけるHWD法によるII−VI族化合物薄
膜形成装置の概略構成図、第２図は従来におけるHWD法
によるII−VI族化合物薄膜形成装置の概略構成図、第３
図は従来装置によって形成したCdS薄膜のＸ線回析パタ
ーンの基板温度依存性を示す図、第４図は本発明の装置
によって形成したCdS薄膜のＸ線回析パターンの基板温
度依存性を示す図である。 １……基板、2,5,8……ヒータ、3,6,9……熱電対、4,7,
10……温度制御部、12……壁面、16……基板ホルダー、
ｌ……光。FIG. 1 is a schematic configuration diagram of a II-VI group compound thin film forming apparatus by the HWD method according to the present invention, and FIG. 2 is a schematic configuration diagram of a conventional II-VI group compound thin film forming apparatus by the HWD method.
The figure shows the substrate temperature dependence of the X-ray diffraction pattern of the CdS thin film formed by the conventional apparatus, and FIG. 4 shows the substrate temperature dependence of the X-ray diffraction pattern of the CdS thin film formed by the apparatus of the present invention. It is a figure. 1 ... Substrate, 2,5,8 ... Heater, 3,6,9 ... Thermocouple, 4,7,
10 …… Temperature controller, 12 …… Wall, 16 …… Board holder,
l ... light.
Claims (5)
る基板ホルダーと、前記基板を加熱し温度制御する手段
と、II−VI族化合物薄膜形成用の蒸発源と前記蒸発源を
保持する蒸発源保持部と、前記蒸発源保持部を加熱し温
度制御する手段と、前記基板ホルダーと前記蒸発源保持
部の両者を結合するように設けられた壁面部と、前記壁
面部を加熱し温度制御する手段と、前記基板ホルダーと
前記蒸発源保持部と前記壁面部とで囲われた空間内を真
空に引く手段と、前記基板ホルダー部に保持されている
基板に光を照射できる手段とを有することを特徴とする
II−VI族化合物薄膜形成装置。1. A substrate holder for holding a substrate for forming a II-VI group compound thin film, means for heating the substrate to control the temperature, an evaporation source for forming a II-VI group compound thin film, and a holding source for the evaporation source. An evaporation source holding part, a means for heating and controlling the temperature of the evaporation source holding part, a wall surface part provided so as to connect both the substrate holder and the evaporation source holding part, and the wall surface part. Means for controlling the temperature; means for drawing a vacuum in the space surrounded by the substrate holder, the evaporation source holding portion and the wall surface portion; and means for irradiating the substrate held by the substrate holder portion with light. Is characterized by having
II-VI compound thin film forming apparatus.
面部とで囲われた空間内の外側から前記基板ホルダー部
に保持されている基板に光を照射する手段を有すること
を特徴とする特許請求の範囲第１項記載のII−VI族化合
物薄膜形成装置。2. A means for irradiating the substrate held by the substrate holder with light from the outside of the space surrounded by the substrate holder, the evaporation source holder and the wall surface portion. The II-VI group compound thin film forming apparatus according to claim 1.
はそれらの固溶体のいずれかであることを特徴とする特
許請求の範囲第１項又は第２項記載のII−VI族化合物薄
膜形成装置。3. The II-VI group compound thin film according to claim 1 or 2, wherein the II-VI group compound is any one of CdS, CdSe, CdTe and solid solutions thereof. Forming equipment.
とする特許請求の範囲第１項，第２項又は第３項のいず
れかに記載のII−VI族化合物薄膜形成装置。4. The II-VI group compound thin film forming apparatus as set forth in claim 1, wherein the substrate is an insulating amorphous substrate.
合物のバンドギャップのエネルギーに相当する光の波長
に比べて短いことを特徴とする特許請求の範囲第１項，
第２項，第３項又は第４項のいずれかに記載のII−VI族
化合物薄膜形成装置。5. The wavelength of the light to be irradiated is shorter than the wavelength of the light corresponding to the energy of the band gap of the II-VI group compound to be formed.
The II-VI group compound thin film forming apparatus as described in any one of the items 2, 3, and 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14519686A JPH0693432B2 (en) | 1986-06-20 | 1986-06-20 | <II>-<VI> Group compound thin film forming apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14519686A JPH0693432B2 (en) | 1986-06-20 | 1986-06-20 | <II>-<VI> Group compound thin film forming apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS631038A JPS631038A (en) | 1988-01-06 |
| JPH0693432B2 true JPH0693432B2 (en) | 1994-11-16 |
Family
ID=15379639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14519686A Expired - Lifetime JPH0693432B2 (en) | 1986-06-20 | 1986-06-20 | <II>-<VI> Group compound thin film forming apparatus |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0693432B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333438C (en) * | 2005-02-02 | 2007-08-22 | 南京大学 | Coaxial air intake for acquiring uniform wide-band gap semiconductor thin film |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0467839U (en) * | 1990-10-23 | 1992-06-16 | ||
| JP2007258468A (en) * | 2006-03-23 | 2007-10-04 | National Institute Of Advanced Industrial & Technology | Visible-light transmitting semiconductor element, and manufacturing method thereof |
-
1986
- 1986-06-20 JP JP14519686A patent/JPH0693432B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333438C (en) * | 2005-02-02 | 2007-08-22 | 南京大学 | Coaxial air intake for acquiring uniform wide-band gap semiconductor thin film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS631038A (en) | 1988-01-06 |
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