JPH10242170A - Manufacture of zinc-contg. ii-vi compd. semiconductor film - Google Patents
Manufacture of zinc-contg. ii-vi compd. semiconductor filmInfo
- Publication number
- JPH10242170A JPH10242170A JP4603197A JP4603197A JPH10242170A JP H10242170 A JPH10242170 A JP H10242170A JP 4603197 A JP4603197 A JP 4603197A JP 4603197 A JP4603197 A JP 4603197A JP H10242170 A JPH10242170 A JP H10242170A
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- JP
- Japan
- Prior art keywords
- solid source
- semiconductor film
- film
- solid
- source
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、亜鉛（Ｚｎ）を
含むII−VI族化合物半導体膜の製造方法に係り、特に結
晶性に優れたｐ型化合物半導体膜を得るための不純物添
加法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a II-VI compound semiconductor film containing zinc (Zn), and more particularly to an impurity doping method for obtaining a p-type compound semiconductor film having excellent crystallinity.
【０００２】[0002]
【従来の技術】ＺｎＳｅやＺｎＳ等のＺｎを含むII−VI
族化合物半導体は、青色発光素子用の半導体材料として
従来より注目されている。しかしこれらの化合物半導体
では、ｎ型は得られるが、自己補償効果によってｐ型半
導体が簡単には得られず、従ってｐｎ接合形成が容易で
はない。2. Description of the Related Art II-VI containing Zn such as ZnSe and ZnS
Group compound semiconductors have been attracting attention as semiconductor materials for blue light emitting devices. However, in these compound semiconductors, an n-type semiconductor can be obtained, but a p-type semiconductor cannot be easily obtained due to a self-compensation effect, and therefore, a pn junction cannot be easily formed.
【０００３】例えば、良質の化合物半導体膜を得る方法
として、ＨＷＥ（Hot Wall Epitaxy）法が知られてい
る。ＨＷＥ装置を用いてｐ型のＺｎＳｅ膜を得るには、
半導体膜の母相となる固体ソース（ＺｎＳｅ）を減圧チ
ャンバ内に配置してこれを加熱蒸発させてホットウォー
ル部で熱分解させる。これと同時に、チャンバ外部に不
純物源として配置した気体ソース（ＮＨ3）をガス導入
管によりチャンバ内のホットウォール部に供給して熱分
解させる。そして分解生成されたＮやＮ2を更に高周波
やＥＣＲにより活性化してＮラジカルを生成する。これ
により、ホットウォール部の上に配置された成膜用基板
にアクセプタ不純物であるＮを添加したｐ型ＺｎＳｅ膜
を形成する。For example, an HWE (Hot Wall Epitaxy) method is known as a method for obtaining a high quality compound semiconductor film. To obtain a p-type ZnSe film using an HWE device,
A solid source (ZnSe) serving as a mother phase of a semiconductor film is placed in a reduced pressure chamber, and is heated and evaporated to be thermally decomposed in a hot wall portion. At the same time, a gas source (NH 3 ) disposed as an impurity source outside the chamber is supplied to a hot wall portion in the chamber through a gas introduction pipe to be thermally decomposed. Then, N and N 2 generated by decomposition are further activated by high frequency or ECR to generate N radicals. Thus, a p-type ZnSe film to which N which is an acceptor impurity is added is formed on the film formation substrate disposed on the hot wall portion.
【０００４】[0004]
【発明が解決しようとする課題】しかし、上述したＺｎ
Ｓｅへのアクセプタ不純物Ｎの添加法では、VI族サイト
への添加のみを考えており、VI族過剰の状態での結晶成
長となるため、結果的に得られるＺｎＳｅ結晶は原子空
孔（II族原子Ｚｎの空孔）が多いものとなる。そしてこ
のＺｎ空孔により、結晶性が劣化し、良質のｐ型半導体
膜が得られない。However, the above-mentioned Zn
In the method of adding the acceptor impurity N to Se, only addition to the group VI site is considered, and the crystal grows in a group VI excess state, so that the resulting ZnSe crystal has atomic vacancies (group II (Vacancies of atomic Zn). And, due to the Zn vacancies, the crystallinity is deteriorated, and a high-quality p-type semiconductor film cannot be obtained.
【０００５】この発明は、上記事情を考慮してなされた
もので、良質のｐ型半導体膜を得ることを可能としたＺ
ｎを含むII−VI族化合物半導体膜の製造方法を提供する
ことを目的としている。The present invention has been made in view of the above circumstances, and has made it possible to obtain a high quality p-type semiconductor film.
It is an object of the present invention to provide a method for manufacturing a II-VI compound semiconductor film containing n.
【０００６】[0006]
【課題を解決するための手段】この発明は、減圧された
チャンバ内で半導体膜の母相となる亜鉛を含むII−VI族
化合物からなる第１の固体ソースを熱分解して成膜用基
板に化合物半導体膜を形成する方法において、前記チャ
ンバ内にＺｎ3Ｎ2を含む第２の固体ソースを配置して、
前記第１の固体ソースと共に第２の固体ソースを熱分解
し、生成されたＮをアクセプタ不純物として添加した化
合物半導体膜を形成することを特徴とする。この発明に
おいて好ましくは、前記第２の固体ソースを収容した第
２の固体ソース容器は、前記第１の固体ソースを収容し
た第１の固体ソース容器と同軸的に第１の固体ソース容
器の下方に配置し、前記成膜用基板は前記第１の固体ソ
ース容器の上方に配置し、かつ前記第１の固体ソース容
器と成膜用基板の間には各固体ソースからの蒸発気体を
熱分解するガス案内管を配置する。According to the present invention, a first solid source made of a group II-VI compound containing zinc, which is a parent phase of a semiconductor film, is thermally decomposed in a reduced-pressure chamber to form a substrate for film formation. In the method of forming a compound semiconductor film, a second solid source containing Zn 3 N 2 is disposed in the chamber,
The second solid source is thermally decomposed together with the first solid source to form a compound semiconductor film in which generated N is added as an acceptor impurity. In the present invention, preferably, the second solid source container containing the second solid source is coaxially below the first solid source container with the first solid source container containing the first solid source. And the film-forming substrate is disposed above the first solid source container, and between the first solid source container and the film-forming substrate, the vaporized gas from each solid source is thermally decomposed. Gas guide tube to be placed.
【０００７】この発明によると、ＺｎＳｅ等への不純物
ソースとして固体ソースである窒化亜鉛（Ｚｎ3Ｎ2）を
用いることにより、熱分解により生成されるＮがアクセ
プタ不純物としてＺｎＳｅに添加されると同時に、Ｚｎ
がＺｎ空孔を補償する働きをする。これにより、原子空
孔の少ない良質の結晶性を有し、かつＺｎ過剰な状態で
結晶成長するため、ＳｅサイトにＮが入り易くなり、高
い正孔濃度を持つｐ型のII−VI族化合物半導体膜を得る
ことができる。また、一般に固体の窒化物はＢＮに代表
されるように蒸気圧が低く、石英容器等に入れて加熱蒸
発させることは難しいが、Ｚｎ3Ｎ2は超高真空下でなく
ても数１００℃程度の加熱で蒸発させることができる。
従って、半導体膜の母相となるＺｎＳｅ等を第１の固体
ソースとし、不純物源となるＺｎ3Ｎ2を含む第２の固体
ソースを用意したＨＷＥ装置を用いて、容易にｐ型Ｚｎ
Ｓｅ膜を形成することができる。According to the present invention, by using zinc nitride (Zn 3 N 2 ) which is a solid source as an impurity source for ZnSe or the like, N generated by thermal decomposition is added to ZnSe as an acceptor impurity at the same time. , Zn
Acts to compensate for Zn vacancies. Thereby, since it has good crystallinity with few atomic vacancies and grows in a Zn-excess state, N easily enters the Se site, and is a p-type II-VI compound having a high hole concentration. A semiconductor film can be obtained. In general, solid nitrides have a low vapor pressure as typified by BN, and it is difficult to heat and evaporate them in a quartz container or the like. However, Zn 3 N 2 has a temperature of several hundred degrees centigrade even under an ultra-high vacuum. Evaporation can be achieved with a moderate degree of heating.
Therefore, p-type Zn can be easily formed by using an HWE device in which ZnSe or the like serving as a mother phase of a semiconductor film is used as a first solid source and a second solid source containing Zn 3 N 2 is used as an impurity source.
An Se film can be formed.
【０００８】[0008]
【発明の実施の形態】以下、図面を参照して、この発明
の実施例を説明する。図１は、この発明の一実施例に用
いたＨＷＥ装置の構成を示す。チャンバ１１はＨＷＥ装
置本体であり、内部は真空ポンプ１２により減圧され
る。チャンバ１１内部には、半導体膜の母相形成用の第
１の固定ソース（この実施例の場合ＺｎＳｅ）を収容す
る筒状の第１の固体ソース容器１３と、不純物源となる
第２の固体ソース（この実施例の場合Ｚｎ3Ｎ2）を収容
する筒状の第２の固体ソース容器１４が同軸的に、かつ
第２の固体ソース容器１４が第１の固体ソース容器１３
の下方に位置するように配置されている。即ち第２の固
体ソース容器１４は、その上端を第１の固体ソース容器
１３の底部を貫通させて、第２の固体ソース容器１４内
部に開口するように配置される。Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 shows a configuration of an HWE device used in one embodiment of the present invention. The chamber 11 is a main body of the HWE device, and the inside thereof is depressurized by a vacuum pump 12. Inside the chamber 11, a cylindrical first solid source container 13 containing a first fixed source (ZnSe in this embodiment) for forming a mother phase of a semiconductor film, and a second solid source serving as an impurity source A cylindrical second solid source container 14 containing a source (Zn 3 N 2 in this embodiment) is coaxial and the second solid source container 14 is a first solid source container 13.
It is arranged so that it may be located under. That is, the second solid source container 14 is arranged so that the upper end thereof penetrates the bottom of the first solid source container 13 and opens inside the second solid source container 14.
【０００９】これら二つの固体ソースの上方には、ホル
ダー１９により保持されヒータ２０により加熱される成
膜用基板１８が配置される。また、固体ソースと基板保
持部の間には、各固体ソースからの蒸発気体を熱分解し
て基板１８の面に案内するガス案内管１６が、図の例で
は第１の固体ソース容器１３と一体に形成されている。
これら固体ソース容器１３，１４及びガス案内管１５は
全て石英管であり、これらの周囲には、加熱ヒータ１６
ａ，１６ｂが配設される。加熱ヒータ１６ａ，１６ｂは
熱遮蔽体１７ａ，１７ｂにより囲まれている。即ちこの
実施例の装置は、母相形成用の固体ソース部Ｂの下に、
不純物源の固体ソース部Ａ（通常、リザーバと呼ばれ
る）が配置され、固体ソース部Ｂの上のガス案内管１５
の部分が各固体ソースからの蒸発気体を熱分解させるホ
ットウォール部Ｃとなっている。Above these two solid sources, a film forming substrate 18 held by a holder 19 and heated by a heater 20 is arranged. Further, between the solid source and the substrate holding portion, a gas guide tube 16 for thermally decomposing the vaporized gas from each solid source and guiding the vaporized gas to the surface of the substrate 18 is provided between the solid source and the first solid source container 13 in the example of FIG. It is formed integrally.
The solid source containers 13 and 14 and the gas guide tube 15 are all quartz tubes, and a heater 16 is provided around them.
a, 16b are provided. The heaters 16a and 16b are surrounded by heat shields 17a and 17b. In other words, the apparatus of this embodiment has a structure under the solid source portion B for forming a mother phase.
A solid source portion A (usually called a reservoir) of an impurity source is disposed, and a gas guide tube 15 above the solid source portion B is provided.
Are hot wall portions C for thermally decomposing the vaporized gas from each solid source.
【００１０】半導体膜に気体ソースを用いて不純物を添
加するためには、チャンバ１１の外部にはＮＨ3ガスを
収容する気体ソースボンベ２１が設けられる。ボンベ２
１からの不純物ガスＮＨ3は、バルブ２２及びマスフロ
ーコントローラ２３を介し、チャンバ１１を貫通するガ
ス導入管２４を介して、ガス案内管１５の底部に供給さ
れるようになっている。即ち外部から不純物ガスを供給
した場合も、その不純物ガスはガス案内管１５において
熱分解されることになる。In order to add impurities to the semiconductor film using a gas source, a gas source cylinder 21 containing NH 3 gas is provided outside the chamber 11. Cylinder 2
The impurity gas NH 3 from 1 is supplied to the bottom of the gas guide tube 15 via a valve 22 and a mass flow controller 23, via a gas introduction tube 24 penetrating the chamber 11. That is, even when an impurity gas is supplied from the outside, the impurity gas is thermally decomposed in the gas guide tube 15.
【００１１】次に具体的に、図１のＨＷＥ装置を用いて
ｐ型ＺｎＳｅ膜を成膜する場合を説明すると、前述のよ
うに第１の固体ソース容器１３にはＺｎＳｅを、第２の
固体ソース容器１４にはＺｎ3Ｎ2を入れる。成膜用基板
１８には、（１００）面を主面とするＧａＡｓ基板を用
いる。チャンバ１１内を１０-6Torr程度まで減圧した状
態で、第１の固体ソース容器１３を６１０〜６９０℃
に、第２の固体ソース容器１４を３５０〜４６０℃にそ
れぞれ加熱し、またガス案内管１５を５６０〜６００℃
に加熱する。これにより各固体ソースは蒸発し、その蒸
発気体はガス案内管１４、即ちホットウォール部Ｃで熱
分解されて基板１８に供給され、基板１８にＺｎＳｅ膜
が成膜される。Next, a case where a p-type ZnSe film is formed using the HWE apparatus of FIG. 1 will be described in detail. As described above, ZnSe is contained in the first solid source container 13 and second solid The source container 14 is filled with Zn 3 N 2 . As the film forming substrate 18, a GaAs substrate having a (100) plane as a main surface is used. With the pressure in the chamber 11 reduced to about 10 −6 Torr, the first solid source container 13 is heated to 610 to 690 ° C.
Then, the second solid source container 14 is heated to 350 to 460 ° C, and the gas guide tube 15 is heated to 560 to 600 ° C.
Heat to As a result, each solid source evaporates, and the evaporated gas is thermally decomposed by the gas guide tube 14, that is, the hot wall portion C, and supplied to the substrate 18, and a ZnSe film is formed on the substrate 18.
【００１２】この実施例においては、不純物源であるＺ
ｎ3Ｎ2が熱分解されて、ＺｎとＮが生成され、Ｎがアク
セプタ不純物となり、ＺｎはＺｎＳｅのＺｎ空孔を補償
する働きをする。またガス案内管１５に導入されたＮＨ
3も熱分解されて、Ｎがアクセプタ不純物としてＺｎＳ
ｅ中に導入される。即ち、ＮＨ3のみを不純物源として
用いる方法と異なり、II族サイトのＺｎ不足を補いなが
ら、VI族サイトへのＮ添加が可能となる。従って、得ら
れるＺｎＳｅ膜はＺｎ空孔の少ない良質の結晶膜とな
り、高い正孔濃度のｐ型ＺｎＳｅ層が得られる。In this embodiment, the impurity source Z
n 3 N 2 is thermally decomposed to generate Zn and N, N becomes an acceptor impurity, and Zn functions to compensate for Zn vacancies in ZnSe. NH introduced into the gas guide tube 15
3 is also thermally decomposed, and N becomes ZnS as an acceptor impurity.
e. That is, unlike the method using only NH 3 as an impurity source, N can be added to the group VI site while supplementing the Zn deficiency at the group II site. Therefore, the obtained ZnSe film becomes a high-quality crystal film having few Zn vacancies, and a p-type ZnSe layer having a high hole concentration can be obtained.
【００１３】この発明は、上記実施例に限られない。例
えば実施例では、ＺｎＳｅ膜を形成したが、ＺｎＳやＺ
ｎＴｅ等、Ｚｎを含む他のII−VI族化合物半導体膜を成
膜する場合に同様にこの発明を適用することができる。
またアクセプタ不純物源として、固体ソースＺｎ3Ｎ2を
用いると同時に、気体ソースＮＨ3を補助的に用いるこ
とは有効である。The present invention is not limited to the above embodiment. For example, in the embodiment, the ZnSe film is formed.
The present invention can be similarly applied to the case of forming another II-VI group compound semiconductor film containing Zn such as nTe.
It is effective to use the solid source Zn 3 N 2 and the gas source NH 3 as an auxiliary source as the acceptor impurity source.
【００１４】[0014]
【発明の効果】以上述べたようにこの発明によれば、Ｚ
ｎを含むII−VI族化合物半導体膜への不純物ソースとし
て固体ソースＺｎ3Ｎ2を用いることにより、熱分解によ
り生成されるＮがアクセプタ不純物としてＺｎＳｅに添
加されると同時に、ＺｎがＺｎ空孔を補償する作用を
し、良質の結晶性を有しかつ高い正孔濃度を持つｐ型の
化合物半導体膜を得ることができる。As described above, according to the present invention, Z
By using the solid source Zn 3 N 2 as an impurity source for the II-VI compound semiconductor film containing n, N generated by thermal decomposition is added to ZnSe as an acceptor impurity, and Zn And a p-type compound semiconductor film having good crystallinity and a high hole concentration can be obtained.
【図１】 この発明の一実施例に用いたＨＷＥ装置の構
成を示す。FIG. 1 shows a configuration of an HWE device used in an embodiment of the present invention.
１１…チャンバ、１２…真空ポンプ、１３…第１の固体
ソース容器、１４…第２の固体ソース容器、１５…ガス
案内管（ホットウォール部）、１６ａ，１６ｂ…ヒー
タ、１７ａ，１７ｂ…熱遮蔽体、１８…成膜用基板、１
９…ホルダー、２０…ヒータ、２１…ガスボンベ、２２
…バルブ、２３…マスフローコントローラ、２４…ガス
導入管、ＺｎＳｅ…第１の固体ソース、Ｚｎ3Ｎ2…第２
の固体ソース。11: chamber, 12: vacuum pump, 13: first solid source container, 14: second solid source container, 15: gas guide tube (hot wall portion), 16a, 16b: heater, 17a, 17b: heat shielding Body, 18 ... substrate for film formation, 1
9 ... holder, 20 ... heater, 21 ... gas cylinder, 22
... valve, 23 ... mass flow controller, 24 ... gas inlet tube, ZnSe ... first solid source, Zn 3 N 2 ... second
Solid sauce.
Claims (2)
となる亜鉛を含むII−VI族化合物からなる第１の固体ソ
ースを熱分解して成膜用基板に化合物半導体膜を形成す
る方法において、 前記チャンバ内にＺｎ3Ｎ2を含む第２の固体ソースを配
置して、前記第１の固体ソースと共に第２の固体ソース
を熱分解し、生成されたＮをアクセプタ不純物として添
加した化合物半導体膜を形成することを特徴とする亜鉛
を含むII−VI族化合物半導体膜の製造方法。1. A method for forming a compound semiconductor film on a deposition substrate by thermally decomposing a first solid source made of a group II-VI compound containing zinc which is a parent phase of a semiconductor film in a reduced-pressure chamber. In the compound, a second solid source containing Zn 3 N 2 is disposed in the chamber, and the second solid source is thermally decomposed together with the first solid source, and the generated N is added as an acceptor impurity. A method for producing a zinc-containing II-VI compound semiconductor film, comprising forming a semiconductor film.
固体ソース容器は、前記第１の固体ソースを収容した第
１の固体ソース容器と同軸的に第１の固体ソース容器の
下方に配置し、前記成膜用基板は前記第１の固体ソース
容器の上方に配置し、かつ前記第１の固体ソース容器と
成膜用基板の間には各固体ソースからの蒸発気体を熱分
解するガス案内管を配置することを特徴とする請求項１
記載の亜鉛を含むII−VI族化合物半導体膜の製造方法。2. A second solid source container accommodating the second solid source is coaxially below the first solid source container accommodating the first solid source container accommodating the first solid source. Disposed, the film-forming substrate is disposed above the first solid source container, and between the first solid source container and the film-forming substrate, the vaporized gas from each solid source is thermally decomposed. The gas guide tube is disposed.
A method for producing a II-VI compound semiconductor film containing zinc as described in the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04603197A JP3633186B2 (en) | 1997-02-28 | 1997-02-28 | Method for producing II-VI compound semiconductor film containing zinc |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04603197A JP3633186B2 (en) | 1997-02-28 | 1997-02-28 | Method for producing II-VI compound semiconductor film containing zinc |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10242170A true JPH10242170A (en) | 1998-09-11 |
| JP3633186B2 JP3633186B2 (en) | 2005-03-30 |
Family
ID=12735683
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04603197A Expired - Fee Related JP3633186B2 (en) | 1997-02-28 | 1997-02-28 | Method for producing II-VI compound semiconductor film containing zinc |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3633186B2 (en) |
-
1997
- 1997-02-28 JP JP04603197A patent/JP3633186B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3633186B2 (en) | 2005-03-30 |
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