JPH10321959A - Manufacture of compound semiconductor - Google Patents

Manufacture of compound semiconductor

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Publication number
JPH10321959A
JPH10321959A JP12845497A JP12845497A JPH10321959A JP H10321959 A JPH10321959 A JP H10321959A JP 12845497 A JP12845497 A JP 12845497A JP 12845497 A JP12845497 A JP 12845497A JP H10321959 A JPH10321959 A JP H10321959A
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JP
Japan
Prior art keywords
compound semiconductor
crystal
group
substrate
plane
Prior art date
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Granted
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JP12845497A
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Japanese (ja)
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JP4002323B2 (en
Inventor
Takeshi Obayashi
健 大林
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Sharp Corp
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Sharp Corp
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  • Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
  • Semiconductor Lasers (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain a uniform, high-quality GaInNAs crystal having a large N(nitrogen) composition. SOLUTION: This is a manufacturing method for a compound semiconductor for producing a laminated construction on a semiconductor substrate, containing at least one layer of a compound semiconductor crystal at least containing both Ga(gallium) and In(indium) as Group III elements and also containing at least N(nitrogen) and As(arsenic) as Group V elements, and the semiconductor substrate comprises a zincblende-type semiconductor crystal and the substrate has a surface which is sloped from (001) plane to a direction of (111) A plane.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、ＩＩＩ族元素とし
て少なくともＧａとＩｎとを共に含み、Ｖ族元素として
少なくともＮとＡｓとを共に含む化合物半導体の製造方
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a compound semiconductor containing at least Ga and In as Group III elements and at least N and As as Group V elements.

【０００２】[0002]

【従来の技術】近年、オプトエレクトロニクス用材料と
してのＩＩＩ−Ｖ族化合物半導体の利用分野を大きく広
げる新しい材料系として、Ｖ族元素としてＮ（窒素）と
Ａｓ（砒素）とを共に含むＩＩＩ−Ｖ族化合物混晶半導
体材料が提案され、注目されている。Ｎ組成の大きなＡ
ｌＧａＮxＡｓ1-x（ｘ＝０．２）系混晶はＳｉ基板に格
子整合する直接遷移型半導体材料となる可能性があるこ
とから光−電子集積回路用の光源材料として、また、Ｎ
組成の小さなＧａＩｎＮyＡｓ1-y（ｙ＝０．０１５〜
０．０３５）系混晶は光ファイバー通信に重要な波長
１．３μｍ，１．５５μｍに相当するバンドギャップを
もつ直接遷移型半導体材料をＧａＡｓ基板に格子整合し
て得られる可能性があり、これらは応用物理誌第６５巻
１９９６年第２号１４８頁（参考文献１）に詳しい。2. Description of the Related Art In recent years, as a new material system which greatly expands the field of use of III-V compound semiconductors as optoelectronic materials, III-V containing both N (nitrogen) and As (arsenic) as group V elements. Group compound mixed crystal semiconductor materials have been proposed and attracted attention. A with large N composition
Since an lGaN x As 1-x (x = 0.2) -based mixed crystal may be a direct transition type semiconductor material lattice-matched to a Si substrate, it may be used as a light source material for an opto-electronic integrated circuit.
GaInN y As 1-y having a small composition (y = 0.015 to
The 0.035) type mixed crystal may be obtained by lattice-matching a direct transition type semiconductor material having a band gap corresponding to wavelengths 1.3 μm and 1.55 μm, which are important for optical fiber communication, to a GaAs substrate. Applied Physics Journal, Vol. 65, 1996, No. 2, p. 148 (Reference 1).

【０００３】特に後者においては、活性層に上記のＧａ
ＩｎＮＡｓ混晶を用い、かつクラッド層にＡｌＧａＡｓ
系あるいはＧａＩｎＰ系化合物半導体を用いることによ
り活性層とクラッド層との間に大きなバンドオフセット
がとれ、従来の同波長域の半導体レーザに比べて格段に
温度特性が向上した通信用半導体レーザが実現される材
料系であることが実証され、特に実用上注目に値する。[0003] In the latter case, in particular, the above Ga is added to the active layer.
AlGaAs is used for the cladding layer using InNAs mixed crystal.
A large band offset can be taken between the active layer and the cladding layer by using a Ga-based or GaInP-based compound semiconductor, and a communication semiconductor laser with significantly improved temperature characteristics compared to a conventional semiconductor laser in the same wavelength region can be realized. It has been proved that it is a material system that can be used especially in practical use.

【０００４】より具体的には、Ｅｌｅｃｔｒｏｎｉｃｓ
Ｌｅｔｔｅｒｓ，１９９６年，第３２巻，１５８５頁
（参考文献２）において、Ｇａ0.75Ｉｎ0.25Ｎ0.005Ａ
ｓ0.995を単一量子井戸活性層の井戸層に用いた半導体
レーザが示され、７７Ｋにおいて波長１．１１３μｍで
のレーザ発振が報告されている。この従来例におけるＧ
ａＩｎＮＡｓから成る層を含む活性層は、分子線エピタ
キシャル成長（Ｍｏｌｅｃｕｌｅｒ Ｂｅａｍ Ｅｐｉ
ｔａｘｙ：ＭＢＥ）法によって作製されており、Ｎ原料
としてラジカル励起されたＮ分子線が用いられている。
基板には、ＧａＡｓ（００１）面が用いられており、５
００℃の基板温度で結晶成長されている。[0004] More specifically, Electronics
Letters, 1996, Vol. 32, p. 1585 (reference 2), Ga 0.75 In 0.25 N 0.005 A
A semiconductor laser using s 0.995 for the well layer of a single quantum well active layer is shown, and laser oscillation at 77K at a wavelength of 1.113 μm is reported. G in this conventional example
The active layer including the layer made of aInNAs is formed by molecular beam epitaxy (Molecular Beam Epi).
taxy: MBE), and a radical-excited N molecular beam is used as the N source.
A GaAs (001) plane is used for the substrate.
The crystal is grown at a substrate temperature of 00 ° C.

【０００５】[0005]

【発明が解決しようとする課題】参考文献２に示された
上記の従来例は波長１．１１３μｍでのレーザ発振であ
り、光ファイバー通信に重要な波長１．３μｍ，１．５
５μｍでのレーザ発振には至っていない。波長１．３μ
ｍ，１．５５μｍに相当するバンドギャップを有するＧ
ａＩｎＮＡｓ混晶をＧａＡｓに格子整合して得るために
は、その組成を、波長１．３μｍに対してはＧａ0.928
Ｉｎ0.072Ｎ0.025Ａｓ0.975、１．５５μｍに対しては
Ｇａ0.904Ｉｎ0.096Ｎ0.034Ａｓ0.966とすればよい。す
なわち、参考文献２に示された従来例よりも、Ｎの組成
比を大きく（０．０２５以上）することになる。The above conventional example shown in Reference 2 is a laser oscillation at a wavelength of 1.113 μm, which is important for optical fiber communication.
Laser oscillation at 5 μm has not been achieved. 1.3μ wavelength
m, G having a band gap corresponding to 1.55 μm
In order to obtain an aInNAs mixed crystal lattice-matched to GaAs, the composition must be Ga 0.928 for a wavelength of 1.3 μm.
For In 0.072 N 0.025 As 0.975 and 1.55 μm , Ga 0.904 In 0.096 N 0.034 As 0.966 may be used. That is, the composition ratio of N is set to be larger (0.025 or more) than the conventional example shown in Reference 2.

【０００６】ところが、本願発明者らが鋭意実験を行っ
た結果、従来の方法で作製されるＧａＩｎＮＡｓ混晶に
おいては、ＮおよびＩｎの組成を増すに連れてその結晶
性が大きく悪化し、波長１．３μｍや１．５５μｍに相
当するバンドギャップをもつＧａＩｎＮＡｓ結晶は半導
体レーザの活性層として用いるのに十分な結晶性をもた
ないことがわかってきた。これはこの組成の結晶が、Ｇ
ａ−Ｉｎ−Ａｓ−Ｎ四元混晶系における非混和領域（ｍ
ｉｓｃｉｂｉｌｉｔｙ ｇａｐ）内に相当する組成であ
ると見られ、非混和領域外のより安定な二元もしくは三
元混晶の種々の化合物の微小領域が結晶内に発生しやす
い傾向があり、多くの結晶欠陥が誘発されることによる
と考えられる。However, as a result of intensive experiments conducted by the present inventors, in GaInNAs mixed crystals produced by the conventional method, the crystallinity greatly deteriorates as the composition of N and In increases, and the wavelength 1 It has been found that a GaInNAs crystal having a band gap corresponding to 0.3 μm or 1.55 μm does not have sufficient crystallinity to be used as an active layer of a semiconductor laser. This is because crystals of this composition
immiscible region (m in a-In-As-N quaternary mixed crystal system
The composition is considered to be equivalent to the composition within an iscibility gap, and small regions of various stable binary or ternary mixed compounds outside the immiscible region tend to be easily generated in the crystal. It is considered that the defect is induced.

【０００７】ただし、Ｊｏｕｒｎａｌ ｏｆ Ｃｒｙｓ
ｔａｌ Ｇｒｏｗｔｈ １６４（１９９６）１７５−１
７９（参考文献３）においては、Ｉｎを含まないＧａＮ
Ａｓの結晶についてはＮの組成で０．１０まで上げても
良好な結晶を作製できることが確認されている。それに
対し、Ｉｎが入ったＧａ−Ｉｎ−Ａｓ−Ｎ四元混晶系に
なると、Ｎの組成がより少ない場合でも結晶性の低下が
起こり、波長１．３μｍ，１．５５μｍでのレーザ発振
に要求される様な組成では良好なＧａＩｎＮＡｓ混晶結
晶が得られない。一方、Ｎを含まないＧａＩｎＡｓもす
べてのＩｎの組成において良好な結晶を作製できる。こ
のことは、ＧａＩｎＮＡｓ混晶結晶においての結晶性の
低下はＮの組成が大きくなることにのみ起因するのでは
なく、Ｎの存在下でＩｎを添加していくことが深く関わ
っていることを示している。これは、Ｉｎの添加により
四元混晶系にすることで非混和領域（ｍｉｓｃｉｂｉｌ
ｉｔｙ ｇａｐ）の組成範囲が拡大することによると推
測される。However, the Journal of Crys
tal Growth 164 (1996) 175-1
79 (Ref. 3) states that GaN containing no In
As for As crystals, it has been confirmed that good crystals can be produced even when the composition of N is increased to 0.10. On the other hand, in the case of a Ga-In-As-N quaternary mixed crystal containing In, crystallinity is reduced even when the composition of N is smaller, and laser oscillation at wavelengths of 1.3 μm and 1.55 μm occurs. With the required composition, a good GaInNAs mixed crystal cannot be obtained. On the other hand, GaInAs containing no N can produce good crystals in all In compositions. This indicates that the decrease in crystallinity in the GaInNAs mixed crystal is not caused only by the increase in the composition of N, but is deeply related to the addition of In in the presence of N. ing. This is because a quaternary mixed crystal system is formed by the addition of In to a non-miscible region (miscibil region).
It is presumed that the composition range of (ity gap) is expanded.

【０００８】本発明は上記の問題を解決することを目的
としたものである。つまり、ＩＩＩ族元素として少なく
ともＧａとＩｎとを共に含み、Ｖ族元素として少なくと
もＮとＡｓとを共に含む化合物半導体混晶において、非
混和領域内に相当する組成でも良好な結晶性を保ったま
ま均一な混晶結晶を作製することができる結晶成長の方
法を提供するものである。特に、波長１．３μｍ，１．
５５μｍに相当するバンドギャップを有するＧａＩｎＮ
Ａｓ混晶結晶を得る製造方法を提供するものである。The present invention has been made to solve the above problems. In other words, in a compound semiconductor mixed crystal containing at least Ga and In as Group III elements and at least N and As as Group V elements, good crystallinity is maintained even with a composition corresponding to an immiscible region. It is an object of the present invention to provide a crystal growth method capable of producing a uniform mixed crystal. In particular, the wavelength 1.3 μm, 1..
GaInN having a band gap corresponding to 55 μm
An object of the present invention is to provide a production method for obtaining an As mixed crystal.

【０００９】[0009]

【課題を解決するための手段】この発明（請求項１）に
係る化合物半導体の製造方法は、ＩＩＩ族元素として少
なくともＧａ（ガリウム）とＩｎ（インジウム）とを共
に含み、Ｖ族元素として少なくともＮ（窒素）とＡｓ
（砒素）とを共に含む化合物半導体結晶を少なくとも１
層含む積層構造を半導体基板上に作製する化合物半導体
の製造方法であって、基板が閃亜鉛鉱型の半導体結晶か
ら成り、その基板が｛００１｝面から｛１１１｝Ａ面方
向へ傾斜された表面を有していることによって上記の目
的を達成する。The method of manufacturing a compound semiconductor according to the present invention (claim 1) includes at least Ga (gallium) and In (indium) as Group III elements and at least N as Group V elements. (Nitrogen) and As
(Arsenic) and at least one compound semiconductor crystal.
A method for producing a compound semiconductor in which a laminated structure including layers is formed on a semiconductor substrate, wherein the substrate is made of a zinc-blende-type semiconductor crystal, and the substrate is inclined from the {001} plane to the {111} A plane. The above object is achieved by having a surface.

【００１０】本願発明者らは、上記に示した従来の結晶
成長の検討手法から観点を変えて、用いる基板の表面の
状態に注目して検討を行った。その結果、基板の表面を
終端している原子の種類が、ＧａＩｎＮＡｓ混晶結晶を
結晶成長する際に大きな影響を与えていることを見い出
した。請求項１による本発明では、基板表面がＩＩＩ族
元素終端面である為に、均一で良好な結晶性を保ったま
まＧａＩｎＮＡｓ混晶結晶を作製することができるよう
になる。The inventors of the present application have studied from the viewpoint of the state of the surface of the substrate to be used by changing the viewpoint from the above-described conventional technique for examining crystal growth. As a result, it has been found that the type of atoms terminating the surface of the substrate has a great influence on the growth of GaInNAs mixed crystal. According to the first aspect of the present invention, since the substrate surface is a group III element termination surface, GaInNAs mixed crystal can be produced while maintaining uniform and good crystallinity.

【００１１】この発明（請求項２）に係る化合物半導体
の製造方法は、その基板が｛００１｝面から｛１１１｝
Ａ面方向へ３度以上３０度以下の角度で傾斜された表面
を有していることによって上記の目的を達成する。[0011] In the method of manufacturing a compound semiconductor according to the present invention (claim 2), the substrate is preferably {111} from {001} plane.
The above object is achieved by having a surface inclined at an angle of 3 degrees or more and 30 degrees or less in the A-plane direction.

【００１２】より好ましくは、その基板が｛００１｝面
から｛１１１｝Ａ面方向へ５度以上１５度以下の角度で
傾斜された表面を有していることによって上記の目的を
達成する。基板の傾斜角度を適切に選ぶことにより、特
に効果的に前記の作用・効果を得ることができる。[0012] More preferably, the above object is achieved by that the substrate has a surface inclined at an angle of 5 ° to 15 ° from the {001} plane to the {111} A plane. By appropriately selecting the inclination angle of the substrate, the above-described functions and effects can be obtained particularly effectively.

【００１３】この発明（請求項３）に係る化合物半導体
の製造方法は、前記積層構造は、６００℃以上７５０℃
以下の温度で結晶成長されることによって上記の目的を
達成する。[0013] In the method for manufacturing a compound semiconductor according to the present invention (claim 3), the laminated structure may be at least 600 ° C and 750 ° C.
The above object is achieved by growing crystals at the following temperatures.

【００１４】結晶成長の温度を適切に選ぶことにより、
特に効果的に前記の作用・効果を得ることができる。By properly selecting the temperature of crystal growth,
Particularly, the above operation and effect can be obtained effectively.

【００１５】この発明（請求項４）に係る化合物半導体
の製造方法は、前記のＩＩＩ族元素として少なくともＧ
ａとＩｎとを共に含み、Ｖ族元素として少なくともＮと
Ａｓとを共に含む化合物半導体結晶は、Ｖ族元素として
結晶中に含まれているＮの組成比 ［Ｎ原子密度］／（［Ｎ原子密度］＋［Ａｓ原子密
度］） が０．０２５以上０．１以下であることによって上記の
目的を達成する。In the method for manufacturing a compound semiconductor according to the present invention (claim 4), at least G
A compound semiconductor crystal containing both a and In and containing at least N and As as a group V element has a composition ratio of N contained in the crystal as a group V element [N atom density] / ([N atom The above object is achieved when the [density] + [As atom density]) is 0.025 or more and 0.1 or less.

【００１６】一定値以上のＮを含んだＡｓとＮとを共に
含むＩＩＩ−Ｖ族化合物半導体混晶に対してこの発明を
適用することで、格段の効果を得ることができる。A remarkable effect can be obtained by applying the present invention to a III-V compound semiconductor mixed crystal containing both As and N containing a certain amount of N or more.

【００１７】この発明（請求項５）に係る化合物半導体
の製造方法は、Ｖ族元素としてＰ（燐）を含む化合物半
導体を積層し、その上にＶ族元素としてＡｓだけを有す
る化合物半導体を少なくとも１分子層以上１０分子層以
下だけ積層し、その上にＩＩＩ族元素として少なくとも
ＧａとＩｎとを共に含み、Ｖ族元素として少なくともＮ
とＡｓとを共に含む化合物半導体結晶を結晶成長する工
程を含んでいることによって上記の目的を達成する。In the method of manufacturing a compound semiconductor according to the present invention (claim 5), a compound semiconductor containing P (phosphorus) as a group V element is laminated, and at least a compound semiconductor having only As as a group V element is formed thereon. One or more molecular layers and 10 or less molecular layers are laminated, and at least Ga and In are both contained as Group III elements, and at least N is contained as Group V elements.
The above object is attained by including a step of growing a compound semiconductor crystal containing both As and As.

【００１８】この工程を行うことにより、Ｐ化合物とＧ
ａＩｎＮＡｓ混晶結晶との界面が急峻になる。By performing this step, the P compound and G
The interface with the aInNAs mixed crystal becomes sharp.

【００１９】この発明（請求項６）に係る化合物半導体
の製造方法は、ＩＩＩ族元素として少なくともＧａとＩ
ｎとを共に含み、Ｖ族元素として少なくともＮとＡｓと
を共に含む化合物半導体結晶を結晶成長する直前に、Ｎ
原料だけを供給する工程を含むことによって上記の目的
を達成する。In the method of manufacturing a compound semiconductor according to the present invention (claim 6), at least Ga and I as Group III elements may be used.
Immediately before crystal growth of a compound semiconductor crystal containing both n and at least N and As as group V elements,
The above object is achieved by including a step of supplying only the raw material.

【００２０】この工程を行うことにより、ＧａＩｎＮＡ
ｓ混晶結晶を結晶成長する直前に、その下地の表面が窒
化される為、その上のＧａＩｎＮＡｓ混晶結晶が結晶成
長の初期からスムースなステップフロー成長が起こるよ
うになる。By performing this step, GaInNA
Immediately before the crystal growth of the s mixed crystal, the surface of the base is nitrided, so that the GaInNAs mixed crystal on it grows smoothly from the initial stage of crystal growth.

【００２１】この発明（請求項７）に係る化合物半導体
の製造方法は、基板として用いる閃亜鉛鉱型の半導体結
晶がＧａＡｓからなることによって上記の目的を達成す
る。In the method of manufacturing a compound semiconductor according to the present invention (claim 7), the above object is achieved by forming a zinc blende type semiconductor crystal used as a substrate from GaAs.

【００２２】基板としてＧａＡｓを用いることにより、
光ファイバー通信に重要な波長１．３μｍ，１．５５μ
ｍに対応するＧａＩｎＮＡｓ混晶結晶を格子整合させて
得ることができる。By using GaAs as a substrate,
1.3 μm, 1.55 μm wavelengths important for optical fiber communication
m can be obtained by lattice-matching a GaInNAs mixed crystal corresponding to m.

【００２３】[0023]

【発明の実施の形態】BEST MODE FOR CARRYING OUT THE INVENTION

（実施の形態１）本発明の実施形態１として、（００
１）面から（１１１）Ａ面方向へ傾斜したＧａＡｓ基板
の上に、ＭＢＥ法を用いてＡｌＧａＡｓ／ＧａＩｎＮＡ
ｓ／ＡｌＧａＡｓからなるダブルヘテロ構造を作製した
場合について示す。(Embodiment 1) As Embodiment 1 of the present invention, (00
AlGaAs / GaInNA is formed on the GaAs substrate inclined from the 1) plane toward the (111) A plane by MBE.
The case where a double hetero structure made of s / AlGaAs is manufactured will be described.

【００２４】（００１）面から（１１１）Ａ面方向へ傾
斜した表面を有するＧａＡｓ基板を準備し、その上に、
Ａｌ分子線，Ｇａ分子線，Ｉｎ分子線，Ａｓ2分子線，
ラジカル励起されたＮ分子線を原料とするＭＢＥ法によ
り化合物半導体の多層膜を結晶成長した。A GaAs substrate having a surface inclined from the (001) plane to the (111) A plane direction is prepared.
Al molecular beam, Ga molecular beam, In molecular beam, As 2 molecular beam,
A multilayer film of a compound semiconductor was grown by MBE using a radical-excited N molecular beam as a raw material.

【００２５】ここで「（００１）面から（１１１）Ａ面
方向へ傾斜した表面」とは、（００１）面の傾斜基板で
あり、Ｇａ原子で終端するステップ端を表面に有するよ
うに傾斜して切り出された基板である。（００１）面か
ら（１１１）Ａ面方向へ５５°傾斜した基板は、（１１
１）Ａ面となる。なお、｛１１１｝Ａ面は｛１１１｝Ｇ
ａ面、｛１１１｝Ｂ面は｛１１１｝Ａｓ面とも呼ぶ。Here, the “surface inclined from the (001) plane to the (111) A plane” is an inclined substrate of the (001) plane, which is inclined so as to have a step end terminated with Ga atoms on the surface. This is the substrate cut out. The substrate tilted 55 ° from the (001) plane toward the (111) A plane is (11)
1) Surface A The {111} A plane is {111} G
The a-plane and {111} B plane are also called {111} As plane.

【００２６】作製した多層膜の構造は、まずＧａＡｓ基
板の上に層厚０．５μｍのＧａＡｓからなるバッファ層
を、その上に層厚０．５μｍのＡｌ0.2Ｇａ0.8Ａｓから
なる第一障壁層を、その上に層厚０．１μｍのＧａ
0.928Ｉｎ0.072Ｎ0.025Ａｓ0.975からなる発光層を、そ
の上に層厚０．５μｍのＡｌ0.2Ｇａ0.8Ａｓからなる第
二障壁層を、その上に保護層として層厚０．５μｍのＧ
ａＡｓが形成されている。この時のＧａ0.928Ｉｎ0.072
Ｎ0.025Ａｓ0.975結晶は、ＧａＡｓに格子整合し、波長
１．３μｍに相当するバンドギャップを有するＧａＩｎ
ＮＡｓ結晶である。結晶成長温度は、多層膜を作製する
間中６５０℃に保持し、結晶成長速度は０．５μｍ／時
間とした。The structure of the formed multilayer film is as follows. First, a buffer layer made of GaAs having a layer thickness of 0.5 μm is formed on a GaAs substrate, and a first barrier layer made of Al 0.2 Ga 0.8 As is formed with a layer thickness of 0.5 μm. With a 0.1 μm thick Ga
A light emitting layer made of 0.928 In 0.072 N 0.025 As 0.975 , a second barrier layer made of Al 0.2 Ga 0.8 As having a thickness of 0.5 μm thereon, a G layer having a thickness of 0.5 μm serving as a protective layer thereon.
aAs is formed. At this time, Ga 0.928 In 0.072
The N 0.025 As 0.975 crystal is GaIn lattice-matched to GaAs and has a band gap corresponding to a wavelength of 1.3 μm.
It is a NAs crystal. The crystal growth temperature was kept at 650 ° C. during the production of the multilayer film, and the crystal growth rate was 0.5 μm / hour.

【００２７】また、ＭＢＥ法による結晶成長は、図１に
示すシーケンスで行った。つまり、ＧａＡｓ基板をＭＢ
Ｅ結晶成長装置内に導入した後、（工程Ａ）Ａｓ2分子
線を照射しながら６５０℃にまで昇温し、ＧａＡｓの清
浄表面を得る。その後、（工程Ｂ）Ｇａ分子線，Ａｓ2
分子線により層厚０．５μｍのＧａＡｓを結晶成長し、
続いて（工程Ｃ）Ａｌ分子線，Ｇａ分子線，Ａｓ2分子
線により層厚０．５μｍのＡｌ0.2Ｇａ0.8Ａｓを得る。
次に（工程Ｄ）Ｎラジカル分子線だけを供給して成長層
最表面のテラスを形成するＡｓ原子の一部を窒化により
Ｎ原子で置き換えた後、（工程Ｅ）Ｇａ分子線，Ｉｎ分
子線，Ａｓ2分子線，Ｎラジカル分子線により層厚０．
１μｍのＧａＩｎＮＡｓ層を得る。再び（工程Ｆ）Ａｌ
分子線，Ｇａ分子線，Ａｓ2分子線により層厚０．５μ
ｍのＡｌ0.2Ｇａ0.8Ａｓを、最後に（工程Ｇ）Ａｌ分子
線を止めて０．５μｍのＧａＡｓを得る。各層を結晶成
長する際の各分子線の強度は、それぞれの層に対して最
適となるように調節した。The crystal growth by the MBE method was performed according to the sequence shown in FIG. That is, the GaAs substrate is changed to MB.
After being introduced into the E crystal growth apparatus, (step A) the temperature is raised to 650 ° C. while irradiating an As 2 molecular beam to obtain a clean surface of GaAs. Then, (Step B) Ga molecular beam, As 2
GaAs having a layer thickness of 0.5 μm is grown by molecular beam,
Subsequently (step C), Al 0.2 Ga 0.8 As having a layer thickness of 0.5 μm is obtained from an Al molecular beam, a Ga molecular beam, and an As 2 molecular beam.
Next, (Step D) After supplying only N radical molecular beams and replacing a part of As atoms forming a terrace on the outermost surface of the growth layer with N atoms by nitriding, (Step E) Ga molecular beams and In molecular beams , As 2 molecular beam and N radical molecular beam.
A 1 μm GaInNAs layer is obtained. Again (Step F) Al
Layer thickness 0.5μ by molecular beam, Ga molecular beam, As 2 molecular beam
m Al 0.2 Ga 0.8 As, and finally (step G), the Al molecular beam is stopped to obtain 0.5 μm GaAs. The intensity of each molecular beam during crystal growth of each layer was adjusted to be optimal for each layer.

【００２８】０°〜６０°の傾斜角を有する基板の上に
作製した試料に関して表面欠陥密度を評価した結果を図
２に示す。傾斜角０°の傾斜していない（００１）面上
に作製された試料と比較して、傾斜基板上では高品質の
ＧａＩｎＮＡｓ混晶を得ることができた。またその傾斜
角度とともに欠陥密度が低下し、最低値をとる。FIG. 2 shows the result of evaluating the surface defect density of a sample manufactured on a substrate having a tilt angle of 0 ° to 60 °. As compared with the sample fabricated on the (001) plane having a tilt angle of 0 ° and not tilted, a high-quality GaInNAs mixed crystal could be obtained on the tilted substrate. Further, the defect density decreases with the inclination angle, and takes the lowest value.

【００２９】従来のように｛００１｝面から傾斜してい
ない面方位を有する基板の上にＧａＩｎＮＡｓ混晶結晶
を結晶成長させた場合結晶性の低下が発生しやすい。こ
れは、この四元混晶の組成が非混和領域（ｍｉｓｃｉｂ
ｉｌｉｔｙ ｇａｐ）内に相当する組成であるため、微
視的には非混和領域外のより安定な二元もしくは三元混
晶の種々の化合物の微小領域が結晶内に発生し、母体の
格子定数の違いなどから多くの結晶欠陥が誘発されるた
めと考えられる。この微小領域の発生は特にＩＩＩ族元
素種が複数ある場合、より誘発されやすい。これは、結
晶成長時には、ＩＩＩ族元素であるＧａ、Ｉｎの成長表
面でのモビリティーがＶ族元素に比べて大きいので、よ
り安定な別のＩＩＩ族組成比を持つ結晶が生成し、結晶
内に複数の相が分離して発生しやすいことによる。特
に、ＧａとＮの結合力が他の組み合わせのものより特に
強いことにより、成長時に特にＧａとＮが優先的に結合
し、ＧａとＮの組成が高い領域が結晶内に発生しやすい
ことが考えられる。このような不均一な領域の存在によ
り表面欠陥密度の増大などの結晶性の悪化が起こってい
ると思われる。これはＩＩＩ族元素がＧａとＩｎの２つ
存在していることにより発生するものであり、Ｉｎの存
在しないＧａＮＡｓ結晶の場合には、ＩＩＩ族元素とし
てはＧａ元素のみのため、仮に成長時にＧａとＮが優先
的に結合したとしても、それにより組成が不均一になる
ことはない。When a GaInNAs mixed crystal is grown on a substrate having a plane orientation not inclined from the {001} plane as in the prior art, the crystallinity tends to be reduced. This is because the composition of the quaternary mixed crystal is in an immiscible region (miscib).
(i.e., the composition of the compound), microscopically, microscopic regions of various compounds of a more stable binary or ternary mixed crystal outside the immiscible region are generated in the crystal, and the lattice constant of the matrix is obtained. It is considered that many crystal defects are induced due to the difference between the two. The generation of this minute region is more likely to be induced particularly when there are a plurality of group III element species. This is because at the time of crystal growth, the mobility of the group III elements Ga and In on the growth surface is larger than that of the group V element, so that a crystal having another more stable group III composition ratio is generated, and the crystal is formed in the crystal. This is because a plurality of phases are likely to be separated and generated. In particular, since the bonding force between Ga and N is particularly stronger than that of other combinations, Ga and N are particularly preferentially bonded during growth, and a region having a high Ga and N composition is likely to be generated in the crystal. Conceivable. It is considered that the presence of such a non-uniform region causes deterioration in crystallinity such as an increase in surface defect density. This is caused by the presence of two group III elements, Ga and In. In the case of a GaNAs crystal without In, only the Ga element is used as the group III element. And N are preferentially bonded, the composition does not become non-uniform.

【００３０】一方でステップ端がＩＩＩ族元素で終端し
た表面を持つ基板、つまり｛１００｝面から｛１１１｝
Ａ面方向へ傾斜した表面をもつ基板を用いた場合、ステ
ップ端はＶ族元素で安定になろうとするので、結晶成長
中に基板に付着したＧａ源とＩｎ源はステップ端に到達
してそのままその位置でＩＩＩ族サイトに取り込まれ
る。その結果、別のＩＩＩ族組成比を持つ結晶の生成が
抑制され、組成の均一性が大きく向上し、ＩｎとＮの組
成の大きな結晶を良好な結晶性で得ることができるよう
になる。このように、ＩＩＩ族サイトで終端している表
面ステップを有する基板を用いることで、非混和領域内
に相当する組成でも均一で良好な結晶性を有するＧａＩ
ｎＮＡｓ混晶結晶を作製することが可能になる新たな効
果が見い出された。On the other hand, a substrate having a surface having a step end terminated with a group III element, that is, from a {100} plane to a {111} plane
When a substrate having a surface inclined in the direction of the A-plane is used, the step end tends to be stabilized by the group V element, so that the Ga source and the In source attached to the substrate during the crystal growth reach the step end and remain as they are. At that position, it is incorporated into the group III site. As a result, the generation of crystals having another group III composition ratio is suppressed, the composition uniformity is greatly improved, and crystals having a large composition of In and N can be obtained with good crystallinity. As described above, by using a substrate having a surface step terminating at a group III site, GaI having uniform and good crystallinity even with a composition corresponding to an immiscible region can be obtained.
A new effect has been found that makes it possible to produce an nNAs mixed crystal.

【００３１】傾斜基板の角度に関しては、図２に見られ
るように３〜３０°で十分な効果が現われ、５〜１５°
とするのがより好ましい。傾斜角度が小さい場合にはス
テップの密度が低い為にその効果が顕著には現われず、
傾斜角度が大きすぎる場合にも結晶性の悪化が生じる。With respect to the angle of the inclined substrate, as shown in FIG.
More preferably, When the inclination angle is small, the effect does not appear remarkably because the density of the step is low,
When the inclination angle is too large, the crystallinity is deteriorated.

【００３２】図３に、（００１）面から（１１１）Ａ面
方向へ１０°傾斜した表面を有するＧａＡｓ基板の上へ
多層構造を作製した時の表面欠陥密度の、結晶成長時の
基板温度の依存性を示す。いずれもＧａＡｓに格子整合
する組成で、波長１．３μｍに相当するバンドギャップ
を有するＧａＩｎＮＡｓ結晶の表面欠陥密度である。基
板温度６００℃から７５０℃の間で表面欠陥密度の低い
試料が得られ、図３中で示されたΔＴの範囲が最適な結
晶成長温度範囲であることがわかる。結晶成長の温度が
低い場合にはステップ端から結晶成長が生じるステップ
フロー成長が起こりにくく、また結晶成長温度が高い場
合には一旦結晶中に取り込まれたＶ族元素が再蒸発する
為に良好な結晶成長が生じない。FIG. 3 shows the surface defect density when a multilayer structure was formed on a GaAs substrate having a surface inclined by 10 ° from the (001) plane to the (111) A plane, and the substrate temperature during crystal growth. Show dependencies. Each is a surface defect density of a GaInNAs crystal having a composition matching with GaAs and having a band gap corresponding to a wavelength of 1.3 μm. A sample having a low surface defect density was obtained at a substrate temperature of 600 ° C. to 750 ° C., and it can be seen that the range of ΔT shown in FIG. 3 is the optimum crystal growth temperature range. When the crystal growth temperature is low, the step flow growth in which crystal growth occurs from the step end is unlikely to occur, and when the crystal growth temperature is high, the group V element once incorporated in the crystal is re-evaporated, which is favorable. No crystal growth occurs.

【００３３】図４に、傾斜角度０°（傾斜していない）
および１０°の基板上に、上記化合物半導体多層膜を、
発光層のＧａ1-xＩｎxＮyＡｓ1-y結晶の組成（ｘ，ｙ）
をさまざまに変えて結晶成長を行い、表面欠陥密度を評
価した結果を示す。図４（ａ）が傾斜角度０°の場合、
図４（ｂ）が傾斜角度１０°の場合である。これによる
と傾斜角度０°の場合、ｙが０．０２５以上では実験し
た範囲内のｘ（０．０１〜０．４）のすべてで表面欠陥
密度が高いのに対し、傾斜角度１０°の場合ｙが０．０
２５以上０．０３以下ではすべての範囲で表面欠陥密度
が十分に低い値となり、またｙが０．１以下ではｘが小
さい範囲では表面欠陥密度が十分低い値となった。FIG. 4 shows an inclination angle of 0 ° (not inclined).
And 10 ° on the substrate, the compound semiconductor multilayer film,
Composition (x, y) of Ga 1-x In x N y As 1-y crystal of light emitting layer
Are shown, the results of crystal growth performed and surface defect density evaluated. FIG. 4A shows a case where the inclination angle is 0 °.
FIG. 4B shows a case where the inclination angle is 10 °. According to this, when the inclination angle is 0 °, when y is 0.025 or more, the surface defect density is high at all x (0.01 to 0.4) within the range of the experiment, while when the inclination angle is 10 °. y is 0.0
When the value was 25 or more and 0.03 or less, the surface defect density was a sufficiently low value in all ranges, and when y was 0.1 or less, the surface defect density was a sufficiently low value when x was small.

【００３４】なお、図１に示したように、ＧａＩｎＮＡ
ｓ層を結晶成長する直前にＮラジカル分子線だけを供給
し、下地のＡｌ0.2Ｇａ0.8Ａｓ層最表面のテラスを形成
するＡｓ原子の一部をＮ原子で置き換え（工程Ｄ）、そ
の後にＧａＩｎＮＡｓ層の結晶成長を開始した（工程
Ｅ）。最初に基板表面のＡｓ原子の一部をＮ原子で置換
しておくと、その後のＡｓとＮとを共に含むＩＩＩ−Ｖ
族化合物半導体混晶の成長がホモエピタキシャル成長と
なるのでステップフロー成長が生じやすく、初期の結晶
成長がスムースに開始され、その上に作製された結晶の
質が向上する。特に電子のド・ブロイ波長よりも薄いＧ
ａＩｎＮＡｓ層を量子井戸層として結晶成長させた場
合、その時に生じる量子効果は、テラスの窒化工程の採
用により著しく増大することがわかった。窒化工程を含
まない場合には、Ａｓ化合物（Ａｌ0.2Ｇａ0.8Ａｓ）と
ＡｓとＮとを共に含むＩＩＩ−Ｖ族化合物半導体混晶
（ＧａＩｎＮＡｓ）との界面とが急俊に切り替わらない
為に量子効果が低減していると考えられる。界面に窒化
工程を入れることで、その組成の切り替えが急俊に生じ
るようになり、良好な界面が得られるようになる。Note that, as shown in FIG.
Immediately before crystal growth of the s layer, only N radical molecular beams are supplied, and part of As atoms forming the terrace on the outermost surface of the underlying Al 0.2 Ga 0.8 As layer is replaced with N atoms (step D). Crystal growth of the layer was started (step E). When part of the As atoms on the substrate surface is first replaced with N atoms, the subsequent III-V containing both As and N
Since the growth of the group compound semiconductor mixed crystal is homoepitaxial growth, step flow growth is likely to occur, and the initial crystal growth is started smoothly, and the quality of the crystal formed thereon is improved. Especially G thinner than the electron's de Broglie wavelength
It was found that when the aInNAs layer was grown as a quantum well layer, the quantum effect generated at that time was significantly increased by adopting the terrace nitriding step. In the case where the nitriding step is not included, since the interface between the As compound (Al 0.2 Ga 0.8 As) and the III-V compound semiconductor mixed crystal (GaInNAs) containing both As and N does not switch rapidly, It is considered that the effect has been reduced. By introducing a nitriding step at the interface, the composition can be switched quickly and a good interface can be obtained.

【００３５】以上のように、本発明により、高品質のＧ
ａＩｎＮＡｓ混晶を得ることができた。さらに、上記の
方法を、１．３μｍの波長域に対応する活性層の作製に
適用して半導体レーザ素子を作製したところ、高性能の
レーザが得られた。As described above, according to the present invention, high quality G
An aInNAs mixed crystal was obtained. Further, when the above method was applied to the production of an active layer corresponding to a wavelength region of 1.3 μm to produce a semiconductor laser device, a high-performance laser was obtained.

【００３６】（実施の形態２）本発明の実施形態２とし
て、（００１）面から（１１１）Ａ面方向へ傾斜したＧ
ａＡｓ基板の上に、有機金属気相成長（Ｍｅｔａｌ Ｏ
ｒｇａｎｉｃ Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄｅｐ
ｏｓｉｔｉｏｎ：ＭＯ−ＣＶＤ）法を用いてＧａＩｎＰ
／ＧａＩｎＮＡｓ／ＧａＩｎＰからなる単一量子井戸構
造を作製した場合について示す。(Embodiment 2) As Embodiment 2 of the present invention, G inclined from the (001) plane to the (111) A plane direction.
Metalorganic vapor phase epitaxy (Metal O.D.
rganic Chemical Vapor Dep
GaInP using the MO: CVD method.
The case where a single quantum well structure composed of / GaInNAs / GaInP is manufactured will be described.

【００３７】（００１）面から（１１１）Ａ面方向へ傾
斜した表面を有するＧａＡｓ基板を準備し、その上に、
トリメチルガリウム（ＴＭＧ），トリメチルインジウム
（ＴＭＩ），アルシン（ＡｓＨ3），フォスフィン（Ｐ
Ｈ3），ジメチルヒドラジン（ＤＭｅＨｙ）を原料ガス
とし、水素（Ｈ2）をキャリアガスとするＭＯ−ＣＶＤ
法により化合物半導体の多層膜を結晶成長した。A GaAs substrate having a surface inclined from the (001) plane to the (111) A plane direction is prepared.
Trimethyl gallium (TMG), trimethyl indium (TMI), arsine (AsH 3 ), phosphine (P
MO-CVD using H 3 ), dimethylhydrazine (DMeHy) as a source gas and hydrogen (H 2 ) as a carrier gas
A compound semiconductor multilayer film was crystal-grown by the method.

【００３８】作製した多層膜の構造は、まずＧａＡｓ基
板の上に層厚０．５μｍのＧａＡｓからなるバッファ層
を、その上にＧａ0.51Ｉｎ0.49Ｐからなる第一障壁層
を、その上に層厚８ｎｍのＧａ0.89Ｉｎ0.11Ｎ0.04Ａｓ
0.96からなる単一量子井戸発光層を、その上に層厚０．
５μｍのＧａ0.51Ｉｎ0.49Ｐからなる第二障壁層を、そ
の上に保護層として層厚０．５μｍのＧａＡｓが形成さ
れている。この時のＧａ0.89Ｉｎ0.11Ｎ0.04Ａｓ0.96結
晶は、ＧａＡｓに格子整合するＧａＩｎＮＡｓ結晶であ
る。結晶成長は常圧で行い、結晶成長温度は多層膜を作
製する間中７００℃に保持し、結晶成長速度は１μｍ／
時間とした。The structure of the manufactured multilayer film is as follows. First, a buffer layer made of GaAs having a thickness of 0.5 μm is formed on a GaAs substrate, a first barrier layer made of Ga 0.51 In 0.49 P is formed thereon, and a layer is formed thereon. 8 nm thick Ga 0.89 In 0.11 N 0.04 As
A single quantum well light-emitting layer of 0.96 , with a layer thickness of 0.
A 0.5 μm-thick GaAs layer is formed as a protective layer on a second barrier layer made of 5 μm Ga 0.51 In 0.49 P. At this time, the Ga 0.89 In 0.11 N 0.04 As 0.96 crystal is a GaInNAs crystal lattice-matched to GaAs. The crystal growth was performed at normal pressure, the crystal growth temperature was maintained at 700 ° C. during the production of the multilayer film, and the crystal growth rate was 1 μm /
Time.

【００３９】また、ＭＯ−ＣＶＤ法による結晶成長は、
図５に示すシーケンスで行った。つまり、ＧａＡｓ基板
をＭＯ−ＣＶＤ結晶成長装置内に導入した後、（工程
Ｉ）ＡｓＨ3とＨ2の雰囲気により７００℃にまで昇温
し、その後、（工程Ｊ）ＴＭＧ，ＡｓＨ3により層厚
０．５μｍのＧａＡｓを結晶成長させ、（工程Ｋ）ＴＭ
Ｇ，ＴＭＩ，ＰＨ3により層厚０．５μｍのＧａ0.51Ｉ
ｎ0.49Ｐを得る。次に（工程Ｌ）ＴＭＧとＡｓＨ3とを
供給して１から３分子層分のＧａＡｓを結晶成長した
後、（工程Ｍ）ＤＭｅＨｙだけを供給して成長層最表面
のテラスを形成するＡｓ原子の一部を窒化によりＮ原子
で置き換えた後、（工程Ｎ）ＴＭＧ，ＴＭＩ，Ａｓ
Ｈ3，ＤＭｅＨｙにより層厚８ｎｍのＧａＩｎＮＡｓ層
を得る。再び（工程Ｏ）ＴＭＧとＡｓＨ3とを供給して
１から３分子層分のＧａＡｓを結晶成長した後、（工程
Ｐ）ＴＭＧ，ＴＭＩ，ＰＨ3より層厚０．５μｍのＧａ
0.51Ｉｎ0.49Ｐを、最後に（工程Ｑ）ＴＭＧ，ＡｓＨ3
で０．５μｍのＧａＡｓを得た。各層を結晶成長する際
の各ガスの流量は、それぞれの層に対して最適となるよ
うに調節した。Further, the crystal growth by the MO-CVD method is as follows.
This was performed according to the sequence shown in FIG. That is, after the GaAs substrate is introduced into the MO-CVD crystal growth apparatus, (Step I) the temperature is raised to 700 ° C. in an atmosphere of AsH 3 and H 2 , and then (Step J) the layer thickness is determined by TMG and AsH 3. A 0.5 μm GaAs crystal is grown (Step K) TM
Ga 0.51 I having a layer thickness of 0.5 μm by G, TMI, PH 3
n 0.49 P is obtained. Next, (step L) TMG and AsH 3 are supplied to grow GaAs for one to three molecular layers, and then (step M) only DMeHy is supplied to form As atoms forming a terrace on the outermost surface of the growth layer. Is partially replaced with N atoms by nitridation, (Step N) TMG, TMI, As
A GaInNAs layer having a thickness of 8 nm is obtained by H 3 and DMeHy. (Step O) TMG and AsH 3 are supplied again to grow GaAs for one to three molecular layers, and then (Step P) Ga with a layer thickness of 0.5 μm from TMG, TMI and PH 3.
0.51 In 0.49 P and finally (Step Q) TMG, AsH 3
Was used to obtain 0.5 μm GaAs. The flow rate of each gas during the crystal growth of each layer was adjusted to be optimal for each layer.

【００４０】各試料の表面欠陥密度を評価したところ、
図２に示した第一実施形態のものと同様の結果が得ら
れ、｛００１｝面から｛１１１｝Ａ面方向へ３〜３０
°、望ましくは５〜１５°だけ傾斜した表面を有するＧ
ａＡｓ基板の上へＧａＩｎＮＡｓ結晶を結晶成長するこ
とでその結晶性が格段に向上することが見い出された。
表面欠陥密度の、結晶成長時の基板温度の依存性も図４
と同様の結果であった。When the surface defect density of each sample was evaluated,
The same result as that of the first embodiment shown in FIG. 2 is obtained, and 3 to 30 from the {001} plane to the {111} A plane direction.
°, preferably with a surface inclined by 5 to 15 °
It has been found that the crystallinity is significantly improved by growing a GaInNAs crystal on an aAs substrate.
The dependence of the surface defect density on the substrate temperature during crystal growth is also shown in FIG.
It was the same result as.

【００４１】なお、図５に示したように、下地のＧａＩ
ｎＰ層の上にＧａＩｎＮＡｓ層を結晶成長する前に、数
分子層程度のＡｓ化合物を成長させ（工程Ｌ）、かつそ
の最表面のテラスを形成するＡｓ原子の一部をＮ原子で
置き換え（工程Ｍ）、その後にＧａＩｎＮＡｓ層の結晶
成長を開始した（工程Ｎ）。Ｐ化合物の上にＧａＩｎＮ
Ａｓ層を直接的に結晶成長させると、結晶成長の初期に
おいてＧａＩｎＮＡｓのステップフロー成長が生じにく
く、傾斜基板を用いた効果が十分に発揮されない傾向が
あった。これに対し、Ｐ化合物の上に、Ａｓ化合物の薄
層を界してから結晶成長を開始することで解決されるこ
とが見い出された。Ａｓ化合物の薄層の厚さは、少なく
とも１分子層以上は必要であるが、Ｐ化合物とＧａＩｎ
ＮＡｓ層とのヘテロ接合のバンドラインナップに影響を
与えないように１０分子層以下であるのが望ましい。As shown in FIG. 5, the underlying GaI
Before crystal growth of the GaInNAs layer on the nP layer, an As compound of several molecular layers is grown (step L), and part of the As atoms forming the terrace on the outermost surface is replaced with N atoms (step L). M) Then, the crystal growth of the GaInNAs layer was started (step N). GaInN on P compound
When the As layer is directly crystal-grown, step flow growth of GaInNAs is unlikely to occur in the initial stage of crystal growth, and the effect of using the inclined substrate tends to be insufficient. On the other hand, it has been found that the problem can be solved by initiating crystal growth after a thin layer of the As compound is bounded on the P compound. The thickness of the thin layer of the As compound is required to be at least one molecular layer or more.
It is desirable that the thickness be 10 molecular layers or less so as not to affect the band lineup of the heterojunction with the NAs layer.

【００４２】また、中間層のＡｓ化合物の上にＧａＩｎ
ＮＡｓ層を結晶成長する時には、界面に窒化工程を入れ
て表面のＡｓ原子の一部をＮ原子で置換しておくと、そ
の後のＶ族元素としてＡｓとＮとを共に含むＩＩＩ−Ｖ
族化合物半導体混晶の成長がホモエピタキシャル成長と
なるのでステップフロー成長が生じやすく、初期の結晶
成長がスムースに開始され、その上の成長層の結晶性が
向上する。また、Ａｓ化合物とＡｓとＮとを共に含むＩ
ＩＩ−Ｖ族化合物半導体混晶の組成との切り替えが急峻
に生じるようになる。Further, GaIn is placed on the As compound of the intermediate layer.
At the time of crystal growth of the NAs layer, a nitridation step is performed at the interface to partially replace As atoms on the surface with N atoms, and then III-V containing both As and N as Group V elements.
Since the growth of the group compound semiconductor mixed crystal is homoepitaxial growth, step flow growth is likely to occur, and the initial crystal growth is smoothly started, and the crystallinity of the grown layer thereon is improved. In addition, I containing both an As compound and As and N
The switching to the composition of the II-V compound semiconductor mixed crystal occurs sharply.

【００４３】以上のように、本発明により、高品質のＧ
ａＩｎＮＡｓ混晶を得ることができた。さらに、上記の
方法を、１．５５μｍの波長域に対応する活性層の作製
に適用して半導体レーザ素子を作製したところ、高性能
のレーザが得られた。As described above, according to the present invention, high quality G
An aInNAs mixed crystal was obtained. Furthermore, when the above method was applied to the production of an active layer corresponding to a wavelength range of 1.55 μm to produce a semiconductor laser device, a high-performance laser was obtained.

【００４４】ところで、これまでに示した全ての実施形
態において、｛００１｝基板の傾斜方向は、｛１１１｝
Ａ面の方向から｛００１｝面内で±１０°程度ずれてい
ても表面ステップはＶ族元素で終端するので同様の効果
が得られた。By the way, in all the embodiments described so far, the inclination direction of the {001} substrate is {111}.
Even when the surface step deviates from the direction of the A-plane by about ± 10 ° within the {001} plane, the same effect can be obtained because the surface step is terminated with the group V element.

【００４５】また、基板は閃亜鉛鉱型の半導体結晶であ
ればＧａＡｓやＧａＰに限定されるものではなく、その
他のＩＩＩ−Ｖ族半導体やＩＩ−ＶＩ族半導体結晶でも
同様の効果が得られた。The substrate is not limited to GaAs or GaP as long as it is a zinc blende type semiconductor crystal. Similar effects can be obtained with other III-V semiconductors and II-VI semiconductor crystals. .

【００４６】また、上記の実施形態では固体原料を用い
たＭＢＥ法およびＭＯ−ＣＶＤ法について述べたが、Ｉ
ＩＩ族原料として固体原料，Ｖ族原料としてＡｓＨ3を
用いたガスソースＭＢＥ（ＧＳ−ＭＢＥ）法、あるいは
ＩＩＩ族原料に有機金属化合物，Ｖ族原料にガス原料に
用いた化学分子線エピタキシャル成長（ＣＢＥ）法など
を用いても同様の効果が得られた。In the above embodiment, the MBE method and the MO-CVD method using solid raw materials have been described.
Gas source MBE (GS-MBE) method using a solid raw material as a group II raw material and AsH 3 as a group V raw material, or a chemical molecular beam epitaxial growth (CBE) using an organic metal compound as a group III raw material and a gas raw material as a group V raw material The same effect was obtained by using the method.

【００４７】また、上記の実施形態ではＩＩＩ族元素と
してＧａ，Ｉｎ，Ａｌ，Ｖ族元素としてＡｓ，Ｎを適宜
含んだ化合物について示したが、その他のＩＩＩ族元素
（Ｂ等）やＶ族元素（Ｐ，Ｓｂ等）や不純物元素（Ｚ
ｎ，Ｂｅ，Ｍｇ，Ｔｅ，Ｓ，Ｓｅ，Ｓｉ等）が適宜含ま
れていても同様の効果が得られる。In the above embodiment, a compound containing Ga, In, Al as a group III element and As and N as a group V element as appropriate is described. However, other group III elements (such as B) and group V elements (P, Sb, etc.) and impurity elements (Z
n, Be, Mg, Te, S, Se, Si, etc.), the same effect can be obtained.

【００４８】なお、これまでの記述の中で「上」と示さ
れた方向は基板から離れる方向を示しており、「下」は
基板へ近づく方向を示している。「下」から「上」の方
向へ向かって結晶成長は進行する。In the above description, the direction indicated as "up" indicates a direction away from the substrate, and the "down" indicates a direction approaching the substrate. Crystal growth proceeds from “down” to “up”.

【００４９】本発明は上記の実施形態に示した結晶組
成，バンドギャップ波長，ヘテロ接合の組み合わせに限
定されることなく、ＩＩＩ族元素として少なくともＧａ
とＩｎとを共に含み、Ｖ族元素として少なくともＮとＡ
ｓとを共に含む化合物半導体結晶であれば、他の組成，
バンドギャップをもつ半導体結晶の作製に対して適用す
ることが可能であることは言うまでもない。また、本発
明は成長層が基板結晶に格子整合する場合に限定される
ものではなく、例えば半導体レーザの歪量子井戸構造な
ど、結晶欠陥を誘発するものでなければ格子不整を有す
る混晶比であっても良い。The present invention is not limited to the combination of the crystal composition, bandgap wavelength, and heterojunction shown in the above embodiment, and at least Ga is used as a group III element.
And In together with at least N and A as Group V elements
If the compound semiconductor crystal contains both s and s, another composition,
It goes without saying that the present invention can be applied to the production of a semiconductor crystal having a band gap. Further, the present invention is not limited to the case where the growth layer lattice-matches to the substrate crystal. For example, in a mixed crystal ratio having a lattice mismatch unless a crystal defect is induced, such as a strained quantum well structure of a semiconductor laser. There may be.

【００５０】また、結晶成長の方法、原料に関しても上
記の具体例に示されたもの以外のものを用いることが可
能である。特にＭＢＥ法，ＣＶＤ法共に、ラジカル励起
されたＮ2，ＮＨ3または有機窒素化合物がＮ源として望
ましい。As for the method of crystal growth and the raw materials, those other than those shown in the above specific examples can be used. In particular, in both the MBE method and the CVD method, radical-excited N 2 , NH 3 or an organic nitrogen compound is preferable as the N source.

【００５１】[0051]

【発明の効果】以上のようにこの発明（請求項１）に係
る化合物半導体の製造方法によれば、ＩＩＩ族元素とし
て少なくともＧａとＩｎとを共に含み、Ｖ族元素として
少なくともＮとＡｓとを共に含む化合物半導体結晶を、
非混和領域内に相当する組成でも相分離することなく極
めて均一で良好な結晶性にて作製することができる。特
に、波長１．３μｍ，１．５５μｍに相当するバンドギ
ャップを有し、半導体レーザの活性層として用いるのに
十分な結晶性を有する化合物半導体混晶を作製すること
ができるようになる。As described above, according to the method for manufacturing a compound semiconductor according to the present invention (claim 1), at least Ga and In are contained together as Group III elements, and at least N and As are contained as Group V elements. The compound semiconductor crystal containing both
Even a composition corresponding to an immiscible region can be produced with very uniform and good crystallinity without phase separation. In particular, a compound semiconductor mixed crystal having a band gap corresponding to wavelengths of 1.3 μm and 1.55 μm and having sufficient crystallinity to be used as an active layer of a semiconductor laser can be manufactured.

【００５２】この発明（請求項２，３）に係る化合物半
導体の製造方法によれば、請求項１の効果をより好適に
得ることができる。According to the method of manufacturing a compound semiconductor according to the present invention (claims 2 and 3), the effect of claim 1 can be more suitably obtained.

【００５３】この発明（請求項４）に係る化合物半導体
の製造方法によれば、従来の結晶成長方法では良好な結
晶を得ることができない大きなＮ組成をもつ結晶が得ら
れるようになる。According to the method of manufacturing a compound semiconductor according to the present invention (claim 4), it is possible to obtain a crystal having a large N composition which cannot obtain a good crystal by the conventional crystal growth method.

【００５４】この発明（請求項５）に係る化合物半導体
の製造方法によれば、Ｐ化合物の上のＡｓとＮとを共に
含むＩＩＩ−Ｖ族化合物半導体混晶が結晶成長の初期か
らスムースなステップフロー成長が起こるようになり、
結晶性が向上する。According to the method of manufacturing a compound semiconductor according to the present invention (claim 5), the III-V compound semiconductor mixed crystal containing both As and N on the P compound is a smooth step from the beginning of the crystal growth. Flow growth occurs,
Crystallinity is improved.

【００５５】この発明（請求項６）に係る化合物半導体
の製造方法によれば、その上のＡｓとＮとを共に含むＩ
ＩＩ−Ｖ族化合物半導体混晶が結晶成長の初期からスム
ースなステップフロー成長が起こるようになり、結晶性
が向上する。また、下地のＡｓ化合物とＶ族元素として
ＡｓとＮとを共に含むＩＩＩ−Ｖ族化合物半導体混晶と
の界面が、量子井戸構造を作製するのに十分なくらいに
急峻になる。According to the method for manufacturing a compound semiconductor according to the present invention (claim 6), the compound semiconductor including both As and N thereon is provided.
In the II-V compound semiconductor mixed crystal, smooth step flow growth occurs from the initial stage of crystal growth, and the crystallinity is improved. Further, the interface between the underlying As compound and the III-V compound semiconductor mixed crystal containing both As and N as the group V element becomes steep enough to produce a quantum well structure.

【００５６】この発明（請求項７）に係る化合物半導体
の製造方法によれば、波長１．３μｍ，１．５５μｍに
対応するバンドギャップを有する均一で良好な組成分布
をもつ化合物半導体混晶を格子整合させて得ることがで
きるようになり、請求項１から５の方法で作製される化
合物半導体混晶を用いて光ファイバー通信に重要な高品
質の発光素子を創出することが可能になる。According to the method of manufacturing a compound semiconductor according to the present invention (claim 7), a compound semiconductor mixed crystal having a band gap corresponding to wavelengths of 1.3 μm and 1.55 μm and having a uniform and favorable composition distribution is latticed. It is possible to obtain a high-quality light-emitting element important for optical fiber communication using the compound semiconductor mixed crystal produced by the method according to any one of the first to fifth aspects.

【図面の簡単な説明】[Brief description of the drawings]

【図１】本発明の第一実施形態における結晶成長のタイ
ムチャートを示す図である。（ａ）は基板温度、（ｂ）
から（ｆ）はそれぞれの分子線のシャッターシーケンス
を示す。FIG. 1 is a diagram showing a time chart of crystal growth in a first embodiment of the present invention. (A) is the substrate temperature, (b)
(F) shows the shutter sequence of each molecular beam.

【図２】本発明の第一実施形態において作製されるＧａ
ＩｎＮＡｓ結晶の表面欠陥密度の、基板の傾斜角度依存
性を示す図である。FIG. 2 shows a Ga produced in the first embodiment of the present invention.
FIG. 3 is a diagram illustrating the dependency of the surface defect density of an InNAs crystal on the tilt angle of a substrate.

【図３】本発明の第一実施形態において作製されるＧａ
ＩｎＮＡｓ結晶の表面欠陥密度の、基板温度依存性を示
す図である。FIG. 3 shows a Ga produced in the first embodiment of the present invention.
FIG. 3 is a diagram illustrating the substrate temperature dependence of the surface defect density of an InNAs crystal.

【図４】本発明の第一実施形態において作製されるＧａ
ＩｎＮＡｓ結晶の表面欠陥の、ＩｎおよびＮの組成に対
する依存性を示す図である。（ａ）傾斜なし５°傾斜、
（ｂ）１０°傾斜。FIG. 4 shows a Ga produced in the first embodiment of the present invention.
FIG. 4 is a diagram showing the dependence of the surface defects of an InNAs crystal on the composition of In and N. (A) 5 ° tilt without tilt,
(B) 10 ° tilt.

【図５】本発明の第二実施形態における結晶成長のタイ
ムチャートを示す図である。（ａ）は基板温度、（ｂ）
から（ｆ）はそれぞれの原料ガスのシーケンスを示す。FIG. 5 is a diagram showing a time chart of crystal growth in a second embodiment of the present invention. (A) is the substrate temperature, (b)
(F) shows the sequence of each source gas.

Claims (7)

【特許請求の範囲】[Claims] 【請求項１】 ＩＩＩ族元素として少なくともＧａ（ガ
リウム）とＩｎ（インジウム）とを共に含み、Ｖ族元素
として少なくともＮ（窒素）とＡｓ（砒素）とを共に含
む化合物半導体結晶を少なくとも１層含む積層構造を半
導体基板上に作製する化合物半導体の製造方法であっ
て、 該半導体基板が閃亜鉛鉱型の半導体結晶から成り、かつ
前記基板が｛００１｝面から｛１１１｝Ａ面方向へ傾斜
させた表面を有していることを特徴とする化合物半導体
の製造方法。At least one layer of a compound semiconductor crystal containing at least Ga (gallium) and In (indium) as a group III element and at least N (nitrogen) and As (arsenic) as a group V element is included. A method for producing a compound semiconductor, wherein a laminated structure is formed on a semiconductor substrate, wherein the semiconductor substrate is made of a zinc blende type semiconductor crystal, and the substrate is inclined from a {001} plane to a {111} A plane. A method for producing a compound semiconductor, characterized by having a bent surface. 【請求項２】 請求項１に記載の化合物半導体の製造方
法において、前記基板が｛００１｝面から｛１１１｝Ａ
面方向へ３度以上３０度以下の角度で傾斜された表面を
有していることを特徴とする化合物半導体の製造方法。2. The method for manufacturing a compound semiconductor according to claim 1, wherein the substrate is {111} A from a {001} plane.
A method for manufacturing a compound semiconductor, comprising a surface inclined at an angle of 3 degrees or more and 30 degrees or less in a plane direction. 【請求項３】 請求項１又は２のいずれかに記載の化合
物半導体の製造方法において、前記積層構造は、６００
℃以上７５０℃以下の温度で結晶成長されることを特徴
とする化合物半導体の製造方法。3. The method of manufacturing a compound semiconductor according to claim 1, wherein said laminated structure has a thickness of 600.
A method for producing a compound semiconductor, wherein a crystal is grown at a temperature of from 750C to 750C. 【請求項４】 請求項１乃至３のいずれかに記載の化合
物半導体の製造方法において、前記のＩＩＩ族元素とし
て少なくともＧａとＩｎとを共に含み、Ｖ族元素として
少なくともＮとＡｓとを共に含む化合物半導体結晶は、
Ｖ族元素として結晶中に含まれているＮの組成比 ［Ｎ原子密度］／（［Ｎ原子密度］＋［Ａｓ原子密
度］） が０．０２５以上０．１以下であることを特徴とする化
合物半導体の製造方法。4. The method for producing a compound semiconductor according to claim 1, wherein said group III element contains at least Ga and In together, and said group V element contains at least N and As together. Compound semiconductor crystals
The composition ratio of N contained in the crystal as a group V element [N atom density] / ([N atom density] + [As atom density]) is 0.025 or more and 0.1 or less. A method for manufacturing a compound semiconductor. 【請求項５】 請求項１乃至４のいずれかに記載の化合
物半導体の製造方法において、Ｖ族元素としてＰ（燐）
を含む化合物半導体を積層し、その上にＶ族元素として
Ａｓだけを有する化合物半導体を少なくとも１分子層以
上１０分子層以下積層し、その上に前記のＩＩＩ族元素
として少なくともＧａとＩｎとを共に含み、Ｖ族元素と
して少なくともＮとＡｓとを共に含む化合物半導体結晶
を結晶成長する工程を含んでいることを特徴とする化合
物半導体の製造方法。5. The method for producing a compound semiconductor according to claim 1, wherein P (phosphorus) is used as a group V element.
Is laminated, and a compound semiconductor having only As as a group V element is laminated thereon at least one molecular layer or more and ten molecular layers or less, and at least Ga and In as the above-mentioned group III element together are formed. A method of manufacturing a compound semiconductor, comprising the step of: crystal growing a compound semiconductor crystal containing at least N and As as group V elements. 【請求項６】 請求項１乃至５のいずれかに記載の化合
物半導体の製造方法において、ＩＩＩ族元素として少な
くともＧａとＩｎとを共に含み、Ｖ族元素として少なく
ともＮとＡｓとを共に含む化合物半導体結晶を結晶成長
する直前に、Ｎ原料だけを供給する工程を含むことを特
徴とする化合物半導体の製造方法。6. The method of manufacturing a compound semiconductor according to claim 1, wherein the compound semiconductor includes at least Ga and In as a group III element and at least N and As as a group V element. A method for producing a compound semiconductor, comprising a step of supplying only an N raw material immediately before growing a crystal. 【請求項７】 請求項１乃至６のいずれかに記載の化合
物半導体の製造方法において、基板として用いる閃亜鉛
鉱型の半導体結晶がＧａＡｓからなることを特徴とする
化合物半導体の製造方法。7. The method for producing a compound semiconductor according to claim 1, wherein the zinc-blende-type semiconductor crystal used as the substrate is made of GaAs.
JP12845497A 1997-05-19 1997-05-19 Method for producing compound semiconductor Expired - Fee Related JP4002323B2 (en)

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JPH10321959A true JPH10321959A (en) 1998-12-04
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100591252B1 (en) * 2001-11-05 2006-06-19 주식회사 비첼 InGaNAs COMPOUND SEMICONDUCTOR THIN FILM AND METHOD FOR GROWTH THEREOF
JP2006339675A (en) * 2006-09-07 2006-12-14 Sharp Corp Nitride semiconductor laser element and semiconductor optical device
JP2008066327A (en) * 2006-09-04 2008-03-21 Sumitomo Electric Ind Ltd Method for growing iii-v compound semiconductor

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100591252B1 (en) * 2001-11-05 2006-06-19 주식회사 비첼 InGaNAs COMPOUND SEMICONDUCTOR THIN FILM AND METHOD FOR GROWTH THEREOF
JP2008066327A (en) * 2006-09-04 2008-03-21 Sumitomo Electric Ind Ltd Method for growing iii-v compound semiconductor
JP2006339675A (en) * 2006-09-07 2006-12-14 Sharp Corp Nitride semiconductor laser element and semiconductor optical device

Also Published As

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