JP2012109557A - Semiconductor substrate, method of manufacturing semiconductor substrate, and vertical resonator surface-emitting laser - Google Patents

Semiconductor substrate, method of manufacturing semiconductor substrate, and vertical resonator surface-emitting laser Download PDF

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JP2012109557A
JP2012109557A JP2011233934A JP2011233934A JP2012109557A JP 2012109557 A JP2012109557 A JP 2012109557A JP 2011233934 A JP2011233934 A JP 2011233934A JP 2011233934 A JP2011233934 A JP 2011233934A JP 2012109557 A JP2012109557 A JP 2012109557A
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Migaku Ichikawa
磨 市川
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Sumitomo Chemical Co Ltd
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    • H01S5/183—Surface-emitting [SE] lasers, e.g. having both horizontal and vertical cavities having only vertical cavities, e.g. vertical cavity surface-emitting lasers [VCSEL]
    • H01S5/18308—Surface-emitting [SE] lasers, e.g. having both horizontal and vertical cavities having only vertical cavities, e.g. vertical cavity surface-emitting lasers [VCSEL] having a special structure for lateral current or light confinement
    • H01S5/18311—Surface-emitting [SE] lasers, e.g. having both horizontal and vertical cavities having only vertical cavities, e.g. vertical cavity surface-emitting lasers [VCSEL] having a special structure for lateral current or light confinement using selective oxidation
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    • H01S5/32—Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures
    • H01S5/3202—Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures grown on specifically orientated substrates, or using orientation dependent growth
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    • H01S5/34—Structure or shape of the active region; Materials used for the active region comprising quantum well or superlattice structures, e.g. single quantum well [SQW] lasers, multiple quantum well [MQW] lasers or graded index separate confinement heterostructure [GRINSCH] lasers
    • H01S5/343—Structure or shape of the active region; Materials used for the active region comprising quantum well or superlattice structures, e.g. single quantum well [SQW] lasers, multiple quantum well [MQW] lasers or graded index separate confinement heterostructure [GRINSCH] lasers in AIIIBV compounds, e.g. AlGaAs-laser, InP-based laser
    • H01S5/34313—Structure or shape of the active region; Materials used for the active region comprising quantum well or superlattice structures, e.g. single quantum well [SQW] lasers, multiple quantum well [MQW] lasers or graded index separate confinement heterostructure [GRINSCH] lasers in AIIIBV compounds, e.g. AlGaAs-laser, InP-based laser with a well layer having only As as V-compound, e.g. AlGaAs, InGaAs
    • H01S5/3432—Structure or shape of the active region; Materials used for the active region comprising quantum well or superlattice structures, e.g. single quantum well [SQW] lasers, multiple quantum well [MQW] lasers or graded index separate confinement heterostructure [GRINSCH] lasers in AIIIBV compounds, e.g. AlGaAs-laser, InP-based laser with a well layer having only As as V-compound, e.g. AlGaAs, InGaAs the whole junction comprising only (AI)GaAs

Abstract

PROBLEM TO BE SOLVED: To reduce the cost of material gases in manufacturing a semiconductor substrate for a vertical resonator surface-emitting laser, and to control the impurity concentration of a p-type semiconductor layer in the semiconductor substrate for the vertical resonator surface-emitting laser.SOLUTION: In a semiconductor substrate for a vertical resonator surface-emitting laser having a p-type crystal layer, the p-type crystal layer is composed of a group III-V compound semiconductor, contains carbon atoms as p-type impurity atoms, and contains hydrogen atoms with a concentration of 6×10cmor more to 6×10cmor less.

Description

本発明は、半導体基板、半導体基板の製造方法および垂直共振器面発光レーザに関する。   The present invention relates to a semiconductor substrate, a method for manufacturing a semiconductor substrate, and a vertical cavity surface emitting laser.

特許文献１には、ＧａＡｓ基板と、ｎ型の下部ＤＢＲ（Distributed Bragg Reflector）と、活性領域と、活性領域上に形成されたｐ型の電流狭窄層と、電流狭窄層上に形成されたｐ型の高濃度ＤＢＲおよびｐ型のＤＢＲとを有するＶＣＳＥＬ（Vertical-Cavity Surface-Emitting Laser）が記載されている。また特許文献１には、ｎ型の下部ＤＢＲ、ｐ型の高濃度ＤＢＲおよびｐ型のＤＢＲは、ＡｌＧａＡｓ層からなる高屈折率層と低屈折率層の対をそれぞれ含むことが記載されている。   Patent Document 1 discloses a GaAs substrate, an n-type lower DBR (Distributed Bragg Reflector), an active region, a p-type current confinement layer formed on the active region, and a p formed on the current confinement layer. A VCSEL (Vertical-Cavity Surface-Emitting Laser) having a high-concentration type DBR and a p-type DBR is described. Patent Document 1 describes that the n-type lower DBR, the p-type high concentration DBR, and the p-type DBR each include a pair of a high refractive index layer and a low refractive index layer made of an AlGaAs layer. .

特許文献２には、Ｓｉ単結晶基板上に、低温成長ＧａＡｓ層、Ｓｉ原子の拡散を抑止するためのＡｌｘＧａ１−ｘＡｓ（ｘ＝０〜０．３）拡散抑止層、高温成長ＧａＡｓ層をこの順に積層させたＧａＡｓ基板が記載されている。ここで特許文献２には、ＡｌｘＧａ１−ｘＡｓ拡散抑止層は、ＭＯＣＶＤ法を用い、原料ガスのアルシン／トリメチルガリウムの圧力比を１０以下として成長させることが記載されている。
特許文献１ 特開２００９−１９４１０３号公報
特許文献２ 特開平５−２３４９０７号公報 Patent Document 2 discloses a low-temperature grown GaAs layer on an Si single crystal substrate, an Al x Ga 1-x As (x = 0 to 0.3) diffusion suppression layer for suppressing the diffusion of Si atoms, and a high-temperature grown GaAs. A GaAs substrate in which layers are stacked in this order is described. Here, Patent Document 2 describes that the Al x Ga 1-x As diffusion suppression layer is grown by using the MOCVD method with a source gas arsine / trimethylgallium pressure ratio of 10 or less.
Patent Document 1 Japanese Patent Application Laid-Open No. 2009-194103 Patent Document 2 Japanese Patent Application Laid-Open No. 5-234907

垂直共振器面発光レーザ（ＶＣＳＥＬ）の層構成に適合した半導体基板の製造において、ＭＯＣＶＤ（Metal Organic Chemical Vapor Deposition）法が用いられる。ＭＯＣＶＤ法によりＧａＡｓ層、ＡｌＧａＡｓ層、ＩｎＧａＡｓ層、ＩｎＧａＡｓＰ層等の３−５族化合物半導体結晶層を成長させる場合、３族原料ガスとしてＡｌ、Ｇａ、Ｉｎ等３族原子の有機化合物が用いられる。また、５族原料ガスとしてＡｓ、Ｐ等５族原子の水素化合物が用いられる。３族原料ガス供給量に対する５族原料ガス供給量のモル比（Ｖ／ＩＩＩ比）を大きくすると、表面が平坦な結晶層を得ることができるので、一般にＶ／ＩＩＩ比を大きくして結晶層を成長させる。   A MOCVD (Metal Organic Chemical Vapor Deposition) method is used in the manufacture of a semiconductor substrate adapted to the layer structure of a vertical cavity surface emitting laser (VCSEL). When a group 3-5 compound semiconductor crystal layer such as a GaAs layer, an AlGaAs layer, an InGaAs layer, or an InGaAsP layer is grown by MOCVD, an organic compound of a group 3 atom such as Al, Ga, or In is used as a group 3 source gas. Further, as a Group 5 source gas, a hydrogen compound of a Group 5 atom such as As or P is used. When the molar ratio (V / III ratio) of the Group 5 source gas supply amount to the Group 3 source gas supply amount is increased, a crystal layer having a flat surface can be obtained. Grow.

しかし、Ｖ／ＩＩＩ比が大きいと、未反応のまま排気される５族原料ガスが多くなるので、原料ガスのロスが大きくなることがある。また、Ｖ／ＩＩＩ比に応じて３−５族化合物半導体にｐ型不純物がドーピングされることがあるので、ｐ型不純物量を適正に制御する必要がある。本発明の目的は、垂直共振器面発光レーザ用の半導体基板の製造において、原料ガスのコストを低減することにある。また、本発明の目的は、垂直共振器面発光レーザ用の半導体基板におけるｐ型半導体層の不純物濃度を容易に制御することにある。   However, when the V / III ratio is large, the amount of the group 5 source gas exhausted unreacted increases, which may increase the loss of the source gas. Moreover, since the p-type impurity may be doped in the group 3-5 compound semiconductor according to the V / III ratio, it is necessary to appropriately control the p-type impurity amount. An object of the present invention is to reduce the cost of source gas in the manufacture of a semiconductor substrate for a vertical cavity surface emitting laser. Another object of the present invention is to easily control the impurity concentration of the p-type semiconductor layer in the semiconductor substrate for the vertical cavity surface emitting laser.

上記課題を解決するために、本発明の第１の態様においては、ｐ型結晶層を有する垂直共振器面発光レーザ用の半導体基板であって、ｐ型結晶層が、３−５族化合物半導体からなり、ｐ型不純物原子として炭素原子を含み、かつ、６×１０１７ｃｍ−３以上、６×１０１９ｃｍ−３以下の濃度の水素原子を含む半導体基板を提供する。 In order to solve the above-mentioned problem, in the first aspect of the present invention, a semiconductor substrate for a vertical cavity surface emitting laser having a p-type crystal layer, wherein the p-type crystal layer is a group 3-5 compound semiconductor. A semiconductor substrate containing carbon atoms as p-type impurity atoms and containing hydrogen atoms at a concentration of 6 × 10 17 cm −3 or more and 6 × 10 19 cm −3 or less is provided.

ｐ型結晶層として、半導体基板が垂直共振器面発光レーザに用いられた場合にコンタクト層として機能するｐ型ＧａＡｓ層が挙げられる。ｐ型ＧａＡｓ層が、１×１０１９ｃｍ−３以上、６×１０１９ｃｍ−３以下の濃度の水素原子を含んでもよい。 Examples of the p-type crystal layer include a p-type GaAs layer that functions as a contact layer when the semiconductor substrate is used in a vertical cavity surface emitting laser. The p-type GaAs layer may include hydrogen atoms having a concentration of 1 × 10 19 cm −3 or more and 6 × 10 19 cm −3 or less.

半導体基板が垂直共振器面発光レーザに用いられた場合にｐ型ミラー層の少なくとも一部として機能するｐ型積層結晶層を有してもよく、ｐ型積層結晶層として、ｐ型ＡｌｍＧａ１−ｍＡｓ（０＜ｍ≦１）からなる第１結晶層と、ｐ型ＡｌｎＧａ１−ｎＡｓ（０≦ｎ＜１、ｍ＞ｎ）からなる第２結晶層とを含む積層結晶層が挙げられ、第１結晶層が、ｐ型結晶層であってもよい。 When the semiconductor substrate is used for a vertical cavity surface emitting laser, the semiconductor substrate may have a p-type stacked crystal layer that functions as at least a part of the p-type mirror layer. As the p-type stacked crystal layer, p-type Al m Ga Multilayer crystal including a first crystal layer made of 1-m As (0 <m ≦ 1) and a second crystal layer made of p-type Al n Ga 1-n As (0 ≦ n <1, m> n) The first crystal layer may be a p-type crystal layer.

第１結晶層として、ｐ型ＡｌｍＧａ１−ｍＡｓ層（０．５０≦ｍ≦１．０）が挙げられる。第１結晶層が、６×１０１７ｃｍ−３以上、２．５×１０１８ｃｍ−３以下の濃度の水素原子を含んでもよい。第２結晶層に含まれる水素原子の濃度が、第１結晶層に含まれる水素原子の濃度より低くてもよい。第１結晶層が、７×１０１７ｃｍ−３以上、５×１０１８ｃｍ−３以下の濃度の酸素原子を含んでもよい。 An example of the first crystal layer is a p-type Al m Ga 1-m As layer (0.50 ≦ m ≦ 1.0). The first crystal layer may include hydrogen atoms having a concentration of 6 × 10 17 cm −3 or more and 2.5 × 10 18 cm −3 or less. The concentration of hydrogen atoms contained in the second crystal layer may be lower than the concentration of hydrogen atoms contained in the first crystal layer. The first crystal layer may include oxygen atoms having a concentration of 7 × 10 17 cm −3 or more and 5 × 10 18 cm −3 or less.

本発明の第２の態様においては、垂直共振器面発光レーザ用の半導体基板の製造方法であって、３族原料ガスと５族原料ガスとを用いたＭＯＣＶＤ法によりｐ型結晶層を成長する段階を有し、３族原料ガスが、３族原子に少なくとも１つのアルキル基が結合した３族原子のアルキル化物を含み、５族原料ガスが、５族原子の水素化物を含み、ｐ型結晶層を成長する段階において、３族原料ガスのモル供給量に対する５族原料ガスのモル供給量の比（Ｖ／ＩＩＩ比）を０．７以上３０以下に制御する半導体基板の製造方法を提供する。   According to a second aspect of the present invention, there is provided a method for manufacturing a semiconductor substrate for a vertical cavity surface emitting laser, wherein a p-type crystal layer is grown by MOCVD using a group 3 source gas and a group 5 source gas. The group 3 source gas includes an alkylated group 3 atom in which at least one alkyl group is bonded to the group 3 atom, the group 5 source gas includes a hydride of the group 5 atom, and a p-type crystal Provided is a method for manufacturing a semiconductor substrate, wherein a ratio of a molar supply amount of a Group 5 source gas to a molar supply amount of a Group 3 source gas (V / III ratio) is controlled to 0.7 or more and 30 or less in a stage of growing a layer. .

ｐ型結晶層を成長する段階において、３族原料ガスおよび５族原料ガスに、炭素化合物を添加してもよい。炭素化合物として、ＣＸ４−ｙＨｙ（ただし、Ｘはハロゲン原子であり、ｙは０以上３以下の整数である。）で表される化合物が挙げられる。ｐ型結晶層を成長する段階において、ｐ型ＡｌｍＧａ１−ｍＡｓ（０＜ｍ≦１）からなる第１結晶層を成長させ、当該方法は、３族原料ガスおよび５族原料ガスを用いたＭＯＣＶＤ法により、ｐ型ＡｌｎＧａ１−ｎＡｓ（０≦ｎ＜１、ｍ＞ｎ）からなる第２結晶層を成長する段階をさらに有し、第１結晶層および第２結晶層を複数回繰り返して成長させることによりｐ型積層結晶層を形成し、第２結晶層を成長する段階において、３族原料ガスおよび５族原料ガスに、ｐ型不純物原子を含有する化合物を添加してもよい。ｐ型不純物原子を含有する化合物として、ＣＸ４−ｙＨｙ（ただし、Ｘはハロゲン原子であり、ｙは０以上３以下の整数である。）で表される化合物が挙げられる。当該方法は、３族原料ガスと５族原料ガスとを用いてｎ型結晶層またはｉ型結晶層を成長する段階を更に有し、ｐ型結晶層を成長する段階におけるＶ／ＩＩＩ比が、ｎ型結晶層またはｉ型結晶層を成長する段階におけるいずれのＶ／ＩＩＩ比よりも小さくてよい。 In the stage of growing the p-type crystal layer, a carbon compound may be added to the group 3 source gas and the group 5 source gas. Examples of the carbon compound include compounds represented by CX 4-y H y (where X is a halogen atom, and y is an integer of 0 or more and 3 or less). In the step of growing the p-type crystal layer, a first crystal layer made of p-type Al m Ga 1-m As (0 <m ≦ 1) is grown, and the method includes a group 3 source gas and a group 5 source gas. The method further comprises growing a second crystal layer made of p-type Al n Ga 1-n As (0 ≦ n <1, m> n) by the MOCVD method used, and the first crystal layer and the second crystal layer In this stage, a compound containing p-type impurity atoms is added to the Group 3 source gas and the Group 5 source gas at the stage of forming the p-type stacked crystal layer by repeating the growth several times and growing the second crystal layer. May be. Examples of the compound containing a p-type impurity atom include a compound represented by CX 4-y H y (where X is a halogen atom, and y is an integer of 0 or more and 3 or less). The method further includes the step of growing an n-type crystal layer or an i-type crystal layer using a Group 3 source gas and a Group 5 source gas, and the V / III ratio in the step of growing the p-type crystal layer is It may be smaller than any V / III ratio in the stage of growing the n-type crystal layer or the i-type crystal layer.

本発明の第３の態様においては、コンタクト層として機能するｐ型結晶層、または、ｐ型ミラー層の少なくとも一部として機能するｐ型結晶層を有し、ｐ型結晶層が、３−５族化合物半導体からなり、ｐ型不純物原子として炭素原子を含み、かつ、６×１０１７ｃｍ−３以上、６×１０１９ｃｍ−３以下の濃度の水素原子を含む垂直共振器面発光レーザを提供する。 In the third aspect of the present invention, a p-type crystal layer that functions as a contact layer or a p-type crystal layer that functions as at least a part of a p-type mirror layer, and the p-type crystal layer is 3-5 A vertical cavity surface emitting laser comprising a group compound semiconductor, containing carbon atoms as p-type impurity atoms, and containing hydrogen atoms at a concentration of 6 × 10 17 cm −3 or more and 6 × 10 19 cm −3 or less To do.

半導体基板１００の断面例を示す。An example of a cross section of a semiconductor substrate 100 is shown. 垂直共振器面発光レーザ２００の断面例を示す。The cross-sectional example of the vertical cavity surface emitting laser 200 is shown.

図１は、半導体基板１００の断面例を示す。半導体基板１００は、ベース基板１０２、バッファ層１０４、ｎ型積層結晶層１０６、ｉ型積層結晶層１０８、ｐ型ＡｌＧａＡｓ層１１０、ｐ型積層結晶層１１２およびｐ型ＧａＡｓ層１１４を有する。   FIG. 1 shows an example of a cross section of a semiconductor substrate 100. The semiconductor substrate 100 includes a base substrate 102, a buffer layer 104, an n-type stacked crystal layer 106, an i-type stacked crystal layer 108, a p-type AlGaAs layer 110, a p-type stacked crystal layer 112, and a p-type GaAs layer 114.

ベース基板１０２は、その上に形成されるエピタキシャル成長層を支持する支持基板である。ベース基板１０２としてｎ型ＧａＡｓ基板が挙げられる。ベース基板１０２にｎ型ＧａＡｓ基板を用いる場合、ｎ型ＧａＡｓ基板の（１００）面または（１００）面と適当なオフ角を有する面にエピタキシャル成長層が形成される。オフ角は、たとえば２°〜１０°の範囲、好ましくは５°が挙げられる。ｎ型ＧａＡｓ基板にドーピングされる不純物原子としてＳｉ、Ｓｅ、Ｓが挙げられる。ｎ型ＧａＡｓ基板のキャリア濃度は、１×１０１７ｃｍ−３〜１×１０１９ｃｍ−３の範囲、好ましくは１×１０１８ｃｍ−３〜４×１０１８ｃｍ−３の範囲が挙げられる。 The base substrate 102 is a support substrate that supports an epitaxial growth layer formed thereon. An example of the base substrate 102 is an n-type GaAs substrate. When an n-type GaAs substrate is used as the base substrate 102, an epitaxial growth layer is formed on the (100) plane of the n-type GaAs substrate or a plane having an appropriate off angle with the (100) plane. The off angle is, for example, in the range of 2 ° to 10 °, preferably 5 °. Examples of impurity atoms doped into the n-type GaAs substrate include Si, Se, and S. The carrier concentration of the n-type GaAs substrate is in the range of 1 × 10 17 cm −3 to 1 × 10 19 cm −3 , preferably in the range of 1 × 10 18 cm −3 to 4 × 10 18 cm −3 .

ベース基板１０２は、サファイア基板、シリコンカーバイド基板、酸化亜鉛基板、または、表面がシリコンである基板であってもよい。ここで、「表面がシリコン」とは、少なくとも基板の表面の一部がシリコンで構成されることを意味する。たとえばＳｉウェハのように基板全体がシリコンで構成されていてもよく、ＳＯＩ（ｓｉｌｉｃｏｎ−ｏｎ−ｉｎｓｕｌａｔｏｒ）基板のように絶縁層の上にシリコン層を有する構造であってもよい。あるいはサファイア基板、ガラス基板、シリコンカーバイド基板、酸化亜鉛基板、ＧａＡｓ基板等シリコン以外の材料からなる基板上にシリコン層が形成されたものでもよい。エピタキシャル成長層と接するベース基板１０２の材料が半導体である場合には、当該半導体材料にｎ型不純物がドーピングされていることが好ましい。ベース基板１０２の全部または一部がｎ型の伝導型を有することにより、ベース基板１０２に電極を接続できる。例えば半導体基板１００が垂直共振器面発光レーザに用いられた場合、ベース基板１０２にレーザのカソード側電極を接続できる。   The base substrate 102 may be a sapphire substrate, a silicon carbide substrate, a zinc oxide substrate, or a substrate whose surface is silicon. Here, “the surface is silicon” means that at least a part of the surface of the substrate is made of silicon. For example, the entire substrate may be made of silicon such as a Si wafer, or a structure having a silicon layer on an insulating layer such as an SOI (silicon-on-insulator) substrate. Alternatively, a silicon layer may be formed on a substrate made of a material other than silicon, such as a sapphire substrate, a glass substrate, a silicon carbide substrate, a zinc oxide substrate, or a GaAs substrate. When the material of the base substrate 102 in contact with the epitaxial growth layer is a semiconductor, the semiconductor material is preferably doped with an n-type impurity. When all or part of the base substrate 102 has n-type conductivity, an electrode can be connected to the base substrate 102. For example, when the semiconductor substrate 100 is used for a vertical cavity surface emitting laser, the cathode electrode of the laser can be connected to the base substrate 102.

バッファ層１０４は、ベース基板１０２の上にエピタキシャル成長により形成されたｎ型３−５族化合物半導体結晶層である。バッファ層１０４は、ベース基板１０２中の欠陥に応じて、ｎ型積層結晶層１０６、ｉ型積層結晶層１０８などにも欠陥が形成されることを抑制する。バッファ層１０４としてｎ型ＧａＡｓ層が挙げられる。バッファ層１０４にｎ型ＧａＡｓ層を用いる場合、ｎ型ＧａＡｓ層の厚さは、１０ｎｍ〜１０００ｎｍの範囲内であることが好ましい。ｎ型ＧａＡｓ層にドーピングされる不純物原子として、Ｓｉ、Ｓｅ、Ｓが挙げられる。ｎ型ＧａＡｓ層のキャリア濃度は、１×１０１８ｃｍ−３〜５×１０１８ｃｍ−３の範囲内であることが好ましい。 The buffer layer 104 is an n-type group 3-5 compound semiconductor crystal layer formed on the base substrate 102 by epitaxial growth. The buffer layer 104 suppresses the formation of defects in the n-type stacked crystal layer 106, the i-type stacked crystal layer 108, and the like in accordance with the defects in the base substrate 102. An example of the buffer layer 104 is an n-type GaAs layer. When an n-type GaAs layer is used for the buffer layer 104, the thickness of the n-type GaAs layer is preferably in the range of 10 nm to 1000 nm. Examples of impurity atoms doped in the n-type GaAs layer include Si, Se, and S. The carrier concentration of the n-type GaAs layer is preferably in the range of 1 × 10 18 cm −3 to 5 × 10 18 cm −3 .

ｎ型積層結晶層１０６は、バッファ層１０４の上にエピタキシャル成長により形成された、複数のｎ型３−５族化合物半導体結晶層からなる積層結晶層である。ｎ型積層結晶層１０６は、半導体基板１００が垂直共振器面発光レーザに用いられた場合に、共振器の一方のミラーであるｎ型ミラー層として機能する。ｎ型積層結晶層１０６は、例えば分布ブラッグ反射器（ＤＢＲ）である。ｎ型積層結晶層１０６は、高屈折率層と低屈折率層を交互に積層した積層構造を複数含んでもよい。高屈折率層と低屈折率層を複数繰り返して配置することで、所定の波長の光の反射率を高くできる。   The n-type stacked crystal layer 106 is a stacked crystal layer made of a plurality of n-type group 3-5 compound semiconductor crystal layers formed on the buffer layer 104 by epitaxial growth. The n-type stacked crystal layer 106 functions as an n-type mirror layer that is one mirror of the resonator when the semiconductor substrate 100 is used in a vertical cavity surface emitting laser. The n-type stacked crystal layer 106 is, for example, a distributed Bragg reflector (DBR). The n-type stacked crystal layer 106 may include a plurality of stacked structures in which high refractive index layers and low refractive index layers are alternately stacked. By repeatedly arranging a plurality of high refractive index layers and low refractive index layers, the reflectance of light having a predetermined wavelength can be increased.

ｎ型積層結晶層１０６に含まれる低屈折率層として、ｎ型ＡｌｑＧａ１−ｑＡｓ（０＜ｑ≦１）層が挙げられる。半導体基板１００が垂直共振器面発光レーザに用いられた場合、当該低屈折率層に用いるｎ型ＡｌｑＧａ１−ｑＡｓ（０＜ｑ≦１）層の厚さは、レーザに要求される発光波長帯に応じて設計される。ｎ型ＡｌｑＧａ１−ｑＡｓ（０＜ｑ≦１）層のＡｌ組成（ｑ）は、０．８〜１．０の範囲内であることが適切である。ｎ型ＡｌｑＧａ１−ｑＡｓ（０＜ｑ≦１）層にドーピングされる不純物原子として、Ｓｉ、Ｓｅ、Ｓが挙げられる。ｎ型ＡｌｑＧａ１−ｑＡｓ（０＜ｑ≦１）層のキャリア濃度は、１×１０１８ｃｍ−３〜３×１０１８ｃｍ−３の範囲内であることが好ましい。 Examples of the low refractive index layer included in the n-type stacked crystal layer 106 include an n-type Al q Ga 1 -q As (0 <q ≦ 1) layer. When the semiconductor substrate 100 is used for a vertical cavity surface emitting laser, the thickness of the n-type Al q Ga 1-q As (0 <q ≦ 1) layer used for the low refractive index layer is required for the laser. It is designed according to the emission wavelength band. The Al composition (q) of the n-type Al q Ga 1 -q As (0 <q ≦ 1) layer is suitably in the range of 0.8 to 1.0. Examples of impurity atoms doped in the n-type Al q Ga 1-q As (0 <q ≦ 1) layer include Si, Se, and S. The carrier concentration of the n-type Al q Ga 1-q As (0 <q ≦ 1) layer is preferably in the range of 1 × 10 18 cm −3 to 3 × 10 18 cm −3 .

ｎ型積層結晶層１０６に含まれる高屈折率層として、ｎ型ＡｌｒＧａ１−ｒＡｓ（０≦ｒ＜１、ｑ＞ｒ）層が挙げられる。ｎ型ＡｌｒＧａ１−ｒＡｓ（０≦ｒ＜１、ｑ＞ｒ）層のＡｌ組成（ｒ）をｎ型ＡｌｑＧａ１−ｑＡｓ（０＜ｑ≦１）層のＡｌ組成（ｑ）より小さくすることで、ｎ型ＡｌｒＧａ１−ｒＡｓ（０≦ｒ＜１、ｑ＞ｒ）層の屈折率をｎ型ＡｌｑＧａ１−ｑＡｓ（０＜ｑ≦１）層の屈折率より大きくできる。半導体基板１００が垂直共振器面発光レーザに用いられた場合に、当該高屈折率層に用いるｎ型ＡｌｒＧａ１−ｒＡｓ（０≦ｒ＜１、ｑ＞ｒ）層の厚さは、レーザに要求される発光波長帯に応じて設計される。ｎ型ＡｌｒＧａ１−ｒＡｓ（０≦ｒ＜１、ｑ＞ｒ）層のＡｌ組成（ｒ）は、０．０〜０．２の範囲内（ただしｎ型ＡｌｑＧａ１−ｑＡｓ（０＜ｑ≦１）層のＡｌ組成（ｑ）より小さい）であることが適切である。ｎ型ＡｌｒＧａ１−ｒＡｓ（０≦ｒ＜１、ｑ＞ｒ）層にドーピングされる不純物原子として、Ｓｉ、Ｓｅ、Ｓが挙げられる。ｎ型ＡｌｒＧａ１−ｒＡｓ（０≦ｒ＜１、ｑ＞ｒ）層のキャリア濃度は、１×１０１８ｃｍ−３〜３×１０１８ｍ−３の範囲内であることが好ましい。 Examples of the high refractive index layer included in the n-type stacked crystal layer 106 include an n-type Al r Ga 1-r As (0 ≦ r <1, q> r) layer. The Al composition (r) of the n - type Al r Ga 1-r As (0 ≦ r <1, q> r) layer is changed to the Al composition ( q of the n-type Al q Ga 1-q As (0 <q ≦ 1) layer). ), The refractive index of the n - type Al r Ga 1-r As (0 ≦ r <1, q> r) layer is made smaller than that of the n - type Al q Ga 1-q As (0 <q ≦ 1) layer. It can be larger than the refractive index. When the semiconductor substrate 100 is used for a vertical cavity surface emitting laser, the thickness of the n-type Al r Ga 1-r As (0 ≦ r <1, q> r) layer used for the high refractive index layer is It is designed according to the emission wavelength band required for the laser. The Al composition (r) of the n-type Al r Ga 1-r As (0 ≦ r <1, q> r) layer is in the range of 0.0 to 0.2 (where n-type Al q Ga 1-q As It is appropriate that it is smaller than the Al composition (q) of the layer (0 <q ≦ 1). Examples of impurity atoms doped in the n-type Al r Ga 1-r As (0 ≦ r <1, q> r) layer include Si, Se, and S. The carrier concentration of the n-type Al r Ga 1-r As (0 ≦ r <1, q> r) layer is preferably in the range of 1 × 10 18 cm −3 to 3 × 10 18 m −3 .

ｎ型ＡｌｑＧａ１−ｑＡｓ（０＜ｑ≦１）層とｎ型ＡｌｒＧａ１−ｒＡｓ（０≦ｒ＜１、ｑ＞ｒ）層との間に、ＡｌｓＧａ１−ｓＡｓのＡｌ組成（ｓ）を当該層の厚さ方向に連続的に変えたｎ型ＡｌｓＧａ１−ｓＡｓ（０≦ｓ≦１）層を配置してもよい。ｎ型ＡｌｑＧａ１−ｑＡｓ層とＡｌｓＧａ１−ｓＡｓ層との界面において、Ａｌ組成（ｓ）はＡｌ組成（ｑ）と略等しくてよい。ｎ型ＡｌｒＧａ１−ｒＡｓ層とＡｌｓＧａ１−ｓＡｓ層との界面において、Ａｌ組成（ｓ）はＡｌ組成（ｒ）と略等しくてよい。Ａｌ組成（ｓ）を連続的に変えることで、ｎ型ＡｌｑＧａ１−ｑＡｓ（０＜ｑ≦１）層およびｎ型ＡｌｒＧａ１−ｒＡｓ（０≦ｒ＜１、ｑ＞ｒ）層の間の電気抵抗を低減できる。ｎ型ＡｌｑＧａ１−ｑＡｓ（０＜ｑ≦１）層およびｎ型ＡｌｒＧａ１−ｒＡｓ（０≦ｒ＜１、ｑ＞ｒ）層の繰り返し回数は、３０〜６０が好ましい。 Between the n-type Al q Ga 1-q As (0 <q ≦ 1) layer and the n-type Al r Ga 1-r As (0 ≦ r <1, q> r) layer, Al s Ga 1-s An n-type Al s Ga 1-s As (0 ≦ s ≦ 1) layer in which the Al composition (s) of As is continuously changed in the thickness direction of the layer may be disposed. At the interface between the n-type Al q Ga 1-q As layer and the Al s Ga 1-s As layer, the Al composition (s) may be substantially equal to the Al composition (q). At the interface between the n-type Al r Ga 1-r As layer and the Al s Ga 1-s As layer, the Al composition (s) may be substantially equal to the Al composition (r). By continuously changing the Al composition (s), the n-type Al q Ga 1-q As (0 <q ≦ 1) layer and the n-type Al r Ga 1-r As (0 ≦ r <1, q> r) ) The electrical resistance between the layers can be reduced. The number of repetitions of the n-type Al q Ga 1-q As (0 <q ≦ 1) layer and the n-type Al r Ga 1-r As (0 ≦ r <1, q> r) layer is preferably 30 to 60.

ｉ型積層結晶層１０８は、ｎ型積層結晶層１０６の上にエピタキシャル成長により形成された、複数のｉ型３−５族化合物半導体結晶層からなる積層結晶層である。ｉ型積層結晶層１０８は、半導体基板１００が垂直共振器面発光レーザに用いられた場合に、活性層として機能する。ｉ型積層結晶層１０８は、２つのｉ型ＡｌＧａＡｓ層１２０がｉ型ＧａＡｓ／ＡｌＧａＡｓ層１２２を挟んで構成した積層結晶層を含む。   The i-type stacked crystal layer 108 is a stacked crystal layer composed of a plurality of i-type group 3-5 compound semiconductor crystal layers formed on the n-type stacked crystal layer 106 by epitaxial growth. The i-type stacked crystal layer 108 functions as an active layer when the semiconductor substrate 100 is used in a vertical cavity surface emitting laser. The i-type stacked crystal layer 108 includes a stacked crystal layer in which two i-type AlGaAs layers 120 are formed with an i-type GaAs / AlGaAs layer 122 interposed therebetween.

ｉ型ＡｌＧａＡｓ層１２０は、半導体基板１００が垂直共振器面発光レーザに用いられた場合に、クラッド層として機能する。半導体基板１００が垂直共振器面発光レーザに用いられた場合に、ｉ型ＡｌＧａＡｓ層１２０の厚さは、レーザに要求される発光波長帯に応じて設計される。ｉ型ＡｌＧａＡｓ層１２０のＡｌ組成は、０．１〜０．９の範囲内であることが適切である。厚さ方向のＡｌ組成を連続的に変化させることによって、ｉ型ＡｌＧａＡｓ層１２０のバンドギャップエネルギが厚さ方向に連続的に変化する。   The i-type AlGaAs layer 120 functions as a cladding layer when the semiconductor substrate 100 is used in a vertical cavity surface emitting laser. When the semiconductor substrate 100 is used for a vertical cavity surface emitting laser, the thickness of the i-type AlGaAs layer 120 is designed according to the emission wavelength band required for the laser. The Al composition of the i-type AlGaAs layer 120 is suitably in the range of 0.1 to 0.9. By continuously changing the Al composition in the thickness direction, the band gap energy of the i-type AlGaAs layer 120 continuously changes in the thickness direction.

ｉ型ＧａＡｓ／ＡｌＧａＡｓ層１２２は、半導体基板１００が垂直共振器面発光レーザに用いられた場合に、発光層として機能する。ｉ型ＧａＡｓ／ＡｌＧａＡｓ層１２２は、ＧａＡｓ層およびＡｌＧａＡｓ層が交互に複数配置された量子井戸構造（ＭＱＷ）を含む。量子井戸構造（ＭＱＷ）は、ＧａＡｓ／ＡｌＧａＡｓ構造に代えて、ＩｎＧａＡｓ／ＧａＡｓ構造、ＩｎＧａＡｓ／ＡｌＧａＡｓ構造、ＧａＡｓ／ＧａＡｓＰ構造、ＩｎＧａＡｓ／ＧａＡｓＰ構造、ＧａＩｎＮＡｓ／ＧａＡｓ構造であってもよい。   The i-type GaAs / AlGaAs layer 122 functions as a light emitting layer when the semiconductor substrate 100 is used in a vertical cavity surface emitting laser. The i-type GaAs / AlGaAs layer 122 includes a quantum well structure (MQW) in which a plurality of GaAs layers and AlGaAs layers are alternately arranged. The quantum well structure (MQW) may be an InGaAs / GaAs structure, an InGaAs / AlGaAs structure, a GaAs / GaAsP structure, an InGaAs / GaAsP structure, or a GaInNAs / GaAs structure instead of a GaAs / AlGaAs structure.

半導体基板１００が垂直共振器面発光レーザに用いられた場合に、量子井戸構造（ＭＱＷ）に含まれるＧａＡｓ層の厚さは、レーザに要求される発光波長帯に応じて設計される。量子井戸構造（ＭＱＷ）に含まれるＡｌＧａＡｓ層の厚さは、５ｎｍ〜１２ｎｍの範囲内であることが好ましい。当該ＡｌＧａＡｓ層のＡｌ組成は、０．１〜０．４の範囲内であることが適切である。ＧａＡｓ層およびＡｌＧａＡｓ層の積層構造の繰り返し数は、２〜６の範囲内であることが適切である。   When the semiconductor substrate 100 is used in a vertical cavity surface emitting laser, the thickness of the GaAs layer included in the quantum well structure (MQW) is designed according to the emission wavelength band required for the laser. The thickness of the AlGaAs layer included in the quantum well structure (MQW) is preferably in the range of 5 nm to 12 nm. The Al composition of the AlGaAs layer is suitably in the range of 0.1 to 0.4. The number of repetitions of the laminated structure of the GaAs layer and the AlGaAs layer is suitably in the range of 2-6.

ｐ型ＡｌＧａＡｓ層１１０は、ｉ型積層結晶層１０８の上にエピタキシャル成長により形成される。ｐ型ＡｌＧａＡｓ層１１０は、半導体基板１００が垂直共振器面発光レーザに用いられた場合に一部が酸化され、酸化狭窄層として機能する。ｐ型ＡｌＧａＡｓ層１１０の厚さは、２０ｎｍ〜４０ｎｍの範囲内であることが好ましい。ｐ型ＡｌＧａＡｓ層１１０のＡｌ組成は、０．９５〜１．０の範囲内であることが適切である。ｐ型ＡｌＧａＡｓ層１１０にドーピングされる不純物原子として、Ｃ（炭素）、Ｚｎが挙げられる。ｐ型ＡｌＧａＡｓ層１１０のキャリア濃度は、１×１０１８ｃｍ−３〜３×１０１８ｃｍ−３の範囲内であることが好ましい。 The p-type AlGaAs layer 110 is formed on the i-type stacked crystal layer 108 by epitaxial growth. The p-type AlGaAs layer 110 is partially oxidized when the semiconductor substrate 100 is used in a vertical cavity surface emitting laser, and functions as an oxidized constriction layer. The thickness of the p-type AlGaAs layer 110 is preferably in the range of 20 nm to 40 nm. The Al composition of the p-type AlGaAs layer 110 is suitably in the range of 0.95 to 1.0. Examples of impurity atoms doped in the p-type AlGaAs layer 110 include C (carbon) and Zn. The carrier concentration of the p-type AlGaAs layer 110 is preferably in the range of 1 × 10 18 cm −3 to 3 × 10 18 cm −3 .

ｐ型積層結晶層１１２は、ｐ型ＡｌＧａＡｓ層１１０の上にエピタキシャル成長により形成された、複数のｐ型３−５族化合物半導体結晶層からなる積層結晶層である。ｐ型積層結晶層１１２は、半導体基板１００が垂直共振器面発光レーザに用いられた場合に、共振器の他方のミラーであるｐ型ミラー層として機能する。ｐ型積層結晶層１１２は、例えば分布ブラッグ反射器（ＤＢＲ）である。ｐ型積層結晶層１１２は、低屈折率層である第１結晶層１３０と高屈折率層である第２結晶層１３２とを積層した積層結晶層を含む。第１結晶層１３０と第２結晶層１３２を積層した積層構造を複数回繰り返して配置することで所定の波長の光の反射率を高くできる。   The p-type stacked crystal layer 112 is a stacked crystal layer made of a plurality of p-type group 3-5 compound semiconductor crystal layers formed on the p-type AlGaAs layer 110 by epitaxial growth. The p-type stacked crystal layer 112 functions as a p-type mirror layer that is the other mirror of the resonator when the semiconductor substrate 100 is used in a vertical cavity surface emitting laser. The p-type stacked crystal layer 112 is, for example, a distributed Bragg reflector (DBR). The p-type stacked crystal layer 112 includes a stacked crystal layer in which a first crystal layer 130 that is a low refractive index layer and a second crystal layer 132 that is a high refractive index layer are stacked. By repeatedly disposing a stacked structure in which the first crystal layer 130 and the second crystal layer 132 are stacked a plurality of times, the reflectance of light having a predetermined wavelength can be increased.

本明細書において、第１結晶層１３０は、例えばｐ型ＡｌｍＧａ１−ｍＡｓ（０＜ｍ≦１）で表される３−５族化合物半導体からなる。第１結晶層１３０が本発明のｐ型結晶層に相当する場合、第１結晶層１３０は、ｐ型不純物原子として炭素原子を含み、かつ、６×１０１７ｃｍ−３以上、６×１０１９ｃｍ−３以下の濃度の水素原子を含む。一方で、第２結晶層１３２は、例えばｐ型ＡｌｎＧａ１−ｎＡｓ（０≦ｎ＜１、ｍ＞ｎ）で表される３−５族化合物半導体からなる。第２結晶層１３２は、ｐ型不純物原子として炭素原子および水素原子のそれぞれを含んでよく、含まなくともよい。 In the present specification, the first crystal layer 130 is made of, for example, a Group 3-5 compound semiconductor represented by p-type Al m Ga 1-m As (0 <m ≦ 1). When the first crystal layer 130 corresponds to the p-type crystal layer of the present invention, the first crystal layer 130 includes carbon atoms as p-type impurity atoms, and is 6 × 10 17 cm −3 or more and 6 × 10 19. It contains hydrogen atoms with a concentration of cm −3 or less. On the other hand, the second crystal layer 132 is made of a Group 3-5 compound semiconductor represented by, for example, p-type Al n Ga 1-n As (0 ≦ n <1, m> n). Second crystal layer 132 may or may not include carbon atoms and hydrogen atoms as p-type impurity atoms.

半導体基板１００が垂直共振器面発光レーザに用いられた場合、第１結晶層１３０に用いられるｐ型ＡｌｍＧａ１−ｍＡｓ（０＜ｍ≦１）層の厚さは、レーザに要求される発光波長帯に応じて設計される。ｐ型ＡｌｍＧａ１−ｍＡｓ（０＜ｍ≦１）層のＡｌ組成（ｍ）は、０．８〜１．０の範囲内であることが適切である。ｐ型ＡｌｍＧａ１−ｍＡｓ（０＜ｍ≦１）層にドーピングされる不純物原子として、Ｃ、Ｚｎが挙げられる。ｐ型ＡｌｍＧａ１−ｍＡｓ（０＜ｍ≦１）層のキャリア濃度は、１×１０１８ｃｍ−３〜４×１０１８ｃｍ−３の範囲内であることが好ましい。 When the semiconductor substrate 100 is used for a vertical cavity surface emitting laser, the thickness of the p-type Al m Ga 1-m As (0 <m ≦ 1) layer used for the first crystal layer 130 is required for the laser. It is designed according to the emission wavelength band. The Al composition (m) of the p-type Al m Ga 1-m As (0 <m ≦ 1) layer is suitably in the range of 0.8 to 1.0. Examples of impurity atoms doped in the p-type Al m Ga 1-m As (0 <m ≦ 1) layer include C and Zn. The carrier concentration of the p-type Al m Ga 1-m As (0 <m ≦ 1) layer is preferably in the range of 1 × 10 18 cm −3 to 4 × 10 18 cm −3 .

第２結晶層１３２としてのｐ型ＡｌｎＧａ１−ｎＡｓ（０≦ｎ＜１、ｍ＞ｎ）層のＡｌ組成（ｎ）をｐ型ＡｌｍＧａ１−ｍＡｓ（０＜ｍ≦１）層のＡｌ組成（ｍ）より小さくすることで、ｐ型ＡｌｎＧａ１−ｎＡｓ（０≦ｎ＜１、ｍ＞ｎ）層の屈折率をｐ型ＡｌｍＧａ１−ｍＡｓ（０＜ｍ≦１）層の屈折率より大きくできる。第２結晶層１３２にｐ型ＡｌｎＧａ１−ｎＡｓ（０≦ｎ＜１、ｍ＞ｎ）層を用いる場合、ｐ型ＡｌｎＧａ１−ｎＡｓ（０≦ｎ＜１、ｍ＞ｎ）層の厚さは、レーザに要求される発光波長帯に応じて設計される。ｐ型ＡｌｎＧａ１−ｎＡｓ（０≦ｎ＜１、ｍ＞ｎ）層のＡｌ組成（ｎ）は、０．０〜０．２の範囲内（ただしｐ型ＡｌｍＧａ１−ｍＡｓ（０＜ｍ≦１）層のＡｌ組成（ｍ）より小さい）であることが適切である。ｐ型ＡｌｎＧａ１−ｎＡｓ（０≦ｎ＜１、ｍ＞ｎ）層にドーピングされる不純物原子として、Ｃ、Ｚｎが挙げられる。ｐ型ＡｌｎＧａ１−ｎＡｓ（０≦ｎ＜１、ｍ＞ｎ）層のキャリア濃度は、１×１０１８ｃｍ−３〜４×１０１８ｃｍ−３の範囲内であることが好ましい。 The Al composition (n) of the p-type Al n Ga 1-n As (0 ≦ n <1, m> n) layer as the second crystal layer 132 is changed to p-type Al m Ga 1-m As (0 <m ≦ 1). ) Layer smaller than the Al composition (m), the refractive index of the p - type Al n Ga 1-n As (0 ≦ n <1, m> n) layer is changed to the p-type Al m Ga 1-m As (0). <M ≦ 1) Can be larger than the refractive index of the layer. When using the second crystal layer 132 p-type Al n Ga 1-n As ( 0 ≦ n <1, m> n) layer, p-type Al n Ga 1-n As ( 0 ≦ n <1, m> n The layer thickness is designed according to the emission wavelength band required for the laser. The Al composition (n) of the p-type Al n Ga 1-n As (0 ≦ n <1, m> n) layer is in the range of 0.0 to 0.2 (however, p-type Al m Ga 1-m As). It is appropriate that it is smaller than the Al composition (m) of the layer (0 <m ≦ 1). Examples of impurity atoms doped in the p-type Al n Ga 1-n As (0 ≦ n <1, m> n) layer include C and Zn. The carrier concentration of the p-type Al n Ga 1-n As (0 ≦ n <1, m> n) layer is preferably in the range of 1 × 10 18 cm −3 to 4 × 10 18 cm −3 .

第１結晶層１３０は、本発明におけるｐ型結晶層の一例である。すなわち、第１結晶層１３０は、垂直共振器面発光レーザ用の半導体基板１００に含まれる３−５族化合物半導体結晶層であり、ｐ型不純物原子として炭素原子を含み、かつ、６×１０１７ｃｍ−３以上、６×１０１９ｃｍ−３以下の濃度の水素原子を含む。また、第１結晶層１３０は、第２結晶層１３２に含まれる水素原子より多くの水素原子を含む。後に説明するように、第１結晶層１３０は、３族原料ガスのモル供給量に対する５族原料ガスのモル供給量の比（Ｖ／ＩＩＩ比）が０．７以上３０以下と小さい条件でエピタキシャル成長させる。３族原料ガスとしてアルキル基を有する有機金属ガスを用いれば、第１結晶層１３０には多くの炭素が不純物としてドーピングされ、アルキル基由来の炭素とともに水素も同時に導入される。その結果、第１結晶層１３０には多くの水素原子を含むようになる。 The first crystal layer 130 is an example of a p-type crystal layer in the present invention. That is, the first crystal layer 130 is a Group 3-5 compound semiconductor crystal layer included in the semiconductor substrate 100 for a vertical cavity surface emitting laser, includes carbon atoms as p-type impurity atoms, and 6 × 10 17. It contains hydrogen atoms at a concentration of cm −3 or more and 6 × 10 19 cm −3 or less. Further, the first crystal layer 130 includes more hydrogen atoms than hydrogen atoms included in the second crystal layer 132. As will be described later, the first crystal layer 130 is epitaxially grown under a condition that the ratio of the molar supply amount of the Group 5 source gas to the molar supply amount of the Group 3 source gas (V / III ratio) is as small as 0.7 or more and 30 or less. Let If an organometallic gas having an alkyl group is used as the group 3 source gas, the first crystal layer 130 is doped with a large amount of carbon as an impurity, and hydrogen is simultaneously introduced together with the carbon derived from the alkyl group. As a result, the first crystal layer 130 contains many hydrogen atoms.

上記した方法により第１結晶層１３０を形成した場合、第１結晶層１３０は、６×１０１７ｃｍ−３以上、２．５×１０１８ｃｍ−３以下の濃度の水素原子を含むようになる。また、第１結晶層１３０は低屈折率に形成する必要からｐ型ＡｌｍＧａ１−ｍＡｓ層（０．５０≦ｍ≦１．０）として形成され、このようなＡｌ組成が高い結晶層を形成する場合には第１結晶層１３０は酸素原子を含むようになる。すなわち、第１結晶層１３０は、７×１０１７ｃｍ−３以上、５×１０１８ｃｍ−３以下の濃度の酸素原子を含む。 When the first crystal layer 130 is formed by the above-described method, the first crystal layer 130 includes hydrogen atoms having a concentration of 6 × 10 17 cm −3 or more and 2.5 × 10 18 cm −3 or less. . The first crystal layer 130 is formed as a p-type Al m Ga 1-m As layer (0.50 ≦ m ≦ 1.0) because it needs to be formed with a low refractive index, and such a crystal layer having a high Al composition. When the first crystal layer 130 is formed, the first crystal layer 130 contains oxygen atoms. That is, the first crystal layer 130 includes oxygen atoms having a concentration of 7 × 10 17 cm −3 or more and 5 × 10 18 cm −3 or less.

第１結晶層１３０と第２結晶層１３２との間に、ＡｌｓＧａ１−ｓＡｓのＡｌ組成（ｓ）を連続的に変えたｐ型ＡｌｓＧａ１−ｓＡｓ（０≦ｓ≦１）層を配置してもよい。Ａｌ組成（ｓ）を連続的に変えることで、第１結晶層１３０と第２結晶層１３２の間の電気抵抗を低減できる。第１結晶層１３０および第２結晶層１３２の繰り返し回数は、１０〜３０が好ましい。 P-type Al s Ga 1-s As (0 ≦ s ≦ 1) in which the Al composition (s) of Al s Ga 1-s As is continuously changed between the first crystal layer 130 and the second crystal layer 132. ) Layers may be arranged. By continuously changing the Al composition (s), the electrical resistance between the first crystal layer 130 and the second crystal layer 132 can be reduced. The number of repetitions of the first crystal layer 130 and the second crystal layer 132 is preferably 10-30.

ｐ型ＧａＡｓ層１１４は、ｐ型積層結晶層１１２の上にエピタキシャル成長により形成されたｐ型３−５族化合物半導体結晶層である。ｐ型ＧａＡｓ層１１４は、他のｐ型半導体層を含んでもよい。ｐ型ＧａＡｓ層１１４は、半導体基板１００が垂直共振器面発光レーザに用いられた場合に、コンタクト層として機能する。ｐ型ＧａＡｓ層１１４の厚さは、１０ｎｍ〜３０ｎｍの範囲内であることが好ましい。ｐ型ＧａＡｓ層１１４にドーピングされる不純物原子として、Ｃ、Ｚｎが挙げられる。ｐ型ＧａＡｓ層１１４のキャリア濃度は、４×１０１９ｃｍ−３〜１×１０２０ｃｍ−３の範囲内であることが好ましい。 The p-type GaAs layer 114 is a p-type group 3-5 compound semiconductor crystal layer formed on the p-type stacked crystal layer 112 by epitaxial growth. The p-type GaAs layer 114 may include other p-type semiconductor layers. The p-type GaAs layer 114 functions as a contact layer when the semiconductor substrate 100 is used for a vertical cavity surface emitting laser. The thickness of the p-type GaAs layer 114 is preferably in the range of 10 nm to 30 nm. Examples of impurity atoms doped in the p-type GaAs layer 114 include C and Zn. The carrier concentration of the p-type GaAs layer 114 is preferably in the range of 4 × 10 19 cm −3 to 1 × 10 20 cm −3 .

ｐ型ＧａＡｓ層１１４は、本発明におけるｐ型結晶層の一例である。すなわち、第１結晶層１３０は、垂直共振器面発光レーザ用の半導体基板１００に含まれる３−５族化合物半導体結晶層であり、ｐ型不純物原子として炭素原子を含み、かつ、６×１０１７ｃｍ−３以上、６×１０１９ｃｍ−３以下の濃度の水素原子を含む。後に説明するように、ｐ型ＧａＡｓ層１１４は、３族原料ガスのモル供給量に対する５族原料ガスのモル供給量の比（Ｖ／ＩＩＩ比）が０．７以上３０以下と小さい条件でエピタキシャル成長させる。３族原料ガスとしてアルキル基を有する有機金属ガスを用いれば、ｐ型ＧａＡｓ層１１４には多くの炭素が不純物としてドーピングされ、アルキル基由来の炭素とともに水素も同時に導入される。その結果、ｐ型ＧａＡｓ層１１４には、１×１０１９ｃｍ−３以上、６×１０１９ｃｍ−３以下の濃度の水素原子を含むようになる。 The p-type GaAs layer 114 is an example of a p-type crystal layer in the present invention. That is, the first crystal layer 130 is a Group 3-5 compound semiconductor crystal layer included in the semiconductor substrate 100 for a vertical cavity surface emitting laser, includes carbon atoms as p-type impurity atoms, and 6 × 10 17. It contains hydrogen atoms at a concentration of cm −3 or more and 6 × 10 19 cm −3 or less. As will be described later, the p-type GaAs layer 114 is epitaxially grown under the condition that the ratio of the molar supply amount of the Group 5 source gas to the molar supply amount of the Group 3 source gas (V / III ratio) is as small as 0.7 or more and 30 or less. Let If an organometallic gas having an alkyl group is used as the Group 3 source gas, the p-type GaAs layer 114 is doped with a large amount of carbon as an impurity, and hydrogen is simultaneously introduced together with the carbon derived from the alkyl group. As a result, the p-type GaAs layer 114 contains hydrogen atoms having a concentration of 1 × 10 19 cm −3 or more and 6 × 10 19 cm −3 or less.

半導体基板１００の製造方法は、以下のとおりである。ベース基板１０２を用意し、ベース基板１０２上にバッファ層１０４、ｎ型積層結晶層１０６、ｉ型積層結晶層１０８、ｐ型ＡｌＧａＡｓ層１１０、ｐ型積層結晶層１１２およびｐ型ＧａＡｓ層１１４を順次エピタキシャル成長により形成する。   The manufacturing method of the semiconductor substrate 100 is as follows. A base substrate 102 is prepared, and a buffer layer 104, an n-type stacked crystal layer 106, an i-type stacked crystal layer 108, a p-type AlGaAs layer 110, a p-type stacked crystal layer 112, and a p-type GaAs layer 114 are sequentially formed on the base substrate 102. It is formed by epitaxial growth.

エピタキシャル成長にはＭＯＣＶＤ法を用いる。ＭＯＣＶＤ法に用いる３族原料ガスは、３族原子に少なくとも１つのアルキル基が結合した３族原子のアルキル化物を含む。３族原料ガスとして、ＴＭＧ（トリメチルガリウム）、ＴＭＡ（トリメチルアルミニウム）、ＴＭＩ（トリメチルインジウム）が挙げられる。５族原料ガスは、５族原子の水素化物を含む。５族原料ガスとして、ＡｓＨ３（アルシン）、ＰＨ３（ホスフィン）が挙げられる。ｎ型不純物ガスとしてＳｉ２Ｈ６（ジシラン）が挙げられ、ｐ型不純物ガスとしてＣＢｒＣｌ３、ジエチル亜鉛（ＤＥＺｎ）が挙げられる。エピタキシャル成長温度は、４００℃〜８００℃の範囲内で制御する。 The MOCVD method is used for epitaxial growth. The group 3 source gas used in the MOCVD method contains an alkylated group 3 atom in which at least one alkyl group is bonded to the group 3 atom. Examples of the group 3 source gas include TMG (trimethylgallium), TMA (trimethylaluminum), and TMI (trimethylindium). The group 5 source gas contains a hydride of group 5 atoms. Examples of the Group 5 source gas include AsH 3 (arsine) and PH 3 (phosphine). Examples of the n-type impurity gas include Si 2 H 6 (disilane), and examples of the p-type impurity gas include CBrCl 3 and diethyl zinc (DEZn). The epitaxial growth temperature is controlled within a range of 400 ° C to 800 ° C.

これら原料ガスの供給量を制御することで各結晶層の組成を制御でき、不純物ガスの供給量を制御することで不純物ドーピング量を制御できる。また、３族原料ガスのモル供給量に対する５族原料ガスのモル供給量の比（Ｖ／ＩＩＩ比）を制御することでエピタキシャル成長層への炭素原子のドーピング量を制御できる。Ｖ／ＩＩＩ比を小さくすることで高価な５族原料ガスが節約できるので、製造コストが低減できる。特に、ｐ型結晶層をエピタキシャル成長させる段階においてＶ／ＩＩＩ比を小さくすれば、ｐ型結晶層内で、３族原料ガス由来の炭素原子がｐ型不純物として機能するので、製造コストを低減するとともにｐ型結晶層の抵抗値を下げることができる。よってｐ型結晶層を成長する段階において、Ｖ／ＩＩＩ比を０．７以上３０以下に制御する。また、ｐ型結晶層を成長する段階におけるＶ／ＩＩＩ比を、それぞれのｎ型３−５族化合物半導体結晶層を成長する段階におけるいずれのＶ／ＩＩＩ比より小さくしてもよい。また、ｐ型結晶層を成長する段階におけるＶ／ＩＩＩ比を、それぞれのｉ型３−５族化合物半導体結晶層を成長する段階におけるいずれのＶ／ＩＩＩ比より小さくしてもよい。   The composition of each crystal layer can be controlled by controlling the supply amount of these source gases, and the impurity doping amount can be controlled by controlling the supply amount of the impurity gas. Further, the doping amount of carbon atoms to the epitaxial growth layer can be controlled by controlling the ratio (V / III ratio) of the molar supply amount of the Group 5 source gas to the molar supply amount of the Group 3 source gas. By reducing the V / III ratio, an expensive group 5 source gas can be saved, so that the manufacturing cost can be reduced. In particular, if the V / III ratio is reduced in the stage of epitaxial growth of the p-type crystal layer, the carbon atoms derived from the group 3 source gas function as p-type impurities in the p-type crystal layer, thereby reducing the manufacturing cost. The resistance value of the p-type crystal layer can be lowered. Therefore, in the stage of growing the p-type crystal layer, the V / III ratio is controlled to 0.7 or more and 30 or less. Further, the V / III ratio in the stage of growing the p-type crystal layer may be smaller than any V / III ratio in the stage of growing the respective n-type group 3-5 compound semiconductor crystal layer. Further, the V / III ratio in the stage of growing the p-type crystal layer may be smaller than any V / III ratio in the stage of growing the respective i-type group 3-5 compound semiconductor crystal layer.

ｐ型結晶層として、ｐ型ＧａＡｓ層１１４または第１結晶層１３０が挙げられる。特に、第１結晶層１３０を成長する段階では、Ｖ／ＩＩＩ比を小さくした条件でエピタキシャル成長する意義は大きい。第１結晶層１３０は第２結晶層１３２よりＡｌ組成を大きくする必要性があるが、Ａｌ組成を大きくするエピタキシャル条件では不純物ガスによるｐ型不純物のドーピング量の制御が難しくなる。しかしＶ／ＩＩＩ比を小さくしてエピタキシャル成長すれば、アルキル基由来の炭素原子が第１結晶層１３０にドーピングされ、当該炭素原子がｐ型不純物として作用するので、Ｖ／ＩＩＩ比を制御することによりｐ型不純物のドーピング量を容易に制御することができる。   Examples of the p-type crystal layer include the p-type GaAs layer 114 or the first crystal layer 130. In particular, at the stage where the first crystal layer 130 is grown, the significance of epitaxial growth under the condition that the V / III ratio is reduced is significant. The first crystal layer 130 needs to have an Al composition larger than that of the second crystal layer 132. However, it is difficult to control the doping amount of the p-type impurity with the impurity gas under the epitaxial conditions in which the Al composition is increased. However, if the V / III ratio is reduced and epitaxial growth is performed, carbon atoms derived from alkyl groups are doped into the first crystal layer 130, and the carbon atoms act as p-type impurities. Therefore, by controlling the V / III ratio, The doping amount of the p-type impurity can be easily controlled.

なお、ｐ型ＧａＡｓ層１１４または第１結晶層１３０を成長する段階において、３族原料ガスおよび５族原料ガスに、炭素化合物を不純物ガスとして添加してもよい。炭素化合物として、ＣＸ４−ｙＨｙ（ただし、Ｘはハロゲン原子であり、ｙは０以上３以下の整数である。）で表される化合物が挙げられる。より具体的にはＣＢｒＣｌ３が挙げられる。このような炭素化合物を不純物ガスとして添加することにより、ｐ型ＧａＡｓ層１１４または第１結晶層１３０の抵抗値を小さくすることができる。３族原料ガスおよび５族原料ガスに、炭素化合物を添加する方法は、特に限定されない。３族原料ガスおよび５族原料ガスの供給に加え、さらに炭素化合物を反応炉内に供給してもよいし、最初から炭素化合物が添加された３族または５族の原料ガスを、反応炉内に供給してもよい。また、これらのガスおよび炭素化合物は、反応炉に入る前に、配管によりそれぞれ混合されてもよいし、それぞれが独立して反応炉内に入ってもよい。 In the stage of growing the p-type GaAs layer 114 or the first crystal layer 130, a carbon compound may be added as an impurity gas to the Group 3 source gas and the Group 5 source gas. Examples of the carbon compound include compounds represented by CX 4-y H y (where X is a halogen atom, and y is an integer of 0 or more and 3 or less). More specifically, CBrCl 3 can be mentioned. By adding such a carbon compound as an impurity gas, the resistance value of the p-type GaAs layer 114 or the first crystal layer 130 can be reduced. The method for adding the carbon compound to the Group 3 source gas and the Group 5 source gas is not particularly limited. In addition to the supply of the group 3 source gas and the group 5 source gas, a carbon compound may be further supplied into the reaction furnace, or the group 3 or group 5 source gas to which the carbon compound has been added from the beginning is supplied into the reaction furnace. May be supplied. In addition, these gases and carbon compounds may be mixed by piping before entering the reaction furnace, or each may enter the reaction furnace independently.

また、第２結晶層１３２を成長する段階において、３族原料ガスおよび５族原料ガスに、ｐ型不純物原子を含有する化合物を添加することができる。ｐ型不純物原子を含有する化合物として、ＣＸ４−ｙＨｙ（ただし、Ｘはハロゲン原子であり、ｙは０以上３以下の整数である。）で表される化合物が挙げられる。より具体的にはＣＢｒＣｌ３が挙げられる。このような炭素化合物を不純物ガスとして添加することにより、第２結晶層１３２の抵抗値を小さくすることができる。 Further, in the stage of growing the second crystal layer 132, a compound containing a p-type impurity atom can be added to the Group 3 source gas and the Group 5 source gas. Examples of the compound containing a p-type impurity atom include a compound represented by CX 4-y H y (where X is a halogen atom, and y is an integer of 0 or more and 3 or less). More specifically, CBrCl 3 can be mentioned. By adding such a carbon compound as an impurity gas, the resistance value of the second crystal layer 132 can be reduced.

図２は、垂直共振器面発光レーザ２００の断面例を示す。垂直共振器面発光レーザ２００は、ベース基板１０２、バッファ層１０４、ｎ型ミラー層２０６、活性層２０８、酸化狭窄層２１０、ｐ型ミラー層２１２、コンタクト層２１４、電極２１６および酸化層２１８を有する。活性層２０８は、クラッド層２２０および発光層２２２を有する。   FIG. 2 shows a cross-sectional example of the vertical cavity surface emitting laser 200. The vertical cavity surface emitting laser 200 includes a base substrate 102, a buffer layer 104, an n-type mirror layer 206, an active layer 208, an oxide constriction layer 210, a p-type mirror layer 212, a contact layer 214, an electrode 216, and an oxide layer 218. . The active layer 208 has a cladding layer 220 and a light emitting layer 222.

ｎ型ミラー層２０６、活性層２０８、酸化狭窄層２１０、ｐ型ミラー層２１２およびコンタクト層２１４の各々は、半導体基板１００のｎ型積層結晶層１０６、ｉ型積層結晶層１０８、ｐ型ＡｌＧａＡｓ層１１０、ｐ型積層結晶層１１２およびｐ型ＧａＡｓ層１１４の各々がメサ加工されて形成されたものである。電極２１６は、コンタクト層２１４に接してドーナツ状に形成された金属層であり、垂直共振器面発光レーザ２００のアノード電極として機能する。酸化層２１８は、メサ加工されたｐ型ＡｌＧａＡｓ層１１０を横方向酸化した酸化層である。活性層２０８は、クラッド層２２０および発光層２２２を含み、クラッド層２２０および発光層２２２の各々は、ｉ型ＡｌＧａＡｓ層１２０およびｉ型ＧａＡｓ／ＡｌＧａＡｓ層１２２の各々がメサ加工されて形成されたものである。なお、図示は省略したが、ベース基板１０２の上面または下面にはカソード電極が形成される。メサ加工は、ｎ型ミラー層２０６の途中、たとえばｎ型ミラー層２０６の上部数層程度の深さで停止してもよい。   The n-type mirror layer 206, the active layer 208, the oxidized constricting layer 210, the p-type mirror layer 212, and the contact layer 214 are respectively the n-type stacked crystal layer 106, the i-type stacked crystal layer 108, and the p-type AlGaAs layer of the semiconductor substrate 100. 110, p-type stacked crystal layer 112 and p-type GaAs layer 114 are each formed by mesa processing. The electrode 216 is a metal layer formed in a donut shape in contact with the contact layer 214 and functions as an anode electrode of the vertical cavity surface emitting laser 200. The oxide layer 218 is an oxide layer obtained by laterally oxidizing the mesa-processed p-type AlGaAs layer 110. The active layer 208 includes a cladding layer 220 and a light emitting layer 222. Each of the cladding layer 220 and the light emitting layer 222 is formed by mesa processing each of the i-type AlGaAs layer 120 and the i-type GaAs / AlGaAs layer 122. It is. Although not shown, a cathode electrode is formed on the upper surface or the lower surface of the base substrate 102. The mesa processing may be stopped in the middle of the n-type mirror layer 206, for example, at a depth of several layers above the n-type mirror layer 206.

垂直共振器面発光レーザ２００の製造方法は以下の通りである。半導体基板１００を製造した後、バッファ層１０４、ｎ型積層結晶層１０６、ｉ型積層結晶層１０８、ｐ型ＡｌＧａＡｓ層１１０、ｐ型積層結晶層１１２およびｐ型ＧａＡｓ層１１４をメサ加工する。その後、メサ加工した半導体基板１００を酸化雰囲気に置き、ｐ型ＡｌＧａＡｓ層１１０を横方向酸化して酸化層２１８を形成する。さらに電極２１６となる金属層を蒸着法またはスパッタ法で形成し、フォトリソグラフィ法またはリフトオフ法により金属層をパターニングして電極２１６を形成する。   The manufacturing method of the vertical cavity surface emitting laser 200 is as follows. After manufacturing the semiconductor substrate 100, the buffer layer 104, the n-type stacked crystal layer 106, the i-type stacked crystal layer 108, the p-type AlGaAs layer 110, the p-type stacked crystal layer 112, and the p-type GaAs layer 114 are mesa processed. Thereafter, the mesa-processed semiconductor substrate 100 is placed in an oxidizing atmosphere, and the p-type AlGaAs layer 110 is laterally oxidized to form an oxide layer 218. Further, a metal layer to be the electrode 216 is formed by an evaporation method or a sputtering method, and the electrode layer 216 is formed by patterning the metal layer by a photolithography method or a lift-off method.

上記した半導体基板１００によれば、Ｖ／ＩＩＩ比を０．７以上３０以下に制御してｐ型ＧａＡｓ層１１４または第１結晶層１３０をエピタキシャル成長するので、５族原料ガスを節約するとともに、ｐ型不純物を多くドーピングしてｐ型ＧａＡｓ層１１４または第１結晶層１３０の抵抗を低減できる。また、Ｖ／ＩＩＩ比を０．７以上３０以下に制御するとともにｐ型不純物ガスとしてＣＸ４−ｙＨｙ（ただし、Ｘはハロゲン原子であり、ｙは０以上３以下の整数である。）で表される化合物を含むガスを添加することにより、ｐ型ＧａＡｓ層１１４、第１結晶層１３０あるいは第２結晶層１３２の抵抗値をさらに低減することができる。 According to the semiconductor substrate 100 described above, since the p-type GaAs layer 114 or the first crystal layer 130 is epitaxially grown by controlling the V / III ratio to 0.7 or more and 30 or less, the group 5 source gas is saved and the p-type GaAs layer 114 is saved. The resistance of the p-type GaAs layer 114 or the first crystal layer 130 can be reduced by doping a large amount of type impurities. Further, the V / III ratio is controlled to 0.7 or more and 30 or less and CX 4-y H y (where X is a halogen atom and y is an integer of 0 to 3) as a p-type impurity gas. The resistance value of the p-type GaAs layer 114, the first crystal layer 130, or the second crystal layer 132 can be further reduced by adding a gas containing a compound represented by:

（実施例）
ベース基板１０２上に、表１に示す結晶層をエピタキシャル成長させた。３族原料ガスとして、ＴＭＧおよびＴＭＡを用いた。５族原料ガスとして、アルシンを用いた。ｎ型不純物ガスとしてジシランを用いた。ｐ型不純物ガスとして、ＣＢｒＣｌ３を用いた。エピタキシャル成長の反応温度は、５７０℃〜６８０℃の範囲で制御した。

Figure 2012109557
(Example)
A crystal layer shown in Table 1 was epitaxially grown on the base substrate 102. TMG and TMA were used as the Group 3 source gas. Arsine was used as the Group 5 source gas. Disilane was used as the n-type impurity gas. CBrCl 3 was used as the p-type impurity gas. The reaction temperature for epitaxial growth was controlled in the range of 570 ° C to 680 ° C.
Figure 2012109557

上記のようにして形成した半導体基板にメサ加工を施し、電極を形成して垂直共振器面発光レーザを作成したところ、正常にレーザ発振が観測された。発振のしきい値電流は０．６ｍＡであった。スロープ効率は０．７９Ｗ／Ａであった。   When mesa processing was performed on the semiconductor substrate formed as described above to form a vertical cavity surface emitting laser by forming electrodes, laser oscillation was normally observed. The threshold current for oscillation was 0.6 mA. The slope efficiency was 0.79 W / A.

（比較例）
比較例として、ベース基板１０２の上に、表２に示す結晶層をエピタキシャル成長させた。ｐ型不純物ガスとしてＤＥＺｎを用いたこと、番号２の結晶層のエピタキシャル成長におけるＶ／ＩＩＩ比を３１としたこと、および番号３〜５結晶層のエピタキシャル成長におけるＶ／ＩＩＩ比を１０６としたこと、の他は実施例の場合と同様である。

Figure 2012109557
(Comparative example)
As a comparative example, the crystal layer shown in Table 2 was epitaxially grown on the base substrate 102. DEZn was used as the p-type impurity gas, the V / III ratio in the epitaxial growth of the number 2 crystal layer was set to 31, and the V / III ratio in the epitaxial growth of the number 3 to 5 crystal layer was set to 106. Others are the same as the case of an Example.
Figure 2012109557

上記のようにして形成した半導体基板に、実施例と同様にメサ加工を施し、電極を形成して垂直共振器面発光レーザを作成したところ、電流上昇に伴い急速にレーザ出力が低下する不具合が多発した。また、発振のしきい値電流は０．８ｍＡと実施例より高く、スロープ効率は０．５９Ｗ／Ａと実施例より低下した。   The semiconductor substrate formed as described above was subjected to mesa processing in the same manner as in the example, and when an electrode was formed to create a vertical cavity surface emitting laser, there was a problem that the laser output decreased rapidly as the current increased. It occurred frequently. The threshold current of oscillation was 0.8 mA, which was higher than that of the example, and the slope efficiency was 0.59 W / A, which was lower than that of the example.

上記した実施例および比較例から、ｐ型ＤＢＲ層の高Ａｌ組成層（第１結晶層１３０に相当する。）の水素濃度が１．３×１０１８ｍ−３以上である場合は、ＶＣＳＥＬ特性が良好であることがわかった。一方、当該水素濃度が２×１０１７ｍ−３未満である場合は、ＶＣＳＥＬ特性が不良であることがわかった。 From the examples and comparative examples described above, when the hydrogen concentration of the high Al composition layer (corresponding to the first crystal layer 130) of the p-type DBR layer is 1.3 × 10 18 m −3 or more, the VCSEL characteristics Was found to be good. On the other hand, when the hydrogen concentration is less than 2 × 10 17 m −3 , it was found that the VCSEL characteristics are poor.

以上、本発明を実施の形態を用いて説明したが、本発明の技術的範囲は上記実施の形態に記載の範囲には限定されない。上記実施の形態に、多様な変更または改良を加えることが可能であることが当業者に明らかである。その様な変更または改良を加えた形態も本発明の技術的範囲に含まれ得ることが、特許請求の範囲の記載から明らかである。   As mentioned above, although this invention was demonstrated using embodiment, the technical scope of this invention is not limited to the range as described in the said embodiment. It will be apparent to those skilled in the art that various modifications or improvements can be added to the above-described embodiment. It is apparent from the scope of the claims that the embodiments added with such changes or improvements can be included in the technical scope of the present invention.

１００ 半導体基板、１０２ ベース基板、１０４ バッファ層、１０６ ｎ型積層結晶層、１０８ ｉ型積層結晶層、１１０ ｐ型ＡｌＧａＡｓ層、１１２ ｐ型積層結晶層、１１４ ｐ型ＧａＡｓ層、１２０ ｉ型ＡｌＧａＡｓ層、１２２ ｉ型ＧａＡｓ／ＡｌＧａＡｓ層、１３０ 第１結晶層、１３２ 第２結晶層、２００ 垂直共振器面発光レーザ、２０６ ｎ型ミラー層、２０８ 活性層、２１０ 酸化狭窄層、２１２ ｐ型ミラー層、２１４ コンタクト層、２１６ 電極、２１８ 酸化層、２２０ クラッド層、２２２ 発光層 100 semiconductor substrate, 102 base substrate, 104 buffer layer, 106 n-type stacked crystal layer, 108 i-type stacked crystal layer, 110 p-type AlGaAs layer, 112 p-type stacked crystal layer, 114 p-type GaAs layer, 120 i-type AlGaAs layer 122 i-type GaAs / AlGaAs layer, 130 first crystal layer, 132 second crystal layer, 200 vertical cavity surface emitting laser, 206 n-type mirror layer, 208 active layer, 210 oxidation confinement layer, 212 p-type mirror layer, 214 contact layer, 216 electrode, 218 oxide layer, 220 clad layer, 222 light emitting layer

Claims (15)

ｐ型結晶層を有する垂直共振器面発光レーザ用の半導体基板であって、
前記ｐ型結晶層が、３−５族化合物半導体からなり、ｐ型不純物原子として炭素原子を含み、かつ、６×１０１７ｃｍ−３以上、６×１０１９ｃｍ−３以下の濃度の水素原子を含む
半導体基板。 A semiconductor substrate for a vertical cavity surface emitting laser having a p-type crystal layer,
The p-type crystal layer is made of a Group 3-5 compound semiconductor, contains carbon atoms as p-type impurity atoms, and has a concentration of 6 × 10 17 cm −3 or more and 6 × 10 19 cm −3 or less. Including semiconductor substrate. 前記ｐ型結晶層が、前記半導体基板が垂直共振器面発光レーザに用いられた場合にコンタクト層として機能するｐ型ＧａＡｓ層である
請求項１に記載の半導体基板。 The semiconductor substrate according to claim 1, wherein the p-type crystal layer is a p-type GaAs layer that functions as a contact layer when the semiconductor substrate is used in a vertical cavity surface emitting laser. 前記ｐ型ＧａＡｓ層が、１×１０１９ｃｍ−３以上、６×１０１９ｃｍ−３以下の濃度の水素原子を含む
請求項２に記載の半導体基板。 The semiconductor substrate according to claim 2, wherein the p-type GaAs layer includes hydrogen atoms having a concentration of 1 × 10 19 cm −3 or more and 6 × 10 19 cm −3 or less. 前記半導体基板が垂直共振器面発光レーザに用いられた場合にｐ型ミラー層として機能するｐ型積層結晶層を有し、
前記ｐ型積層結晶層が、ｐ型ＡｌｍＧａ１−ｍＡｓ（０＜ｍ≦１）からなる第１結晶層と、ｐ型ＡｌｎＧａ１−ｎＡｓ（０≦ｎ＜１、ｍ＞ｎ）からなる第２結晶層とを含む積層結晶層であり、
前記第１結晶層が、前記ｐ型結晶層である
請求項１に記載の半導体基板。 A p-type stacked crystal layer that functions as a p-type mirror layer when the semiconductor substrate is used in a vertical cavity surface emitting laser;
The p-type stacked crystal layer includes a first crystal layer made of p-type Al m Ga 1-m As (0 <m ≦ 1), and a p-type Al n Ga 1-n As (0 ≦ n <1, m>). a laminated crystal layer including a second crystal layer made of n),
The semiconductor substrate according to claim 1, wherein the first crystal layer is the p-type crystal layer. 前記第２結晶層に含まれる水素原子の濃度が、前記第１結晶層に含まれる水素原子の濃度より低い
請求項４に記載の半導体基板。 The semiconductor substrate according to claim 4, wherein the concentration of hydrogen atoms contained in the second crystal layer is lower than the concentration of hydrogen atoms contained in the first crystal layer. 前記第１結晶層が、ｐ型ＡｌｍＧａ１−ｍＡｓ層（０．５０≦ｍ≦１．０）である
請求項４または５に記載の半導体基板。 The semiconductor substrate according to claim 4, wherein the first crystal layer is a p-type Al m Ga 1-m As layer (0.50 ≦ m ≦ 1.0). 前記第１結晶層が、６×１０１７ｃｍ−３以上、２．５×１０１８ｃｍ−３以下の濃度の水素原子を含む
請求項４から６の何れか一項に記載の半導体基板。 The semiconductor substrate according to claim 4, wherein the first crystal layer includes hydrogen atoms having a concentration of 6 × 10 17 cm −3 or more and 2.5 × 10 18 cm −3 or less. 前記第１結晶層が、７×１０１７ｃｍ−３以上、５×１０１８ｃｍ−３以下の濃度の酸素原子を含む
請求項４から７のいずれか一項に記載の半導体基板。 The semiconductor substrate according to claim 4, wherein the first crystal layer includes oxygen atoms having a concentration of 7 × 10 17 cm −3 or more and 5 × 10 18 cm −3 or less. 垂直共振器面発光レーザ用の半導体基板の製造方法であって、
前記方法は、３族原料ガスと５族原料ガスとを用いたＭＯＣＶＤ法によりｐ型結晶層を成長する段階を有し、
前記３族原料ガスが、３族原子に少なくとも１つのアルキル基が結合した３族原子のアルキル化物を含み、
前記５族原料ガスが、５族原子の水素化物を含み、
前記ｐ型結晶層を成長する段階において、前記３族原料ガスのモル供給量に対する前記５族原料ガスのモル供給量の比（Ｖ／ＩＩＩ比）を０．７以上３０以下に制御する
半導体基板の製造方法。 A method of manufacturing a semiconductor substrate for a vertical cavity surface emitting laser,
The method includes the step of growing a p-type crystal layer by MOCVD using a Group 3 source gas and a Group 5 source gas,
The Group 3 source gas contains an alkylated group 3 atom in which at least one alkyl group is bonded to the Group 3 atom;
The group 5 source gas contains a hydride of group 5 atoms,
In the step of growing the p-type crystal layer, the ratio (V / III ratio) of the molar supply amount of the Group 5 source gas to the molar supply amount of the Group 3 source gas is controlled to 0.7 to 30. Semiconductor substrate Manufacturing method. 前記ｐ型結晶層を成長する段階において、前記３族原料ガスおよび前記５族原料ガスに、炭素化合物を添加する
請求項９に記載の半導体基板の製造方法。 The method for manufacturing a semiconductor substrate according to claim 9, wherein a carbon compound is added to the group 3 source gas and the group 5 source gas in the step of growing the p-type crystal layer. 前記炭素化合物が、ＣＸ４−ｙＨｙ（ただし、Ｘはハロゲン原子であり、ｙは０以上３以下の整数である。）で表される
請求項１０に記載の半導体基板の製造方法。 The method for producing a semiconductor substrate according to claim 10, wherein the carbon compound is represented by CX 4-y H y (where X is a halogen atom, and y is an integer of 0 or more and 3 or less). 請求項９から１１の何れか一項に記載の半導体基板の製造方法であって、
前記ｐ型結晶層を成長する段階において、ｐ型ＡｌｍＧａ１−ｍＡｓ（０＜ｍ≦１）からなる第１結晶層を成長させ、
前記方法は、前記３族原料ガスおよび前記５族原料ガスを用いたＭＯＣＶＤ法により、ｐ型ＡｌｎＧａ１−ｎＡｓ（０≦ｎ＜１、ｍ＞ｎ）からなる第２結晶層を成長する段階をさらに有し、
前記第１結晶層および前記第２結晶層を複数回繰り返して成長させることにより、ｐ型積層結晶層を形成し、
前記第２結晶層を成長する段階において、前記３族原料ガスおよび前記５族原料ガスに、ｐ型不純物原子を含有する化合物を添加する
半導体基板の製造方法。 A method for manufacturing a semiconductor substrate according to any one of claims 9 to 11,
In the step of growing the p-type crystal layer, a first crystal layer made of p-type Al m Ga 1-m As (0 <m ≦ 1) is grown.
In the method, a second crystal layer made of p-type Al n Ga 1-n As (0 ≦ n <1, m> n) is grown by MOCVD using the Group 3 source gas and the Group 5 source gas. And further comprising:
Forming the p-type stacked crystal layer by repeatedly growing the first crystal layer and the second crystal layer a plurality of times;
A method of manufacturing a semiconductor substrate, wherein a compound containing a p-type impurity atom is added to the group 3 source gas and the group 5 source gas in the stage of growing the second crystal layer. 前記ｐ型不純物原子を含有する化合物が、ＣＸ４−ｙＨｙ（ただし、Ｘはハロゲン原子であり、ｙは０以上３以下の整数である。）で表される
請求項１２に記載の半導体基板の製造方法。 The semiconductor according to claim 12, wherein the compound containing the p-type impurity atom is represented by CX 4-y H y (where X is a halogen atom, and y is an integer of 0 or more and 3 or less). A method for manufacturing a substrate. 前記方法は、３族原料ガスと５族原料ガスとを用いてｎ型結晶層またはｉ型結晶層を成長する段階を更に有し、
前記ｐ型結晶層を成長する段階における前記Ｖ／ＩＩＩ比が、前記ｎ型結晶層または前記ｉ型結晶層を成長する段階におけるいずれの前記Ｖ／ＩＩＩ比よりも小さい
請求項９から１３のいずれか一項に記載の半導体基板の製造方法。 The method further includes growing an n-type crystal layer or an i-type crystal layer using a group 3 source gas and a group 5 source gas,
The V / III ratio in the stage of growing the p-type crystal layer is smaller than any of the V / III ratios in the stage of growing the n-type crystal layer or the i-type crystal layer. A method for manufacturing a semiconductor substrate according to claim 1. コンタクト層として機能するｐ型結晶層、または、ｐ型ミラー層の少なくとも一部として機能するｐ型結晶層を有し、
前記ｐ型結晶層が、３−５族化合物半導体からなり、ｐ型不純物原子として炭素原子を含み、かつ、６×１０１７ｃｍ−３以上、６×１０１９ｃｍ−３以下の濃度の水素原子を含む
垂直共振器面発光レーザ。 A p-type crystal layer that functions as a contact layer, or a p-type crystal layer that functions as at least part of a p-type mirror layer;
The p-type crystal layer is made of a Group 3-5 compound semiconductor, contains carbon atoms as p-type impurity atoms, and has a concentration of 6 × 10 17 cm −3 or more and 6 × 10 19 cm −3 or less. Including vertical cavity surface emitting laser.
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