JP2008270760A - Semiconductor wafer and manufacturing method, and semiconductor element - Google Patents

Semiconductor wafer and manufacturing method, and semiconductor element Download PDF

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JP2008270760A
JP2008270760A JP2008061866A JP2008061866A JP2008270760A JP 2008270760 A JP2008270760 A JP 2008270760A JP 2008061866 A JP2008061866 A JP 2008061866A JP 2008061866 A JP2008061866 A JP 2008061866A JP 2008270760 A JP2008270760 A JP 2008270760A
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inp substrate
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gainnassb
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JP5515162B2 (en
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Kohei Miura
広平 三浦
Yasuhiro Inoguchi
康博 猪口
Mitsutaka Tsubokura
光隆 坪倉
Hiroshi Okada
浩 岡田
Yuichi Kawamura
裕一 河村
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Osaka University NUC
Sumitomo Electric Industries Ltd
Osaka Prefecture University PUC
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Sumitomo Electric Industries Ltd
Osaka Prefecture University PUC
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a semiconductor wafer having satisfactory surface smoothness for GaInNAsSb on an InP substrate and a semiconductor laminated structure with low crystal defect density, and to provide its manufacturing method and a semiconductor element. <P>SOLUTION: The method for manufacturing a semiconductor wafer comprises the steps of fixing the InP substrate 1 to a substrate-fixing part of an MBE device, and growing Ga<SB>1-x</SB>In<SB>x</SB>N<SB>y</SB>Sb<SB>z</SB>As<SB>1-y</SB>(0.4≤x≤0.8, 0<y≤0.2, 0≤z≤0.1), with a lattice constant difference to the InP substrate of not lower than -0.5% nor higher than +0.5% on the InP substrate, up to a film thickness of not smaller than 0.5 μm with a substrate-surface temperature measured by a pyrometer of >490°C and ≤530°C. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、半導体ウエハ、その製造方法および半導体素子に関するものである。   The present invention relates to a semiconductor wafer, a manufacturing method thereof, and a semiconductor element.

動植物または動植物由来の物質の分析、環境ガス分析、夜間の監視カメラ等には、近赤外光を感知できる受光素子が用いられる。この受光素子には、InGaAsなどの吸収端波長が1.7μm程度の化合物半導体が用いられているが、より長い波長域まで受光感度を拡大することが望ましい。また上記の波長域の発光素子の要求も高い。上記の波長域またはそれより長波長側に対応するバンドギャップエネルギを持つ化合物半導体として、Nを含むGaInNAsに着目し、GaInNAs層(膜厚7nm)を量子井戸構造に組み込んだ発光部の半導体レーザや、無歪光吸収層GaInNAs(膜厚0.5μm)のフォトダイオードが提案されている(特許文献1)。   A light-receiving element capable of sensing near-infrared light is used for the analysis of animals and plants or substances derived from animals and plants, environmental gas analysis, nighttime surveillance cameras, and the like. For this light receiving element, a compound semiconductor having an absorption edge wavelength of about 1.7 μm, such as InGaAs, is used, but it is desirable to expand the light receiving sensitivity to a longer wavelength region. There is also a high demand for light-emitting elements in the above wavelength range. Focusing on GaInNAs containing N as a compound semiconductor having a band gap energy corresponding to the above wavelength range or longer wavelength side, a semiconductor laser of a light emitting unit incorporating a GaInNAs layer (thickness 7 nm) in a quantum well structure, A photodiode having a non-strained light absorption layer GaInNAs (film thickness: 0.5 μm) has been proposed (Patent Document 1).

上述のGaInNAsは、原理的には近赤外域の長波長側に受光感度を拡大することはできるが、結晶性の良好なGaInNAsは成膜が難しく、実用化には至っていない。このため、GaAs基板上に歪単一量子井戸活性層にGaInNAs層(膜厚7nm)を配置した半導体レーザにおいて、上記のGaInNAsの結晶性を改善する検討がなされた(特許文献2)。この検討において、GaAs障壁層にGaInNAs井戸層を成長する際の成長温度を調査して、成長温度が350℃〜490℃のとき、滑らかな表面を持つGaInNAs層(膜厚7nm)を得ることができるとしている。成長温度が上記の温度範囲より高い場合、または低い場合には、GaInNAs表面に起伏が生じ、表面が荒れることが述べられている。なお、成長温度というとき、通常、基板表面をパイロメータ(通常、成膜装置に備え付けられている)で測定した温度をいう。
特開平9−219563号公報 特開平11−87848号公報
Although the above-described GaInNAs can in principle increase the light receiving sensitivity to the long wavelength side in the near infrared region, GaInNAs with good crystallinity is difficult to form and has not yet been put into practical use. For this reason, in a semiconductor laser in which a GaInNAs layer (film thickness: 7 nm) is arranged in a strained single quantum well active layer on a GaAs substrate, studies have been made to improve the crystallinity of the GaInNAs (Patent Document 2). In this examination, the growth temperature when a GaInNAs well layer is grown on the GaAs barrier layer is investigated, and when the growth temperature is 350 ° C. to 490 ° C., a GaInNAs layer (film thickness 7 nm) having a smooth surface can be obtained. I can do it. It is stated that when the growth temperature is higher or lower than the above temperature range, the GaInNAs surface is undulated and the surface becomes rough. Note that the growth temperature usually refers to a temperature obtained by measuring the substrate surface with a pyrometer (usually provided in a film forming apparatus).
JP-A-9-219563 JP-A-11-87848

上記のような、GaInNAsの結晶性の改善の取り組みがなされたにも拘らず、実験対象の化合物半導体に限って有効な方法が検討されているため、その方法がなぜ有効なのか等の原因究明は不十分である。このため、より基本的な原因究明と汎用性のある改善方法を見出すことを可能とする実験データの累積が求められている。とくに、近赤外域において、産業上、重要な地位を占めるInP基板におけるGaInNAsのエピタキシャル成長層の結晶性改善、とくに表面平滑性の改善が望まれている。本発明は、InP基板上に結晶性および表面平滑性が良好なGaInNAs層を形成することによって得ることができる、結晶欠陥密度の低い半導体ウエハ、半導体素子および半導体ウエハの製造方法を提供することを目的とする。   In spite of the efforts to improve the crystallinity of GaInNAs as described above, a method effective only for the compound semiconductor to be tested has been studied. Is insufficient. For this reason, there is a demand for accumulation of experimental data that makes it possible to find a more basic cause and find a versatile improvement method. In particular, in the near infrared region, it is desired to improve the crystallinity of an epitaxially grown layer of GaInNAs on an InP substrate, which occupies an important industrial position, particularly to improve the surface smoothness. The present invention provides a semiconductor wafer having a low crystal defect density, a semiconductor element, and a method for manufacturing the semiconductor wafer, which can be obtained by forming a GaInNAs layer having good crystallinity and surface smoothness on an InP substrate. Objective.

本発明の半導体素子の製造方法は、InP基板をMBE(Molecular Beam Epitaxy)装置の基板取付部に取り付ける工程と、InP基板上に該InP基板との格子定数差が−0.5%以上+0.5%以下の範囲のGa1−xInSbzAs1−y(0.4≦x≦0.8、0<y≦0.2、0≦z≦0.1)を、パイロメータで測定の基板表面温度490℃超え530℃以下の状態で膜厚0.5μm以上に成長させる工程とを備えることを特徴とする。 The method of manufacturing a semiconductor device according to the present invention includes a step of attaching an InP substrate to a substrate mounting portion of an MBE (Molecular Beam Epitaxy) apparatus, and a lattice constant difference between the InP substrate on the InP substrate is −0.5% or more +0. Ga 1-x In x N y Sb z As 1-y (0.4 ≦ x ≦ 0.8, 0 <y ≦ 0.2, 0 ≦ z ≦ 0.1) in the range of 5% or less And a step of growing to a film thickness of 0.5 μm or more in a state where the substrate surface temperature of the measurement exceeds 490 ° C. and is 530 ° C. or less.

上記の方法によって、表面平滑性の良好なGa1−xInAs1−y層を含み、結晶欠陥密度の低い半導体積層構造の半導体ウエハを得ることができる。Sbを含ませることにより、とくに表面性状を良好にすることができる。 By the above method, a semiconductor wafer having a semiconductor multilayer structure including a Ga 1-x In x N y As 1-y layer with good surface smoothness and a low crystal defect density can be obtained. By including Sb, the surface properties can be particularly improved.

本発明の半導体ウエハは、上記の製造方法で製造され、Ga1−xInSbzAs1−y(0.4≦x≦0.8、0<y≦0.2、0≦z≦0.1)のAFM(Atom Force Microscopy)で測定のRmsラフネスが10nm以下であることを特徴とする。これによって、Ga1−xInSbzAs1−y層にエピタキシャル成長する上層との界面における格子欠陥密度を減らすことができる。このため、たとえば受光素子の場合、pn接合やpin接合を形成した構造において、界面における高格子欠陥密度に起因する暗電流増大を防ぐことができる。 The semiconductor wafer of the present invention is manufactured by the above-described manufacturing method, and Ga 1-x In x N y Sb z As 1-y (0.4 ≦ x ≦ 0.8, 0 <y ≦ 0.2, 0 ≦ Rms roughness measured by AFM (Atom Force Microscopy) with z ≦ 0.1) is 10 nm or less. This can reduce the lattice defect density at the interface between the upper layer to be epitaxially grown on Ga 1-x In x N y Sb z As 1-y layer. For this reason, for example, in the case of a light receiving element, an increase in dark current due to a high lattice defect density at the interface can be prevented in a structure in which a pn junction or a pin junction is formed.

また、本発明の半導体ウエハは、InP基板と、そのInP基板上に位置する膜厚0.5μm以上のGa1−xInSbzAs1−y(0.4≦x≦0.8、0<y≦0.2、0≦z≦0.1)層とを備える。そして、Ga1−xInSbzAs1−y層とInP基板との格子定数差が−0.5%以上+0.5%以下の範囲内にあり、Ga1−xInSbzAs1−y層と、該Ga1−xInSbzAs1−y層に接して位置する上層との界面が、AFMで測定のRmsラフネス10nm以下に相当する凹凸を有することを特徴とする。 In addition, the semiconductor wafer of the present invention includes an InP substrate and Ga 1-x In x N y Sb z As 1-y (0.4 ≦ x ≦ 0. 8, 0 <y ≦ 0.2, 0 ≦ z ≦ 0.1) layers. The difference in lattice constant between the Ga 1-x In x N y Sb z As 1-y layer and the InP substrate is in the range of −0.5% or more and + 0.5% or less, and Ga 1−x In x N and y Sb z as 1-y layer, an interface between the upper layer positioned in contact with the Ga 1-x in x N y Sb z as 1-y layer, the irregularities correspond to the following Rms roughness 10nm measured by AFM It is characterized by having.

上記の構成により、近赤外域の長波長側に対応する吸収端波長を持ち、表面平滑性に優れた活性層または受光層を含む、結晶欠陥密度の低い積層構造の半導体素子を形成することができる。ここで、界面のRmsラフネスは、半導体素子のGa1−xInSbzAs1−y層より上の各層をエッチングして除いた後、AFM(Atomic Force Microscopy:原子間力顕微鏡)によって、内蔵する自動測定操作により求めることができる。この場合、5μm×5μmの視野におけるRmsラフネスとする。また、エッチングにおいて材料選択度が芳しくない場合、断面における界面を観察して、一次元的に界面の粗さを求め、上記Rmsラフネス10nm以下に相当する凹凸か否かを判断してもよい。すなわち、断面における界面の凹凸のAFM測定によって、Rmsラフネス(5μm×5μm)10nm以下を代替してもよい。上記断面の観察には、透過型電子顕微鏡電子顕微鏡(Transmission Electron Microscopy:TEM)もしくは高分解能走査型電子顕微鏡(High Resolution Scanning Electron Microscopy:HR−SEM)を用いてもよい。 With the above configuration, it is possible to form a semiconductor element having a laminated structure with a low crystal defect density, including an active layer or a light receiving layer having an absorption edge wavelength corresponding to the long wavelength side in the near infrared region and excellent surface smoothness. it can. Here, the Rms roughness of the interface is determined by removing each layer above the Ga 1-x In x N y Sb z As 1-y layer of the semiconductor element by etching and then AFM (Atomic Force Microscopy). Can be obtained by a built-in automatic measurement operation. In this case, the Rms roughness in the visual field of 5 μm × 5 μm is used. Further, when the material selectivity is not good in etching, the interface in the cross section may be observed to obtain the roughness of the interface in a one-dimensional manner, and it may be determined whether or not the unevenness corresponds to the Rms roughness of 10 nm or less. That is, Rms roughness (5 μm × 5 μm) of 10 nm or less may be substituted by AFM measurement of the unevenness of the interface in the cross section. For observation of the cross section, a transmission electron microscope (TEM) or a high resolution scanning electron microscope (HR-SEM) may be used.

本発明の半導体素子は、上記のいずれかの半導体ウエハを用いて作製されたことを特徴とする。この構成により、近赤外域の長波長側に対応する吸収端波長を持ち、表面平滑性に優れた活性層または受光層を含む、結晶欠陥密度の低い積層構造の半導体素子を得ることができる。なお本発明の半導体素子は、上記の構成が満たされれば、受光素子や発光素子に限定されずその他の半導体素子を包含するものである。   The semiconductor element of the present invention is manufactured using any one of the above semiconductor wafers. With this configuration, it is possible to obtain a semiconductor device having a laminated structure with a low crystal defect density, including an active layer or a light receiving layer having an absorption edge wavelength corresponding to the long wavelength side in the near infrared region and having excellent surface smoothness. The semiconductor element of the present invention includes other semiconductor elements without being limited to the light receiving element and the light emitting element as long as the above configuration is satisfied.

上記の半導体素子を、フォトダイオードとすることができる。これによって、暗電流の少ない、近赤外域の長波長側に受光感度を有するフォトダイオードを得ることができる。 The semiconductor element can be a photodiode. As a result, a photodiode having a small light current and a light receiving sensitivity on the long wavelength side in the near infrared region can be obtained.

本発明によれば、近赤外域において、産業上、重要な地位を占めるInP基板上に、結晶性および表面平滑性が良好なGa1−xInSbzAs1−y(0.4≦x≦0.8、0<y≦0.2、0≦z≦0.1)をエピタキシャル成長することができ、この結果、結晶欠陥密度の低い半導体積層構造の半導体ウエハ、半導体素子および半導体ウエハの製造方法を得ることができる。 According to the present invention, Ga 1-x In x N y Sb z As 1-y (0...) Having good crystallinity and surface smoothness on an InP substrate that occupies an industrially important position in the near infrared region. 4 ≦ x ≦ 0.8, 0 <y ≦ 0.2, 0 ≦ z ≦ 0.1), and as a result, a semiconductor wafer, a semiconductor element, and a semiconductor having a semiconductor stacked structure with a low crystal defect density A wafer manufacturing method can be obtained.

図1は、本発明の実施の形態の半導体素子におけるフォトダイオードを構成する半導体積層構造を示す断面図である。Sをドープしたn型InP基板1上にInGaAsバッファ層2が位置し、その上に、Ga1−xInSbzAs1−y(0.4≦x≦0.8、0<y≦0.2、0≦z≦0.1)(以後、「GaInNAsSb」と記す)層3およびAlInAs層4が順次、エピタキシャル成長している。なお、Sbを含まない状態(z=0)以外の状態がない場合のGaInNAsSb層3を、GaInNAs層3と記す。 FIG. 1 is a cross-sectional view showing a semiconductor stacked structure constituting a photodiode in a semiconductor element according to an embodiment of the present invention. An InGaAs buffer layer 2 is positioned on an n-type InP substrate 1 doped with S, and Ga 1-x In x N y Sb z As 1-y (0.4 ≦ x ≦ 0.8, 0 < (y ≦ 0.2, 0 ≦ z ≦ 0.1) (hereinafter referred to as “GaInNAsSb”) layer 3 and AlInAs layer 4 are sequentially epitaxially grown. The GaInNAsSb layer 3 when there is no state other than a state not containing Sb (z = 0) is referred to as a GaInNAs layer 3.

たとえば、図1の半導体積層構造10をフォトダイオードに用いる場合には、図2に示すように、GaInNAsSb層3を受光層とし、その上層のAlInAs層4を窓層とする。次いで、AlInAs窓層4の上に不純物導入用拡散マスクパターン5を形成し、その不純物導入用拡散マスクパターン5からp型不純物のZn等をGaInNAsSb受光層3に届くように導入してp型領域15を形成する。このp型領域15の形成により、GaInNAsSb受光層3に、pn接合またはpin接合が形成される。p型領域にはp部電極12がオーミック接触するようにAuZnで形成され、またInP基板1の裏面にn部電極11が、やはりオーミック接触するようにAuGeNiで形成される。   For example, when the semiconductor laminated structure 10 of FIG. 1 is used for a photodiode, as shown in FIG. 2, the GaInNAsSb layer 3 is used as a light receiving layer, and the AlInAs layer 4 thereabove is used as a window layer. Next, an impurity introduction diffusion mask pattern 5 is formed on the AlInAs window layer 4, and p-type impurity Zn or the like is introduced from the impurity introduction diffusion mask pattern 5 so as to reach the GaInNAsSb light-receiving layer 3 to form a p-type region. 15 is formed. By forming the p-type region 15, a pn junction or a pin junction is formed in the GaInNAsSb light receiving layer 3. The p-type region is formed of AuZn so that the p-type electrode 12 is in ohmic contact, and the n-type electrode 11 is formed of AuGeNi on the back surface of the InP substrate 1 so as to be in ohmic contact.

上記のp部電極12およびn部電極11には逆バイアス電圧が印加され、空乏層をGaInNAsSb受光層3に広げ、光の入射を待機する。GaInNAsSb受光層3の吸収端波長(近赤外域の長波長側)より短い波長の光が入射されたとき、光電流が生じ、光の入射を検知することができる。上記のGaInNAsSb受光層3の表面の平滑性が良くないと、良好な結晶性の窓層4を成長できず、またGaInNAsSb受光層3と窓層4との界面に高い格子欠陥密度が形成される。このため、pn接合またはpin接合の端に格子欠陥密度の高い部分が位置することになり、暗電流の増大をもたらし、受光感度を劣化させる。このため、GaInNAsSb受光層3の表面のRmsラフネスを10nm以下にするのがよい。または断面で観察して、GaInNAsSb受光層3とAlINAs窓層4との界面の凹凸を、Rmsラフネス10nm以下相当とするのがよい。   A reverse bias voltage is applied to the p-part electrode 12 and the n-part electrode 11, and the depletion layer is spread over the GaInNAsSb light-receiving layer 3 and waits for the incidence of light. When light having a wavelength shorter than the absorption edge wavelength (near-wavelength long wavelength side) of the GaInNAsSb light-receiving layer 3 is incident, a photocurrent is generated, and the incidence of light can be detected. If the surface of the GaInNAsSb light-receiving layer 3 is not smooth, the window layer 4 having good crystallinity cannot be grown, and a high lattice defect density is formed at the interface between the GaInNAsSb light-receiving layer 3 and the window layer 4. . For this reason, a portion having a high lattice defect density is located at the end of the pn junction or the pin junction, resulting in an increase in dark current and a deterioration in light receiving sensitivity. For this reason, the Rms roughness of the surface of the GaInNAsSb light receiving layer 3 is preferably 10 nm or less. Alternatively, it is preferable that the roughness of the interface between the GaInNAsSb light-receiving layer 3 and the AlINAs window layer 4 is equivalent to an Rms roughness of 10 nm or less when observed in a cross section.

次に、図1に示す半導体積層構造10の製造方法について、図3および図4を用いて説明する。図3は製造方法の各工程の流れを、また図4はMBE製造装置を示す図である。まず標準的な製造方法を、図3のステップにしたがって説明する。標準的な製造方法では、はじめに図4に示すMBE成膜装置30の基板取付部33に、InP基板1を取り付ける(図3のステップS1)。基板取付部33には赤外線加熱装置33が内蔵され、パイロメータ等の温度表示を見ながら、外部から設定温度を制御できるように配線されている。次いで、InP基板1上にInGaAsバッファ層2をエピタキシャル成長させる(ステップS2)。次いで、MBE法により、InGaAsバッファ層2上にGaInNAsSb層3をエピタキシャル成長させる(ステップS3)。InP基板を含む積層構造体10は、回転および加熱機構を備える基板取付部33に取り付けられ、上記のように加熱され、回転状態とされる。成膜には、層を構成する元素に対応して蒸発源の分子線セル(E形電子銃)が配置されており、固相元素がIn、Ga、Sb、Asの場合には、In、Ga、SbおよびAsの各分子線を出射する分子線セルが、各別に配置されている。図4では、分子線セルは、ガスセル31を含んで3つ示されているが、何個か省略されている。半導体素子の作製のために、GaInNAsSb層3に上層、たとえば窓層をエピタキシャル成長させる(ステップS4)。ここで、図4において、各段階の半導体積層構造10はInP基板1を含んでいる。また、基板温度というとき、パイロメータで測定される各段階の半導体積層構造の表面温度をいう。   Next, a method for manufacturing the semiconductor multilayer structure 10 shown in FIG. 1 will be described with reference to FIGS. FIG. 3 shows the flow of each process of the manufacturing method, and FIG. 4 shows the MBE manufacturing apparatus. First, a standard manufacturing method will be described according to the steps in FIG. In the standard manufacturing method, first, the InP substrate 1 is attached to the substrate attaching portion 33 of the MBE film forming apparatus 30 shown in FIG. 4 (step S1 in FIG. 3). An infrared heating device 33 is built in the board mounting portion 33 and wired so that the set temperature can be controlled from the outside while viewing the temperature display of a pyrometer or the like. Next, the InGaAs buffer layer 2 is epitaxially grown on the InP substrate 1 (step S2). Next, the GaInNAsSb layer 3 is epitaxially grown on the InGaAs buffer layer 2 by MBE (step S3). The laminated structure 10 including the InP substrate is attached to the substrate attachment portion 33 having a rotation and heating mechanism, heated as described above, and brought into a rotation state. In the film formation, a molecular beam cell (E-type electron gun) as an evaporation source is arranged corresponding to the elements constituting the layer. When the solid phase element is In, Ga, Sb, As, In, Molecular beam cells that emit molecular beams of Ga, Sb, and As are arranged separately. In FIG. 4, three molecular beam cells including the gas cell 31 are shown, but some of them are omitted. In order to manufacture the semiconductor element, an upper layer, for example, a window layer is epitaxially grown on the GaInNAsSb layer 3 (step S4). Here, in FIG. 4, the semiconductor multilayer structure 10 at each stage includes the InP substrate 1. Further, the substrate temperature refers to the surface temperature of the semiconductor laminated structure at each stage measured by a pyrometer.

次に、上述の標準的な製造方法に対する変形例1および変形例2の製造方法を、図3にしたがって説明する。
(変形例1):変形例1では、成膜方法は問わず(図4のMBE成膜装置30を使用してもよいし、使用しなくてもよい)、予めInGaAsバッファ層2を成膜してあるInP基板を基板取付部33に取り付けることができる(図3の破線のコースに対応する)。この変形例1では、ステップS1では予めInGaAsバッファ層2を成膜してあるInP基板を基板取付部33に取り付け、ステップS2をとばして、ステップS3に移る製造方法を用いてもよい。
(変形例2):変形例2では、InGaAsバッファ層を省略して直接にInP基板1上にGaInNAsSb層3を成長させることができる。この変形例2のInGaAsバッファ層を省略する製造方法は、図3において、ステップS2を省略して、ステップS1から直ちにステップS3に移行する。そして、予めInGaAsバッファ層を形成したInP基板を基板取付部に取り付ける必要は、当然、ない。
(変形例3):変形例3では、InP基板1上にInGaAsバッファ層2とGaInNAsSb層3を成長し、別の成膜装置(たとえばMOVPE(Metal Organic Vapor
Phase Epitaxy)成膜装置)でステップ4における上層(たとえばInP層)を成長する。
Next, the manufacturing method of the modification 1 and the modification 2 with respect to the above-mentioned standard manufacturing method is demonstrated according to FIG.
(Modification 1): In Modification 1, the InGaAs buffer layer 2 is formed in advance regardless of the film formation method (the MBE film formation apparatus 30 in FIG. 4 may or may not be used). The InP substrate can be attached to the substrate attachment portion 33 (corresponding to the course indicated by the broken line in FIG. 3). In the first modification, the manufacturing method may be used in which the InP substrate on which the InGaAs buffer layer 2 is formed in advance is attached to the substrate attaching portion 33 in step S1, step S2 is skipped, and the process proceeds to step S3.
(Modification 2): In Modification 2, the GaInNAsSb layer 3 can be grown directly on the InP substrate 1 without the InGaAs buffer layer. In the manufacturing method in which the InGaAs buffer layer according to the second modification is omitted, step S2 is omitted in FIG. 3, and the process immediately proceeds from step S1 to step S3. Of course, it is not necessary to attach the InP substrate on which the InGaAs buffer layer has been formed in advance to the substrate mounting portion.
(Modification 3): In Modification 3, an InGaAs buffer layer 2 and a GaInNAsSb layer 3 are grown on an InP substrate 1, and another film forming apparatus (for example, MOVPE (Metal Organic Vapor) is formed.
The upper layer (for example, InP layer) in step 4 is grown in the (Phase Epitaxy) film forming apparatus).

化学組成や成膜速度の調整のために、セルシャッタや基板シャッタの開閉を調整するが、その制御のために附属する計算機が用いられる。基板温度等は、パイロメータによって測定される。RHEED(reflection high electron energy diffraction)観察のために、電子が浅い入射角度で積層構造体10に入射するようにRHEED電子銃が配置され、その回折像を得るための蛍光スクリーン(RHEEDスクリーン)およびその回折像を撮像するカメラが回折方向位置に設けられる。RHEEDは、積層構造体10の結晶性の評価、成膜素過程の把握等のために用いられる。また、質量分析装置、ビームモニタ、水晶膜厚計などの観察装置が取り付けられている。分子線などのうちで積層構造体10に組み込まれなかったものは、真空排気系へと排気される。また、液体窒素シュラウドは、分子線が衝突して発生した不純物の吸着などのために用いられる。成膜装置内は、ゲートバルブを介在させて真空排気系と連通している。   In order to adjust the chemical composition and the film forming speed, the opening and closing of the cell shutter and the substrate shutter are adjusted, and an attached computer is used for the control. The substrate temperature or the like is measured by a pyrometer. For RHEED (reflection high electron energy diffraction) observation, a RHEED electron gun is arranged so that electrons are incident on the laminated structure 10 at a shallow incident angle, and a fluorescent screen (RHEED screen) for obtaining a diffraction image thereof, and its A camera that captures the diffraction image is provided at a position in the diffraction direction. The RHEED is used for evaluating the crystallinity of the laminated structure 10, grasping the film forming process, and the like. In addition, observation devices such as a mass spectrometer, a beam monitor, and a quartz film thickness meter are attached. Among the molecular beams and the like, those that are not incorporated into the laminated structure 10 are exhausted to the vacuum exhaust system. The liquid nitrogen shroud is used for adsorption of impurities generated by collision of molecular beams. The film forming apparatus communicates with the vacuum exhaust system via a gate valve.

GaInNAsSb層を形成する際に、基板取付部33の赤外線加熱装置を制御して基板温度を490℃超え530℃以下にする。基板温度を490℃超え530℃以下の温度に保つことにより、成長するGaInNAsSb層3の表面平滑性を向上することができる。基板温度は上述のように、パイロメータによって確認することができる。   When forming the GaInNAsSb layer, the substrate temperature is controlled to be over 490 ° C. and below 530 ° C. by controlling the infrared heating device of the substrate mounting portion 33. By maintaining the substrate temperature at a temperature higher than 490 ° C. and lower than 530 ° C., the surface smoothness of the growing GaInNAsSb layer 3 can be improved. As described above, the substrate temperature can be confirmed by a pyrometer.

窒素(N)をGaInNAsSb層に導入するために、窒素ガスをガスラインに供給し、窒素プラズマセル31で窒素の励起状態を得て、この励起状態の窒素分子線を積層構造体10に照射する。   In order to introduce nitrogen (N) into the GaInNAsSb layer, nitrogen gas is supplied to the gas line, an excited state of nitrogen is obtained by the nitrogen plasma cell 31, and the laminated structure 10 is irradiated with this excited molecular nitrogen beam. .

上述のように、基板温度を490℃超え530℃以下にすることにより、GaInNAsSb層3の表面平滑性は良好になるが、その場合、AFM像により、AFMに内蔵されている機構などを用いて表面をスキャンしてRmsラフネスを自動的に求めることができる。AFM装置は、数多くの会社から市販されており、いずれのAFM装置を用いても、それほど性能に大きな差はない。本発明の実施の形態において、GaInNAsSb層3の表面のRmsラフネスは、10nm以下とすることができる。   As described above, the surface smoothness of the GaInNAsSb layer 3 is improved by setting the substrate temperature to be higher than 490 ° C. and lower than 530 ° C. However, in that case, using the mechanism incorporated in the AFM based on the AFM image. The surface can be scanned to automatically determine Rms roughness. AFM apparatuses are commercially available from many companies, and there is not much difference in performance regardless of which AFM apparatus is used. In the embodiment of the present invention, the Rms roughness of the surface of the GaInNAsSb layer 3 can be 10 nm or less.

また、半導体素子を作製した後、半導体積層構造10の断面を露出して、GaInNAsSb層3とその上層であるAlInAs層4との界面において、表面粗さを評価することができる。図5は、断面において界面の凹凸を評価する類推的な方法を説明するための図である。図5において、一視野の界面のマクロの長さは2μm程度として、GaInNAsSb層3の、視野における最高高さと最低高さの差Δhまたは高低差を求める。このΔhを少なくとも30視野、望ましくは50視野以上で求めて、算術平均により平均値とする。本発明の実施の形態においては、表面Rms10nm以下からの類推により、上記の平均高低差が30nm以下であるのが好ましい。   Further, after the semiconductor element is manufactured, the cross section of the semiconductor multilayer structure 10 is exposed, and the surface roughness can be evaluated at the interface between the GaInNAsSb layer 3 and the AlInAs layer 4 which is the upper layer. FIG. 5 is a diagram for explaining an analogy method for evaluating unevenness of an interface in a cross section. In FIG. 5, the macro length of the interface of one visual field is set to about 2 μm, and the difference Δh or the height difference between the maximum height and the minimum height in the visual field of the GaInNAsSb layer 3 is obtained. This Δh is obtained in at least 30 visual fields, preferably 50 visual fields or more, and is averaged by arithmetic average. In the embodiment of the present invention, the average height difference is preferably 30 nm or less by analogy from the surface Rms of 10 nm or less.

(InP基板上へのGaInNAsSb層の成長)
次に、本発明の実施の形態において、InP基板上にGaInNAsSb層を形成する際の基板温度の影響について、上記特許文献2に開示の内容と比較しながら説明する。図6(a)は、基板温度542℃〜544℃で、Nを含まないInGaAs層をInP基板1にエピタキシャル成長させた場合のInGaAs層の表面を光学顕微鏡で観察した結果を示す図であり、また図6(b)はその模式図である。図6(a),(b)によれば、基板温度が542℃程度になると、As抜けが原因の粗大な表面欠陥が発生する。表面欠陥の径は100μmにも達する巨大なものであり、このような表面欠陥が生じては、結晶性は大きく劣化して仕上げた半導体積層構造はほとんど使い物にならない。As抜けの問題は、特許文献2では触れておらず、本発明における特有の問題である。
(Growth of GaInNAsSb layer on InP substrate)
Next, in the embodiment of the present invention, the influence of the substrate temperature when forming the GaInNAsSb layer on the InP substrate will be described in comparison with the content disclosed in the above-mentioned Patent Document 2. FIG. 6A is a diagram showing a result of observing the surface of the InGaAs layer with an optical microscope when an InGaAs layer not containing N is epitaxially grown on the InP substrate 1 at a substrate temperature of 542 ° C. to 544 ° C. FIG. 6B is a schematic diagram thereof. According to FIGS. 6A and 6B, when the substrate temperature reaches about 542 ° C., coarse surface defects due to As missing are generated. The diameter of the surface defect is as large as 100 μm. If such a surface defect occurs, the crystallinity is greatly deteriorated and the finished semiconductor laminated structure is hardly usable. The problem of As missing is not mentioned in Patent Document 2, and is a problem peculiar to the present invention.

Nを含むGaInNAsSbにおいても、基板温度が高い場合、As抜けが生じ、巨大な表面欠陥を防止することはできない。GaInNAsSb層成長のための基板温度は、したがってAs抜けが生じない温度範囲としなければならず、これによって基板温度の上限が決まる。GaInNAsSbのAs抜けを防止するには、上記のInGaAsの成長の知見を含め、GaInNAsSb自体の成長実験での知見より、基板温度を530℃以下にする必要がある。   Even in GaInNAsSb containing N, when the substrate temperature is high, As is lost and a huge surface defect cannot be prevented. Therefore, the substrate temperature for the growth of the GaInNAsSb layer must be in a temperature range in which As is not lost, and this determines the upper limit of the substrate temperature. In order to prevent GaInNAsSb from coming out of As, it is necessary to set the substrate temperature to 530 ° C. or less based on the knowledge of the growth experiment of GaInNAsSb itself, including the knowledge of the growth of InGaAs.

本発明の実施の形態において、MBE法による成膜の基板温度は490℃超えとする。特許文献2において、GaAs基板上に厚み7nm程度のGaInNAsSbを成長させる温度範囲を350℃以上490℃以下としていることと明白に相違する。この点について、次のような結晶上の相違が原因と考えられる。
(1)本発明におけるGaInNAsSb層の膜厚は0.5μm(500nm)以上であり、上記特許文献2の膜厚7nmと比較して、非常に厚い。膜厚が極端に薄い場合、基板温度を高めにすると、凝集等が生じ、途切れてしまい、非常に薄くて平坦な膜を形成しにくい。上記の基板温度の差の一因に、膜厚の相違も考えられる。すなわち、基板温度の高温側の設定は、本発明と、特許文献2に開示の発明とでは、異なる現象をもとにして設定している。
(2)InP基板上に成長するGaInNAsSbは、GaAs基板上のGaInNAsSbよりも、基板との格子定数の相違が小さく、基板による結晶歪が小さい。また、In組成はInP基板上のGaInNAsSbのほうが大きい。このため、Gaの濃度が高くIn濃度が低い相領域と、In濃度が高くGa濃度が低い相領域とに相分離する温度範囲が、GaAs基板上に成長させるほうが低温域になるためと考えられる。膜厚が薄いことも相分離温度の低温側シフトに作用している可能性もある。その結果、特許文献2に開示の発明においては、相分離温度の上限は、350℃程度になるのに対して、InP基板上では490℃程度になる。この結果、特許文献2に開示の発明では基板温度の低温側限界は350℃となったのに対して、本発明の場合、基板温度の低温側限界は490℃超えとなった。
上記の(1)および(2)の一方、または両方が、上述の基板温度の相違に影響している。
In the embodiment of the present invention, the substrate temperature for film formation by MBE is over 490 ° C. In Patent Document 2, the temperature range in which GaInNAsSb having a thickness of about 7 nm is grown on a GaAs substrate is clearly different from 350 ° C. or more and 490 ° C. or less. This is considered to be caused by the following crystal difference.
(1) The film thickness of the GaInNAsSb layer in the present invention is 0.5 μm (500 nm) or more, which is very thick compared to the film thickness of 7 nm in Patent Document 2. When the film thickness is extremely thin, if the substrate temperature is raised, aggregation or the like occurs and breaks, making it difficult to form a very thin and flat film. A difference in film thickness is also considered as one cause of the difference in the substrate temperature. That is, the setting of the substrate temperature on the high temperature side is set based on different phenomena between the present invention and the invention disclosed in Patent Document 2.
(2) GaInNAsSb grown on an InP substrate has a smaller difference in lattice constant from the substrate than GaInNAsSb on a GaAs substrate, and crystal distortion due to the substrate is small. The In composition is larger for GaInNAsSb on the InP substrate. For this reason, it is considered that the temperature range in which phase separation into a phase region having a high Ga concentration and a low In concentration and a phase region having a high In concentration and a low Ga concentration is performed on a GaAs substrate is a lower temperature region. . The thin film thickness may also affect the low temperature side shift of the phase separation temperature. As a result, in the invention disclosed in Patent Document 2, the upper limit of the phase separation temperature is about 350 ° C., whereas it is about 490 ° C. on the InP substrate. As a result, in the invention disclosed in Patent Document 2, the lower limit of the substrate temperature is 350 ° C., whereas in the present invention, the lower limit of the substrate temperature is over 490 ° C.
One or both of the above (1) and (2) affect the above-described difference in substrate temperature.

(実施例1)
次に、実施例により本発明の作用効果を説明する。試験体の本発明例1および比較例1を用いて、GaInNAs層の表面平滑性を調査した。上記試験体は、図1に示す構成を持ち、次の手順により作製した。
(本発明例1):Sをドープした面方位(100)のInP基板1上に、MBE法により、Siドープn型InGaAsバッファ層2をエピタキシャル成長した。膜厚は1.5μmであり、In組成は53%であり、キャリア濃度は5×1016cm−3とした。次に、GaInNAs層3をMBE法によりエピタキシャル成長した。III族のGa組成は46%、In組成54%とし、またV族のN組成は1.5%、As組成は98.5%とした。膜厚は2.5μmとした。ドーピングは行っていない。次にAlInAs層4をMBE法でエピタキシャル成長した。In組成は52%であり、InP基板に格子整合させている。膜厚は0.6μmとした。上記のGaInNAs層3を成長させる際の基板温度は、502℃とした。
(比較例1):本発明例1と同じように、MBE法により、Sをドープした面方位(100)のInP基板上に、順次、InGaAs層2、GaInNAs層3、AlInAs層4を順次、エピタキシャル成長して、半導体積層構造10を形成した。各半導体層の組成は、本発明例1と同じにした。相違点は、比較例1では、GaInNAs層3を成長する際の基板温度は484℃とした。
Example 1
Next, the function and effect of the present invention will be described with reference to examples. Using Example 1 of the present invention and Comparative Example 1, the surface smoothness of the GaInNAs layer was investigated. The test specimen had the configuration shown in FIG. 1 and was manufactured by the following procedure.
(Invention Example 1): A Si-doped n-type InGaAs buffer layer 2 was epitaxially grown on an InP substrate 1 having a surface orientation (100) doped with S by MBE. The film thickness was 1.5 μm, the In composition was 53%, and the carrier concentration was 5 × 10 16 cm −3 . Next, the GaInNAs layer 3 was epitaxially grown by the MBE method. The group III Ga composition was 46%, the In composition 54%, the group V N composition 1.5%, and the As composition 98.5%. The film thickness was 2.5 μm. Doping is not performed. Next, the AlInAs layer 4 was epitaxially grown by the MBE method. The In composition is 52% and is lattice matched to the InP substrate. The film thickness was 0.6 μm. The substrate temperature for growing the GaInNAs layer 3 was 502 ° C.
(Comparative Example 1): In the same manner as Example 1 of the present invention, an InGaAs layer 2, a GaInNAs layer 3, and an AlInAs layer 4 were sequentially formed on an InP substrate having a surface orientation (100) doped with S by MBE. The semiconductor multilayer structure 10 was formed by epitaxial growth. The composition of each semiconductor layer was the same as Example 1 of the present invention. The difference is that in Comparative Example 1, the substrate temperature when growing the GaInNAs layer 3 was 484 ° C.

上記本発明例1および比較例1の試験体について、GaInNAs層3を成長させた時点で、GaInNAs層3の表面を、5μm×5μmの領域についてAFMで観察した。本発明例1の表面について、図7(a)にAFM像を、また図7(b)にその模式図を示す。比較例1について、図8(a)にAFM像を、また図8(b)にその模式図を示す。図7(a)に示す「Zrange」は、Z方向すなわち凹凸方向のフルスケールを意味する。したがって図7(a)では凹凸方向のフルスケールを50nmとして撮像しているのに対して、図8(a)では同方向のフルスケールを100nmとしている。すなわち比較例1では凹凸が大きく、フルスケールを本発明例1の2倍にしないと、適切なAFM像を得ることができないことを示している。逆に言えば、図7(a)では、拡大して表面の微細な凹凸を撮像している。   About the test body of the said invention example 1 and the comparative example 1, when the GaInNAs layer 3 was grown, the surface of the GaInNAs layer 3 was observed by AFM about the area | region of 5 micrometers x 5 micrometers. FIG. 7A shows an AFM image and FIG. 7B shows a schematic diagram of the surface of Example 1 of the present invention. For Comparative Example 1, FIG. 8A shows an AFM image, and FIG. 8B shows a schematic diagram thereof. “Zrange” shown in FIG. 7A means a full scale in the Z direction, that is, the uneven direction. Accordingly, in FIG. 7A, the full scale in the concave-convex direction is taken as 50 nm, whereas in FIG. 8A, the full scale in the same direction is taken as 100 nm. That is, in Comparative Example 1, the unevenness is large, and it is indicated that an appropriate AFM image cannot be obtained unless the full scale is doubled that of Example 1 of the present invention. In other words, in FIG. 7A, an enlarged image of fine irregularities on the surface is captured.

図7(a),(b)と図8(a),(b)とを比較して一目瞭然であるが、本発明例1では、拡大した倍率によってその緻密で均一な凹凸が認められるのに比して、比較例1では倍率を小さくしたにも拘わらず粗大な凸状物が間欠的に位置している。上記の両試験体に対してRmsラフネス(5μm×5μm)を求めると、本発明例1では3.5nmであった。一方、比較例1では14.7nmと、本発明例1の約4倍のRmsラフネスとなった。本実施例より、MBE法によるGaInNAsの成長において、基板温度502℃(本発明例1)と、基板温度484℃(比較例1)と、20℃の相違によって、GaInNAs層の表面性状が激変することが判明した。   FIG. 7 (a), (b) and FIG. 8 (a), (b) are obvious at a glance, but in Example 1 of the present invention, the dense and uniform irregularities are recognized by the enlarged magnification. In contrast, in Comparative Example 1, coarse projections are intermittently positioned despite the reduction in magnification. When Rms roughness (5 μm × 5 μm) was obtained for both the above-mentioned specimens, it was 3.5 nm in Example 1 of the present invention. On the other hand, in Comparative Example 1, the Rms roughness was 14.7 nm, which is about 4 times that of Example 1 of the present invention. From this example, in the growth of GaInNAs by the MBE method, the surface properties of the GaInNAs layer change drastically due to the difference of 20 ° C. between the substrate temperature of 502 ° C. (Example 1 of the present invention) and the substrate temperature of 484 ° C. (Comparative Example 1). It has been found.

(実施例2)
MBE法によるGaInNAsの結晶性の基板温度の影響について、さらに調査を行った。試験方法は次の要領で行った。
(試験方法):MBE法により、InP基板(100)上にIn0.57Ga0.43As層(膜厚0.15μm)をバッファ層としてGa0.43In0.571−xAs(膜厚1μm)を成長した。Asの供給にはバルブクラッキングセルを用いた。窒素源であるRF(Radio
Frequency)プラズマ放電条件および成長速度は固定した。成長温度(基板温度)を変えた結晶のX線ロッキング曲線およびフォトルミネッセンス(PL)発光強度を測定し、結果を図9および図10にそれぞれ示した。
(結果):X線ロッキング曲線より、基板温度460℃以下ではGaInNAs層の回折ピークがブロードとなり、また480℃でもGaInNAsの回折ピークはそれ以上の温度の回折ピークに比べてブロードで、ピーク強度がやや低い。このため、最良の結晶性を得るためには、490℃を超え500℃または515℃程度に基板温度を上げる必要がある。また、PL発光強度については、成長温度480℃より成長温度500℃のほうが非常に高く、結晶性が良好である。またAs/III フラックス比、すなわちIII族元素(Ga,In)とAsとの分圧比、は大きいほうが結晶性は良好となる。
(Example 2)
Further investigation was performed on the influence of the substrate temperature on the crystallinity of GaInNAs by the MBE method. The test method was performed as follows.
(Test method): By an MBE method, an In 0.57 Ga 0.43 As layer (film thickness: 0.15 μm) is formed on the InP substrate (100) as a buffer layer, and Ga 0.43 In 0.57 N 1-x As x (film thickness 1 μm) was grown. A valve cracking cell was used to supply As. RF (Radio), a nitrogen source
Frequency) Plasma discharge conditions and growth rate were fixed. X-ray rocking curves and photoluminescence (PL) emission intensities of crystals with different growth temperatures (substrate temperatures) were measured, and the results are shown in FIGS. 9 and 10, respectively.
(Result): From the X-ray rocking curve, the diffraction peak of the GaInNAs layer becomes broader at a substrate temperature of 460 ° C. or lower, and the diffraction peak of GaInNAs is broader than the diffraction peak at a temperature higher than 480 ° C. Slightly low. Therefore, in order to obtain the best crystallinity, it is necessary to raise the substrate temperature to over 500 ° C. or 515 ° C. exceeding 490 ° C. Further, the PL emission intensity is much higher at the growth temperature of 500 ° C. than the growth temperature of 480 ° C., and the crystallinity is good. Further, the crystallinity becomes better as the As / III flux ratio, that is, the partial pressure ratio between the group III element (Ga, In) and As is larger.

実施例2によれば、480℃の基板温度ではGaInNAsの結晶性はベストではなく、それより高温の500℃または515℃で良好な結晶性が得られることを確認することができた。高温側については、図6(a),(b)に示した540℃程度におけるAs抜けの問題を考慮しなければならない。図6〜図10に示す現象を総合することにより、490℃超え530℃以下の狭い範囲に、InP基板上に良好な表面平滑性のGaInNAs層を成長できる基板温度の条件があることを合理性をもって確認することができた。   According to Example 2, it was confirmed that the crystallinity of GaInNAs was not the best at a substrate temperature of 480 ° C., and good crystallinity was obtained at a higher temperature of 500 ° C. or 515 ° C. On the high temperature side, the problem of As missing at about 540 ° C. shown in FIGS. 6A and 6B must be considered. By combining the phenomena shown in FIG. 6 to FIG. 10, it is rational that there is a substrate temperature condition in which a GaInNAs layer having good surface smoothness can be grown on an InP substrate in a narrow range of 490 ° C. to 530 ° C. I was able to confirm with.

(実施例3)
次に、Sbの表面平滑性に及ぼす効果を確認した実施例3について説明する。本実施例3における試験体である本発明例2は、図1に示す構成を持ち、zがゼロでないGaInNAsSb層3を含むものであり、次の手順により作製した。
(本発明例2):SをドープしたInP基板1上に、MBE法により、InGaAsバッファ層2をエピタキシャル成長した。InGaAsバッファ層2の成長条件(組成、膜厚、ドーピング)は、上記実施例1における本発明例1と同じである。次に、Sbを含むGaInNAsSb層3をMBE法によりエピタキシャル成長した。このときの基板温度は500℃とした。III族のGa組成は45%、In組成55%とし、またV族のN組成は1.5%、As組成は95.9%、Sb組成は2.6%とした。膜厚は2.5μmとした。ドーピングは行っていない。次にAlInAs層4をMBE法でエピタキシャル成長した。AlInAsの成長条件は、実施例1における本発明例1と同じである。
(Example 3)
Next, Example 3 in which the effect of Sb on the surface smoothness was confirmed will be described. Example 2 of the present invention, which is a test body in Example 3, includes the GaInNAsSb layer 3 having the configuration shown in FIG. 1 and with z not zero, and was prepared by the following procedure.
(Invention Example 2): An InGaAs buffer layer 2 was epitaxially grown on the S-doped InP substrate 1 by MBE. The growth conditions (composition, film thickness, doping) of the InGaAs buffer layer 2 are the same as those of Example 1 of the present invention in Example 1 above. Next, the GaInNAsSb layer 3 containing Sb was epitaxially grown by the MBE method. The substrate temperature at this time was 500 ° C. The group III Ga composition was 45%, the In composition 55%, the group V N composition 1.5%, the As composition 95.9%, and the Sb composition 2.6%. The film thickness was 2.5 μm. Doping is not performed. Next, the AlInAs layer 4 was epitaxially grown by the MBE method. The growth conditions of AlInAs are the same as those of Example 1 of the present invention in Example 1.

本発明例2について、GaInNAsSb層3を成長させた時点で、GaInNAsSb層3の表面を、5μm×5μmの領域についてAFMで観察した。本発明例2の表面について、図11(a)にAFM像を、また図11(b)にその模式図を示す。本発明例2では、Sbを含むため表面平滑性に優れ、Zrange10nmと、図7や図8の場合よりも格段に大きく拡大することにより、ようやく微小な凹凸を認めることができる。したがってSbを含ませることにより、GaInNAsSb層3の表面平滑性は格段に良好になる。   With respect to Inventive Example 2, when the GaInNAsSb layer 3 was grown, the surface of the GaInNAsSb layer 3 was observed with an AFM in a 5 μm × 5 μm region. FIG. 11A shows an AFM image and FIG. 11B shows a schematic diagram of the surface of Example 2 of the present invention. In Example 2 of the present invention, since Sb is included, the surface smoothness is excellent, and Zrange 10 nm can be finally recognized by microscopically enlarging larger than in the case of FIGS. 7 and 8. Therefore, by including Sb, the surface smoothness of the GaInNAsSb layer 3 is remarkably improved.

本発明例2に対してRmsラフネス(5μm×5μm)を求めると、0.27nmであった。この本発明例2のRmsラフネスの測定結果を、実施例1における試験体である本発明例1および比較例1と合わせて、表1に示す。   When Rms roughness (5 μm × 5 μm) was obtained for Example 2 of the present invention, it was 0.27 nm. The measurement results of Rms roughness of Example 2 of the present invention are shown in Table 1 together with Example 1 of the present invention and Comparative Example 1 which are test bodies in Example 1.

Figure 2008270760
Figure 2008270760

表1によれば、基板温度を高くすることにより、Rmsラフネスは1/4程度に改善される。基板温度を高くした上でGaInNAsにSbを含ませることにより、基板温度を高くする方策のみをとった場合に比べて、Rmsラフネスを1/10以上抑制することができる。   According to Table 1, the Rms roughness is improved to about ¼ by increasing the substrate temperature. By adding Sb to GaInNAs after increasing the substrate temperature, the Rms roughness can be suppressed by 1/10 or more compared to the case where only measures for increasing the substrate temperature are taken.

(実施の形態以外の形態)
1.半導体素子の形態
フォトダイオードとしての形態以外に、任意の素子であってよい。膜厚が0.5μm以上であれば、発光素子と受光素子とを問わず何でもよい。
2.バッファ層および窓層の材料
フォトダイオードとする場合、格子整合バッファ層は、InP基板に格子整合する限り何でもよく、最も広くは、InGaAl1−x−yAs(0≦x≦1、0≦y≦1)およびInPのいずれかに限定されない。また、そして、窓層については、何でもよく、InAlAsおよびInPに限定されない。
(Forms other than the embodiment)
1. Form of Semiconductor Element Other than the form as a photodiode, any element may be used. Any film thickness may be used regardless of the light emitting element and the light receiving element as long as the film thickness is 0.5 μm or more.
2. Material of Buffer Layer and Window Layer When a photodiode is used, the lattice matching buffer layer may be anything as long as it is lattice matched to the InP substrate, and most widely, In x Ga y Al 1-xy As (0 ≦ x ≦ 1, 0 ≦ y ≦ 1) and InP. The window layer may be anything and is not limited to InAlAs and InP.

上記において、本発明の実施の形態および実施例について説明を行ったが、上記に開示された本発明の実施の形態および実施例は、あくまで例示であって、本発明の範囲はこれら発明の実施の形態に限定されない。本発明の範囲は、特許請求の範囲の記載によって示され、さらに特許請求の範囲の記載と均等の意味および範囲内でのすべての変更を含むものである。   Although the embodiments and examples of the present invention have been described above, the embodiments and examples of the present invention disclosed above are merely examples, and the scope of the present invention is the implementation of these inventions. It is not limited to the form. The scope of the present invention is indicated by the description of the scope of claims, and further includes meanings equivalent to the description of the scope of claims and all modifications within the scope.

本発明の半導体ウエハ、半導体素子および半導体ウエハの製造方法を用いることにより、表面平滑性に優れたGaInNAsSb層を得ることができ、半導体積層構造の結晶性を向上することができる。このため、たとえば近赤外域の長波長側において暗電流が少なく、受光感度に優れたフォトダイオード等を得ることができる。   By using the semiconductor wafer, the semiconductor element, and the method for manufacturing a semiconductor wafer of the present invention, a GaInNAsSb layer having excellent surface smoothness can be obtained, and the crystallinity of the semiconductor multilayer structure can be improved. For this reason, for example, a photodiode having a low dark current on the long wavelength side in the near-infrared region and excellent in light receiving sensitivity can be obtained.

本発明の実施の形態の半導体素子におけるエピタキシャル積層構造を説明するための図である。It is a figure for demonstrating the epitaxial laminated structure in the semiconductor element of embodiment of this invention. 図1の積層構造をもとにしたフォトダイオードを示す図である。It is a figure which shows the photodiode based on the laminated structure of FIG. 本発明の実施の形態の半導体素子の製造方法を説明するための図である。It is a figure for demonstrating the manufacturing method of the semiconductor element of embodiment of this invention. MBE成膜装置を説明する図である。It is a figure explaining an MBE film-forming apparatus. GaInNAsSb層と上層との界面で、GaInNAsSb層の表面粗さを求める方法を示す図である。It is a figure which shows the method of calculating | requiring the surface roughness of a GaInNAsSb layer in the interface of a GaInNAsSb layer and an upper layer. 基板温度が本発明の実施の形態より高い場合に生じるAs抜けに起因する表面欠陥を示す図であり、(a)は光学顕微鏡像であり、(b)はその模式図である。It is a figure which shows the surface defect resulting from As omission produced when a substrate temperature is higher than embodiment of this invention, (a) is an optical microscope image, (b) is the schematic diagram. (a)は、実施例1における本発明例1のAFM像であり、(b)はその模式図である。(A) is an AFM image of Example 1 of the present invention in Example 1, and (b) is a schematic diagram thereof. (a)は、実施例1における比較例1のAFM像であり、(b)はその模式図である。(A) is the AFM image of the comparative example 1 in Example 1, (b) is the schematic diagram. 実施例2におけるGaInNAsの結晶性に及ぼす基板温度の影響を示す、X線ロッキング曲線を示す図である。FIG. 4 is a diagram showing an X-ray rocking curve showing the influence of the substrate temperature on the crystallinity of GaInNAs in Example 2. 実施例2におけるGaInNAsの結晶性に及ぼす基板温度の影響を示す、フォトルミネッセンス発光強度を示す図である。It is a figure which shows the photoluminescence light emission intensity which shows the influence of the substrate temperature which acts on the crystallinity of GaInNAs in Example 2. FIG. (a)は、実施例3における本発明例2のAFM像であり、(b)はその模式図である。(A) is an AFM image of Example 2 of the present invention in Example 3, and (b) is a schematic diagram thereof.

符号の説明Explanation of symbols

1 InP基板、2 InGaAs層、3 GaInNAsSb層、4 AlInAs層、5 不純物拡散用マスクパターン、10 半導体積層構造、11 n部電極、12 p部電極、15 p型領域、30 MBE成膜装置、31 窒素プラズマセル、33 基板取付部。

DESCRIPTION OF SYMBOLS 1 InP substrate, 2 InGaAs layer, 3 GaInNAsSb layer, 4 AlInAs layer, 5 Impurity diffusion mask pattern, 10 Semiconductor laminated structure, 11 n part electrode, 12 p part electrode, 15 p type area | region, 30 MBE film-forming apparatus, 31 Nitrogen plasma cell, 33 substrate mounting part.

Claims (5)

InP基板をMBE(Molecular Beam Epitaxy)装置の基板取付部に取り付ける工程と、
前記InP基板上に該InP基板との格子定数差が−0.5%以上+0.5%以下の範囲のGa1−xInSbzAs1−y(0.4≦x≦0.8、0<y≦0.2、0≦z≦0.1)を、パイロメータで測定の基板表面温度490℃超え530℃以下の状態で膜厚0.5μm以上に成長させる工程とを備えることを特徴とする、半導体ウエハの製造方法。
Attaching the InP substrate to the substrate mounting portion of the MBE (Molecular Beam Epitaxy) device;
Ga 1-x In x N y Sb z As 1-y (0.4 ≦ x ≦ 0) in which the lattice constant difference with the InP substrate is in the range of −0.5% to + 0.5% on the InP substrate. .8, 0 <y ≦ 0.2, 0 ≦ z ≦ 0.1) is grown to a film thickness of 0.5 μm or more in a state where the substrate surface temperature measured with a pyrometer is over 490 ° C. and below 530 ° C. A method for producing a semiconductor wafer, comprising:
請求項1の製造方法で製造され、Ga1−xInSbzAs1−y(0.4≦x≦0.8、0<y≦0.2、0≦z≦0.1)のAFM(Atom Force Microscopy)で測定のRmsラフネスが10nm以下であることを特徴とする、半導体ウエハ。 Produced by the production method according to claim 1, Ga 1-x In x N y Sb z As 1-y (0.4 ≦ x ≦ 0.8,0 <y ≦ 0.2,0 ≦ z ≦ 0.1 A semiconductor wafer characterized in that the Rms roughness measured by AFM (Atom Force Microscopy) is 10 nm or less. InP基板と、
前記InP基板上に位置する膜厚0.5μm以上のGa1−xInSbzAs1−y(0.4≦x≦0.8、0<y≦0.2、0≦z≦0.1)層とを備え、
前記Ga1−xInSbzAs1−y層と前記InP基板との格子定数差が−0.5%以上+0.5%以下の範囲内にあり、
前記Ga1−xInSbzAs1−y層と、該Ga1−xInSbzAs1−y層に接して位置する上層との界面が、AFMで測定のRmsラフネス10nm以下に相当する凹凸を有することを特徴とする、半導体ウエハ。
An InP substrate;
Ga 1-x In x N y Sb z As 1-y (0.4 ≦ x ≦ 0.8, 0 <y ≦ 0.2, 0 ≦ z) having a film thickness of 0.5 μm or more located on the InP substrate. ≦ 0.1) layer,
The lattice constant difference between the Ga 1-x In x N y Sb z As 1-y layer and the InP substrate is in the range of −0.5% or more and + 0.5% or less,
Said Ga 1-x In x N y Sb z As 1-y layer, an interface between the upper layer positioned in contact with the Ga 1-x In x N y Sb z As 1-y layer, Rms measured by AFM A semiconductor wafer having irregularities corresponding to a roughness of 10 nm or less.
請求項2または3に記載の半導体ウエハを用いて作製されたことを特徴とする、半導体素子。   A semiconductor device manufactured using the semiconductor wafer according to claim 2. 前記半導体素子が、フォトダイオードであることを特徴とする、請求項4に記載の半導体素子。   The semiconductor device according to claim 4, wherein the semiconductor device is a photodiode.
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