JP6480244B2 - Vapor growth method - Google Patents

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JP6480244B2
JP6480244B2 JP2015081146A JP2015081146A JP6480244B2 JP 6480244 B2 JP6480244 B2 JP 6480244B2 JP 2015081146 A JP2015081146 A JP 2015081146A JP 2015081146 A JP2015081146 A JP 2015081146A JP 6480244 B2 JP6480244 B2 JP 6480244B2
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gallium nitride
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英志 高橋
英志 高橋
佐藤　裕輔
裕輔 佐藤
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Nuflare Technology Inc
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Description

本発明は、シリコン基板上に窒化ガリウムを形成する気相成長方法に関する。   The present invention relates to a vapor phase growth method for forming gallium nitride on a silicon substrate.

高品質な半導体膜を成膜する方法として、ウェハ等の基板に気相成長により単結晶膜を成長させるエピタキシャル成長技術がある。エピタキシャル成長では、ウェハを加熱しながら、成膜の原料となるソースガス等のプロセスガスをウェハ表面に供給する。ウェハ表面ではソースガスの熱反応等が生じ、ウェハ表面にエピタキシャル単結晶膜が成膜される。   As a method for forming a high-quality semiconductor film, there is an epitaxial growth technique in which a single crystal film is grown on a substrate such as a wafer by vapor phase growth. In epitaxial growth, a process gas such as a source gas, which is a raw material for film formation, is supplied to the wafer surface while heating the wafer. A thermal reaction of the source gas occurs on the wafer surface, and an epitaxial single crystal film is formed on the wafer surface.

近年、発光デバイスやパワーデバイスの材料として、窒化ガリウム（ＧａＮ）系の半導体デバイスが注目されている。ＧａＮ系の半導体膜を成膜するエピタキシャル成長技術として、有機金属気相成長法（ＭＯＣＶＤ法）がある。   In recent years, gallium nitride (GaN) -based semiconductor devices have attracted attention as materials for light-emitting devices and power devices. As an epitaxial growth technique for forming a GaN-based semiconductor film, there is a metal organic chemical vapor deposition method (MOCVD method).

例えば、シリコン（Ｓｉ）基板上に窒化ガリウム膜を形成する場合、窒化ガリウム膜の膜厚が厚くなると、シリコンと窒化ガリウムの熱膨張係数等の違いに起因して窒化ガリウム膜にクラックが発生するという問題がある。特許文献１には、この問題を解決するために、窒化アルミニウム（ＡｌＮ）のバッファ層をシリコン基板上に形成した後、第１の圧力で第１の窒化ガリウムを形成し、第１の圧力よりも低い第２の圧力で窒化ガリウムを形成する方法が記載されている。   For example, when a gallium nitride film is formed on a silicon (Si) substrate, a crack occurs in the gallium nitride film due to a difference in thermal expansion coefficient between silicon and gallium nitride as the film thickness of the gallium nitride film increases. There is a problem. In Patent Document 1, in order to solve this problem, after forming a buffer layer of aluminum nitride (AlN) on a silicon substrate, first gallium nitride is formed at a first pressure, and from the first pressure, Describes a method of forming gallium nitride at a lower second pressure.

特開２００６−１２８６２６号公報JP 2006-128626 A

本発明が解決しようとする課題は、シリコン基板上に窒化ガリウムを形成する際のクラックの発生を抑制する気相成長方法を提供することである。   The problem to be solved by the present invention is to provide a vapor phase growth method that suppresses the generation of cracks when gallium nitride is formed on a silicon substrate.

本発明の一態様の気相成長方法は、シリコン基板上に単結晶の窒化アルミニウム膜を形成し、前記窒化アルミニウム膜上に単結晶の窒化アルミニウムガリウム膜を形成し、前記窒化アルミニウムガリウム膜上に単結晶の第１の窒化ガリウム膜を形成し、前記第１の窒化ガリウム膜上に、前記第１の窒化ガリウム膜の形成よりも高い温度且つ高い成長速度で単結晶の第２の窒化ガリウムを形成する気相成長方法であって、前記第１の窒化ガリウム膜を島状に形成し、前記第１の窒化ガリウム膜の高さの平均を１０ｎｍ以上５０ｎｍ以下とし、前記第２の窒化ガリウム膜を、前記窒化アルミニウムガリウム膜及び前記第１の窒化ガリウム膜に接するように形成する。
In the vapor phase growth method of one embodiment of the present invention, a single crystal aluminum nitride film is formed over a silicon substrate, a single crystal aluminum gallium nitride film is formed over the aluminum nitride film, and the aluminum gallium nitride film is formed over the aluminum gallium nitride film. A single-crystal first gallium nitride film is formed, and a single-crystal second gallium nitride is formed on the first gallium nitride film at a higher temperature and higher growth rate than the formation of the first gallium nitride film. In the vapor phase growth method to be formed, the first gallium nitride film is formed in an island shape, the average height of the first gallium nitride film is set to 10 nm or more and 50 nm or less, and the second gallium nitride film is formed. In contact with the aluminum gallium nitride film and the first gallium nitride film .

上記態様の気相成長方法において、前記第１の窒化ガリウム膜形成時のＶ／ＩＩＩ比が前記第２の窒化ガリウム膜形成時のＶ／ＩＩＩ比より大きいことが望ましい。   In the vapor phase growth method of the above aspect, it is desirable that a V / III ratio at the time of forming the first gallium nitride film is larger than a V / III ratio at the time of forming the second gallium nitride film.

上記態様の気相成長方法において、前記第１の窒化ガリウム膜形成時の成長速度が３μｍ／ｈｏｕｒ以下であることが望ましい。   In the vapor phase growth method of the above aspect, it is desirable that the growth rate when forming the first gallium nitride film is 3 μm / hour or less.

上記態様の気相成長方法において、前記第１の窒化ガリウム膜形成時の温度が９５０℃以上１０５０℃未満であり、前記第２の窒化ガリウム膜形成時の温度が１０００℃以上１１００℃未満であることが望ましい。   In the vapor phase growth method of the above aspect, the temperature at the time of forming the first gallium nitride film is 950 ° C. or higher and lower than 1050 ° C., and the temperature at the time of forming the second gallium nitride film is 1000 ° C. or higher and lower than 1100 ° C. It is desirable.

本発明によれば、シリコン基板上に窒化ガリウム膜を形成する際のクラックの発生を抑制する気相成長方法を提供することが可能となる。   ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the vapor phase growth method which suppresses generation | occurrence | production of the crack at the time of forming a gallium nitride film | membrane on a silicon substrate.

実施形態の気相成長方法のプロセスフロー図。The process flow figure of the vapor phase growth method of an embodiment. 実施形態の気相成長方法を示す模式断面図。The schematic cross section which shows the vapor phase growth method of embodiment. 実施形態の気相成長方法を示す模式断面図。The schematic cross section which shows the vapor phase growth method of embodiment. 実施形態の気相成長方法を示す模式断面図。The schematic cross section which shows the vapor phase growth method of embodiment.

以下、本発明の実施形態について図面を参照しつつ説明する。   Embodiments of the present invention will be described below with reference to the drawings.

実施形態の気相成長方法は、シリコン基板上に単結晶の窒化アルミニウム膜を形成し、窒化アルミニウム膜上に単結晶の窒化アルミニウムガリウム膜を形成し、窒化アルミニウム膜上に単結晶の第１の窒化ガリウム膜を形成し、第１の窒化ガリウム膜上に、第１の窒化ガリウムの形成よりも高い温度且つ高い成長速度で単結晶の第２の窒化ガリウム膜を形成する。   In the vapor phase growth method of the embodiment, a single crystal aluminum nitride film is formed on a silicon substrate, a single crystal aluminum gallium nitride film is formed on the aluminum nitride film, and a single crystal first gallium nitride film is formed on the aluminum nitride film. A gallium nitride film is formed, and a single-crystal second gallium nitride film is formed on the first gallium nitride film at a higher temperature and a higher growth rate than the formation of the first gallium nitride.

図１は、実施形態の気相成長方法のプロセスフロー図である。また、図２−図４は、実施形態の気相成長方法を示す模式断面図である。   FIG. 1 is a process flow diagram of a vapor phase growth method according to an embodiment. 2 to 4 are schematic cross-sectional views showing the vapor phase growth method of the embodiment.

本実施形態の気相成長方法は、シリコン（Ｓｉ）基板準備ステップ（Ｓ１００）、窒化アルミニウム膜（ＡｌＮ）形成ステップ（Ｓ１１０）、窒化アルミニウムガリウム膜（ＡｌＧａＮ）形成ステップ（Ｓ１２０）、第１の窒化ガリウム膜（ＧａＮ）形成ステップ（Ｓ１３０）、第２の窒化ガリウム膜（ＧａＮ）形成ステップ（Ｓ１４０）を備えている。本実施形態では、ＭＯＣＶＤ法により成膜が行われる。   The vapor phase growth method of this embodiment includes a silicon (Si) substrate preparation step (S100), an aluminum nitride film (AlN) formation step (S110), an aluminum gallium nitride film (AlGaN) formation step (S120), and a first nitridation step. A gallium film (GaN) formation step (S130) and a second gallium nitride film (GaN) formation step (S140) are provided. In the present embodiment, film formation is performed by the MOCVD method.

まず、例えば、水素（Ｈ２）中で、１１００℃でベークし、自然酸化膜を除去した（１１１）面の単結晶のシリコン基板１０を準備する（Ｓ１００）。シリコン基板１０の厚さは、例えば、３００μｍ以上１５００μｍ以下である。 First, for example, a (111) -plane single crystal silicon substrate 10 is prepared by baking at 1100 ° C. in hydrogen (H 2 ) to remove the natural oxide film (S100). The thickness of the silicon substrate 10 is, for example, not less than 300 μm and not more than 1500 μm.

次に、シリコン基板１０上に単結晶の窒化アルミニウム（ＡｌＮ）膜１２を形成する（Ｓ１１０）。窒化アルミニウム膜１２は、シリコン基板１０上にエピタキシャル成長させる。   Next, a single crystal aluminum nitride (AlN) film 12 is formed on the silicon substrate 10 (S110). The aluminum nitride film 12 is epitaxially grown on the silicon substrate 10.

窒化アルミニウム膜１２は、シリコン基板１０を加熱し、例えば、水素（Ｈ２）で希釈されたトリメチルアルミニウム（ＴＭＡ）と、水素（Ｈ２）で希釈されたアンモニア（ＮＨ３）をソースガスとして供給することにより成長させる。ＴＭＡはアルミニウム（Ａｌ）のソースガスであり、アンモニアは窒素（Ｎ）のソースガスである。 Aluminum nitride film 12, the silicon substrate 10 is heated, for example, hydrogen trimethylaluminum diluted with (H 2) (TMA), supply hydrogen ammonia diluted with (H 2) (NH 3) as a source gas To grow. TMA is a source gas of aluminum (Al), and ammonia is a source gas of nitrogen (N).

窒化アルミニウム膜１２の成長温度は、例えば、１０００℃以上１２００℃以下とする。窒化アルミニウム膜１２の結晶性を向上させる観点から、成長温度は１０００℃以上であることが望ましい。窒化アルミニウム膜１２の膜厚は、例えば、２００ｎｍ以上３００ｎｍ以下とする。   The growth temperature of the aluminum nitride film 12 is, for example, 1000 ° C. or more and 1200 ° C. or less. From the viewpoint of improving the crystallinity of the aluminum nitride film 12, the growth temperature is desirably 1000 ° C. or higher. The film thickness of the aluminum nitride film 12 is, for example, not less than 200 nm and not more than 300 nm.

窒化アルミニウム膜１２は、シリコン基板１０上にガリウム（Ｇａ）を含む単結晶膜をエピタキシャル成長させる際に、シリコンとガリウムとの反応が生じ、ガリウムを含む単結晶膜の膜質が劣化することや、シリコン基板がメルトバックすることを抑制する。また、シリコンと、ガリウムを含む単結晶膜との格子不整合を緩和するバッファ層として機能する。   When the aluminum nitride film 12 is epitaxially grown on a silicon substrate 10 containing a single crystal film containing gallium (Ga), a reaction between silicon and gallium occurs, and the quality of the single crystal film containing gallium deteriorates. The substrate is prevented from melting back. In addition, it functions as a buffer layer that alleviates lattice mismatch between silicon and a single crystal film containing gallium.

次に、窒化アルミニウム膜１２上に、単結晶の窒化アルミニウムガリウム（ＡｌＸＧａ（１−Ｘ）Ｎ、ただし０＜Ｘ＜１）膜１４を形成する（Ｓ１２０、図２）。窒化アルミニウムガリウム膜１４は、窒化アルミニウム膜１２上にエピタキシャル成長させる Next, a single crystal aluminum gallium nitride (Al X Ga (1-X) N, where 0 <X <1) film 14 is formed on the aluminum nitride film 12 (S120, FIG. 2). The aluminum gallium nitride film 14 is epitaxially grown on the aluminum nitride film 12.

窒化アルミニウムガリウム膜１４は、シリコン基板１０を加熱し、例えば、水素（Ｈ２）で希釈されたトリメチルアルミニウム（ＴＭＡ）とトリメチルガリウム（ＴＭＧ）、水素（Ｈ２）で希釈されたアンモニア（ＮＨ３）をソースガスとして供給することにより成長させる。ＴＭＡはアルミニウム（Ａｌ）のソースガスであり、ＴＭＧはガリウム（Ｇａ）のソースガスであり、アンモニアは窒素（Ｎ）のソースガスである。 The aluminum gallium nitride film 14 heats the silicon substrate 10 and, for example, trimethylaluminum (TMA) diluted with hydrogen (H 2 ), trimethylgallium (TMG), and ammonia (NH 3 ) diluted with hydrogen (H 2 ). ) As a source gas. TMA is a source gas of aluminum (Al), TMG is a source gas of gallium (Ga), and ammonia is a source gas of nitrogen (N).

窒化アルミニウムガリウム膜１４の成長温度は、例えば、１０００℃以上１２００℃以下とする。窒化アルミニウムガリウム膜１４の膜厚は、例えば、１５０ｎｍ以上５００ｎｍ以下とする。   The growth temperature of the aluminum gallium nitride film 14 is, for example, 1000 ° C. or more and 1200 ° C. or less. The film thickness of the aluminum gallium nitride film 14 is, for example, not less than 150 nm and not more than 500 nm.

窒化アルミニウムガリウム膜１４は、窒化アルミニウム膜１２と、窒化アルミニウムガリウム膜１４の上層に形成される単結晶ガリウム膜との格子不整合を緩和するバッファ層として機能する。格子不整合を緩和する観点から、窒化アルミニウムガリウム膜１４中のアルミニウム含有量を、窒化アルミニウムガリウム膜１４から窒化アルミニウムガリウム膜１４の上層に形成される単結晶ガリウム膜に向かう方向に低減させることが望ましい。また、窒化アルミニウムガリウム膜１４は、窒化アルミニウム膜１２から伸びる転位の向きを曲げて、転位が上層に形成される単結晶ガリウム膜に伸びることを抑制する機能を備える。   The aluminum gallium nitride film 14 functions as a buffer layer that alleviates lattice mismatch between the aluminum nitride film 12 and the single crystal gallium film formed on the aluminum gallium nitride film 14. From the viewpoint of alleviating lattice mismatch, the aluminum content in the aluminum gallium nitride film 14 can be reduced in the direction from the aluminum gallium nitride film 14 toward the single crystal gallium film formed in the upper layer of the aluminum gallium nitride film 14. desirable. The aluminum gallium nitride film 14 has a function of bending the dislocation extending from the aluminum nitride film 12 and suppressing the dislocation from extending to the single crystal gallium film formed in the upper layer.

次に、窒化アルミニウムガリウム膜１４上に単結晶の第１の窒化ガリウム（ＧａＮ）膜１６を形成する（Ｓ１３０、図３）。第１の窒化ガリウム膜１６は、窒化アルミニウムガリウム膜１４上に島状にエピタキシャル成長させた島状膜である。   Next, a single crystal first gallium nitride (GaN) film 16 is formed on the aluminum gallium nitride film 14 (S130, FIG. 3). The first gallium nitride film 16 is an island film that is epitaxially grown in an island shape on the aluminum gallium nitride film 14.

第１の窒化ガリウム膜１６は、シリコン基板１０を加熱し、例えば、水素（Ｈ２）で希釈されたトリメチルガリウム（ＴＭＧ）、水素（Ｈ２）で希釈されたアンモニア（ＮＨ３）をソースガスとして供給することにより成長させる。ＴＭＧはガリウム（Ｇａ）のソースガスであり、アンモニアは窒素（Ｎ）のソースガスである。 The first gallium nitride film 16, the silicon substrate 10 is heated, for example, hydrogen trimethyl gallium (TMG) diluted with (H 2), hydrogen ammonia diluted with (H 2) (NH 3) a source gas Grow by supplying as. TMG is a source gas of gallium (Ga), and ammonia is a source gas of nitrogen (N).

その際、島状の第１の窒化ガリウム膜１６の高さ（図３中のｈ）の平均を例えば１０ｎｍ以上１００ｎｍ以下、幅（図３中のｗ）の平均を１０ｎｍ以上５０ｎｍとする。第１の窒化ガリウム膜１６の高さは、例えば、第１の窒化ガリウム膜１６成長後の断面をＳＥＭ（Ｓｃａｎｎｉｎｇ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｅ）で観察することで求めることが可能である。   At this time, the average height (h in FIG. 3) of the island-shaped first gallium nitride film 16 is, for example, 10 nm to 100 nm, and the average width (w in FIG. 3) is 10 nm to 50 nm. The height of the first gallium nitride film 16 can be obtained, for example, by observing a cross section after the growth of the first gallium nitride film 16 with an SEM (Scanning Electron Microscope).

そして、第１の窒化ガリウム膜１６形成時のＶ／ＩＩＩ比を、例えば１０００以上とする。ここで、Ｖ／ＩＩＩ比とは、窒化ガリウムをエピタキシャル成長する際のガリウム（ＩＩＩ族元素）のソースガスであるＴＭＧと、窒素（Ｖ族元素）のソースガスであるアンモニアの流量比である。各ソースガスの流量単位は、μｍｏｌ／ｍｉｎである。   The V / III ratio at the time of forming the first gallium nitride film 16 is set to 1000 or more, for example. Here, the V / III ratio is a flow ratio of TMG, which is a source gas of gallium (Group III element), and ammonia, which is a source gas of nitrogen (Group V element), when epitaxially growing gallium nitride. The unit of flow rate of each source gas is μmol / min.

また、第１の窒化ガリウム膜１６形成時の成長速度を、例えば３μｍ／ｈｏｕｒ以下、温度を、例えば９５０℃以上１０５０℃未満、圧力を、例えば２０ｋＰａ以上３５ｋＰａ以下とする。   Further, the growth rate at the time of forming the first gallium nitride film 16 is, for example, 3 μm / hour or less, the temperature is, for example, 950 ° C. or more and less than 1050 ° C., and the pressure is, for example, 20 kPa or more and 35 kPa or less.

次に、島状の第１の窒化ガリウム膜１６上に第１の窒化ガリウム膜１６の形成よりも、高い温度且つ高い成長速度で単結晶の第２の窒化ガリウム（ＧａＮ）膜１８を形成する（Ｓ１４０、図４）。第２の窒化ガリウム膜１８は、第１の窒化ガリウム膜１６上に層状にエピタキシャル成長させる。   Next, a single crystal second gallium nitride (GaN) film 18 is formed on the island-shaped first gallium nitride film 16 at a higher temperature and a higher growth rate than the formation of the first gallium nitride film 16. (S140, FIG. 4). The second gallium nitride film 18 is epitaxially grown in layers on the first gallium nitride film 16.

第２の窒化ガリウム膜１８は、シリコン基板１０を加熱し、例えば、水素（Ｈ２）で希釈されたトリメチルガリウム（ＴＭＧ）、水素（Ｈ２）で希釈されたアンモニア（ＮＨ３）をソースガスとして供給することにより成長させる。ＴＭＧはガリウム（Ｇａ）のソースガスであり、アンモニアは窒素（Ｎ）のソースガスである。 The second gallium nitride film 18, the silicon substrate 10 is heated, for example, hydrogen trimethyl gallium (TMG) diluted with (H 2), hydrogen ammonia diluted with (H 2) (NH 3) a source gas Grow by supplying as. TMG is a source gas of gallium (Ga), and ammonia is a source gas of nitrogen (N).

第２の窒化ガリウム膜１８の膜厚は、例えば、３μｍ以上１０μｍ以下とする。第２の窒化ガリウム膜１８の膜厚は、例えば、第２の窒化ガリウム膜１８の成長後の断面をＳＥＭで観察することで求めることが可能である。   The film thickness of the second gallium nitride film 18 is, for example, 3 μm or more and 10 μm or less. The film thickness of the second gallium nitride film 18 can be obtained, for example, by observing a cross section after the growth of the second gallium nitride film 18 with an SEM.

第２の窒化ガリウム膜１８形成時のＶ／ＩＩＩ比を１０００以下とする。また、第２の窒化ガリウム膜１８形成時の成長速度を、第１の窒化ガリウム膜１６形成時の成長速度より高く、例えば３μｍ／ｈｏｕｒ以上とする。また、第２の窒化ガリウム膜１８形成時の温度を、例えば、１０００℃以上１１００℃未満、圧力を、例えば、２０ｋＰａ以上３５ｋＰａ以下とし、第１の窒化ガリウム膜１６形成時の圧力と同一とする。   The V / III ratio when forming the second gallium nitride film 18 is set to 1000 or less. Further, the growth rate at the time of forming the second gallium nitride film 18 is higher than the growth rate at the time of forming the first gallium nitride film 16, for example, 3 μm / hour or more. Further, the temperature at the time of forming the second gallium nitride film 18 is, for example, 1000 ° C. or more and less than 1100 ° C., and the pressure is, for example, 20 kPa or more and 35 kPa or less. .

なお、第２の窒化ガリウム膜１８の一部又は全部に、例えば、シリコン（Ｓｉ）やマグネシウム（Ｍｇ）等のドーパントを添加することができる。   For example, a dopant such as silicon (Si) or magnesium (Mg) can be added to part or all of the second gallium nitride film 18.

次に、実施形態の作用及び効果について説明する。   Next, the operation and effect of the embodiment will be described.

シリコン基板上に窒化ガリウム膜を形成する場合、窒化ガリウム膜の膜厚が厚くなると、シリコンと窒化ガリウムの熱膨張係数等の違いに起因して窒化ガリウム膜にクラックが発生するおそれがある。これは、窒化ガリウム膜の形成中に、窒化ガリウム膜に引張応力が発生することにより生じると考えられる。特に、窒化ガリウム膜の成長速度を速くした場合に、クラックが発生しやすくなる。   When a gallium nitride film is formed on a silicon substrate, if the gallium nitride film is thick, cracks may occur in the gallium nitride film due to a difference in thermal expansion coefficient between silicon and gallium nitride. This is considered to be caused by tensile stress generated in the gallium nitride film during the formation of the gallium nitride film. In particular, cracks are likely to occur when the growth rate of the gallium nitride film is increased.

本実施形態では、第１の窒化ガリウム膜１６を島状に３次元的に成長させる。この際、窒化アルミニウムガリウム膜１４表面における核形成の密度を、島状の第１の窒化ガリウム膜１６が十分な高さに成長する前に側面で接触してしまうことのないように制御する。その後、第２の窒化ガリウム膜１８を、第１の窒化ガリウム膜１６よりも速い成長速度で層状に成長させる。この方法により、窒化ガリウム膜の形成を、窒化ガリウム膜に圧縮応力をかけた状態で行うことが可能となる。したがって、クラックの発生を抑制しつつ、窒化ガリウム膜の高速成長が実現できる。また、結晶欠陥の低減した窒化ガリウム膜を成膜することが可能となる。   In the present embodiment, the first gallium nitride film 16 is grown three-dimensionally in an island shape. At this time, the density of nucleation on the surface of the aluminum gallium nitride film 14 is controlled so that the island-shaped first gallium nitride film 16 does not come into contact with the side surface before growing to a sufficient height. Thereafter, the second gallium nitride film 18 is grown in layers at a faster growth rate than the first gallium nitride film 16. By this method, the gallium nitride film can be formed in a state where compressive stress is applied to the gallium nitride film. Therefore, high-speed growth of the gallium nitride film can be realized while suppressing the generation of cracks. In addition, a gallium nitride film with reduced crystal defects can be formed.

第１の窒化ガリウム膜１６を島状に形成する際、島状の第１の窒化ガリウム膜１６の高さ（図３中のｈ）の平均を１０ｎｍ以上１００ｎｍ以下、幅（図３中のｗ）の平均を１０ｎｍ以上５０ｎｍ以下とすることが望ましい。上記範囲を下回ると、第２の窒化ガリウム膜１８成膜の際に、第２の窒化ガリウム膜１８の応力が圧縮応力とならないおそれがある。また、第２の窒化ガリウム膜１８の結晶性が劣化する恐れがある。上記範囲を上回ると、第２の窒化ガリウム膜１８の表面モフォロジーが劣化する恐れがある。第２の窒化ガリウム膜１８の表面を平坦にする観点から、第１の窒化ガリウム膜１６の高さの平均が５０ｎｍ以下であることが望ましい。   When the first gallium nitride film 16 is formed in an island shape, the average height (h in FIG. 3) of the island-shaped first gallium nitride film 16 is 10 nm to 100 nm and the width (w in FIG. 3). ) Is preferably 10 nm to 50 nm. If it is below the above range, the stress of the second gallium nitride film 18 may not be a compressive stress when the second gallium nitride film 18 is formed. Further, the crystallinity of the second gallium nitride film 18 may be deteriorated. If the above range is exceeded, the surface morphology of the second gallium nitride film 18 may deteriorate. From the viewpoint of flattening the surface of the second gallium nitride film 18, the average height of the first gallium nitride film 16 is desirably 50 nm or less.

第１の窒化ガリウム膜１６形成時のＶ／ＩＩＩ比が１０００以上であることが、第１の窒化ガリウム膜１６の成長速度を抑え、結晶性を向上させ、島状に３次元的に成長させる観点から望ましい。第１の窒化ガリウム膜１６形成時の成長速度は３μｍ／ｈｏｕｒ以下、温度は９５０℃以上１０５０℃未満、圧力は２０ｋＰａ以上３５ｋＰａ以下であることが、第１の窒化ガリウム膜１６の、結晶性を向上させ、島状に３次元的に成長させる観点から望ましい。   When the first gallium nitride film 16 is formed, the V / III ratio is 1000 or more, the growth rate of the first gallium nitride film 16 is suppressed, the crystallinity is improved, and the three-dimensional growth is performed in an island shape. Desirable from a viewpoint. When the first gallium nitride film 16 is formed, the growth rate is 3 μm / hour or less, the temperature is 950 ° C. or more and less than 1050 ° C., and the pressure is 20 kPa or more and 35 kPa or less. It is desirable from the viewpoint of improving and growing in an island shape three-dimensionally.

また、第２の窒化ガリウム膜１８の成長速度を速くし、生産性をあげる観点から、第２の窒化ガリウム膜１８形成時のＶ／ＩＩＩ比が１０００以下であることが望ましく、５００以下であることがより望ましい。第２の窒化ガリウム膜１８形成時のＶ／ＩＩＩ比は、第１の窒化ガリウム膜１６形成時のＶ／ＩＩＩ比よりも小さいことが望ましい。そして、第２の窒化ガリウム膜１８の成長速度は、３μｍ／ｈｏｕｒ以上であることが、生産性をあげる観点から望ましい。   Further, from the viewpoint of increasing the growth rate of the second gallium nitride film 18 and increasing the productivity, the V / III ratio at the time of forming the second gallium nitride film 18 is desirably 1000 or less, and is 500 or less. It is more desirable. The V / III ratio when the second gallium nitride film 18 is formed is desirably smaller than the V / III ratio when the first gallium nitride film 16 is formed. The growth rate of the second gallium nitride film 18 is desirably 3 μm / hour or more from the viewpoint of increasing productivity.

さらに、第２の窒化ガリウム膜１８の成長速度を第１の窒化ガリウム膜１６の成長速度を速くする観点から、１０００℃以上１１００℃未満であって、第１の窒化ガリウム膜１６の形成よりも高い温度で、第２の窒化ガリウム膜１８の形成を行う。そして、生産性を向上させる観点から、第２の窒化ガリウム膜１８形成時の圧力は、圧力は２０ｋＰａ以上３５ｋＰａ以下であって、第１の窒化ガリウム膜１６形成時の圧力と略同一であることが望ましい。   Further, from the viewpoint of increasing the growth rate of the second gallium nitride film 18, the growth rate of the first gallium nitride film 16 is 1000 ° C. or more and less than 1100 ° C., which is higher than the formation of the first gallium nitride film 16. The second gallium nitride film 18 is formed at a high temperature. From the viewpoint of improving productivity, the pressure at the time of forming the second gallium nitride film 18 is not less than 20 kPa and not more than 35 kPa, and is substantially the same as the pressure at the time of forming the first gallium nitride film 16. Is desirable.

本実施形態の気相成長方法によれば、シリコン基板上に膜厚の厚い窒化ガリウムを形成する際のクラックの発生を抑制することが可能となる。また、結晶欠陥の低減した膜厚の厚い窒化ガリウム膜を、高速で成膜することが可能となる。   According to the vapor phase growth method of the present embodiment, it is possible to suppress the generation of cracks when a thick gallium nitride film is formed on a silicon substrate. In addition, a thick gallium nitride film with reduced crystal defects can be formed at high speed.

以上、具体例を参照しつつ本発明の実施形態について説明した。上記、実施形態はあくまで、例として挙げられているだけであり、本発明を限定するものではない。また、各実施形態の構成要素を適宜組み合わせてもかまわない。   The embodiments of the present invention have been described above with reference to specific examples. The above embodiment is merely given as an example and does not limit the present invention. Moreover, you may combine the component of each embodiment suitably.

実施形態では、気相成長方法等で、本発明の説明に直接必要としない部分等については記載を省略したが、必要とされる等を適宜選択して用いることができる。その他、本発明の要素を具備し、当業者が適宜設計変更しうる全ての気相成長方法は、本発明の範囲に包含される。本発明の範囲は、特許請求の範囲及びその均等物の範囲によって定義されるものである。   In the embodiment, the description of the portions that are not directly required for the description of the present invention in the vapor phase growth method and the like is omitted, but the required portions can be appropriately selected and used. In addition, all vapor phase growth methods that include elements of the present invention and that can be appropriately modified by those skilled in the art are included in the scope of the present invention. The scope of the present invention is defined by the appended claims and equivalents thereof.

１０ シリコン基板
１２ 窒化アルミニウム膜
１４ 窒化アルミニウムガリウム膜
１６ 第１の窒化ガリウム膜
１８ 第２の窒化ガリウム膜 10 Silicon substrate 12 Aluminum nitride film 14 Aluminum gallium nitride film 16 First gallium nitride film 18 Second gallium nitride film

Claims (4)

シリコン基板上に単結晶の窒化アルミニウム膜を形成し、
前記窒化アルミニウム膜上に単結晶の窒化アルミニウムガリウム膜を形成し、
前記窒化アルミニウムガリウム膜上に単結晶の第１の窒化ガリウム膜を形成し、
前記第１の窒化ガリウム膜上に、前記第１の窒化ガリウム膜の形成よりも高い温度且つ高い成長速度で、単結晶の第２の窒化ガリウム膜を形成する気相成長方法であって、
前記第１の窒化ガリウム膜を島状に形成し、前記第１の窒化ガリウム膜の高さの平均を１０ｎｍ以上５０ｎｍ以下とし、
前記第２の窒化ガリウム膜を、前記窒化アルミニウムガリウム膜及び前記第１の窒化ガリウム膜に接するように形成する気相成長方法。 A single crystal aluminum nitride film is formed on a silicon substrate,
Forming a single crystal aluminum gallium nitride film on the aluminum nitride film;
Forming a single-crystal first gallium nitride film on the aluminum gallium nitride film;
A vapor phase growth method for forming a single-crystal second gallium nitride film on the first gallium nitride film at a higher temperature and higher growth rate than the formation of the first gallium nitride film ,
The first gallium nitride film is formed in an island shape, and the average height of the first gallium nitride film is 10 nm or more and 50 nm or less,
A vapor phase growth method in which the second gallium nitride film is formed in contact with the aluminum gallium nitride film and the first gallium nitride film . 前記第１の窒化ガリウム膜形成時のＶ／ＩＩＩ比が前記第２の窒化ガリウム膜形成時のＶ／ＩＩＩ比より大きい請求項１記載の気相成長方法。 The first vapor phase growth method of the V / III ratio greater than claim 1 Symbol placement upon V / III ratio during the gallium film forming nitride the second gallium nitride film. 前記第１の窒化ガリウム膜形成時の成長速度が３μｍ／ｈｏｕｒ以下である請求項１又は請求項２記載の気相成長方法。 3. The vapor phase growth method according to claim 1, wherein a growth rate at the time of forming the first gallium nitride film is 3 μm / hour or less. 前記第１の窒化ガリウム膜形成時の温度が９５０℃以上１０５０℃未満であり、前記第２の窒化ガリウム膜形成時の温度が１０００℃以上１１００℃未満である請求項１乃至請求項３いずれか一項記載の気相成長方法。
It said first temperature during the gallium nitride film is less than 950 ° C. or higher 1050 ° C., claims 1 to any one of claims 3 temperature during the second gallium nitride film is 1100 below ° C. 1000 ° C. or higher The vapor phase growth method according to one item.
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