JP3184717B2 - GaN single crystal and method for producing the same - Google Patents
GaN single crystal and method for producing the sameInfo
- Publication number
- JP3184717B2 JP3184717B2 JP24296794A JP24296794A JP3184717B2 JP 3184717 B2 JP3184717 B2 JP 3184717B2 JP 24296794 A JP24296794 A JP 24296794A JP 24296794 A JP24296794 A JP 24296794A JP 3184717 B2 JP3184717 B2 JP 3184717B2
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- gan single
- gan
- crystal
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は、青色発光ダイオード等
のＧａＮ単結晶基板として好適に用いることができる高
品質なＧａＮ単結晶、および、その製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high quality GaN single crystal which can be suitably used as a GaN single crystal substrate for a blue light emitting diode or the like, and a method for producing the same.
【０００２】[0002]
【従来の技術】発光ディスプレイ等における多色化の要
求や、通信・記録等におけるデータ密度向上の要求によ
って、青色から紫外線波長領域に至る短波長の発光が可
能な半導体デバイスの出現が強く求められている。この
青色〜紫外発光デバイス用の半導体材料として、 III−
Ｖ系化合物半導体では最もバンドギャップの広い窒化物
であるＧａＮ系単結晶が着目されている。ＧａＮは、直
接遷移型バンド構造を有するため高効率の発光が可能で
あり、かつ、室温でのバンドギャップが約３．４ｅＶと
大きいため青色〜紫外発光を呈し、上記半導体デバイス
の要求に好適な材料である。しかし、ＧａＮは、結晶成
長温度が高く、また結晶成長温度付近での窒素の平衡蒸
気圧が高いため、融液から高品質で大型の単結晶を製造
することは極めて困難である。従って、ＧａＮ系単結晶
の成長は、耐熱性に優れたサファイア基板またはＳｉＣ
基板上への、ＭＯＶＰＥ（Metal Organic Vapor Phase
Epitaxy ）またはＭＢＥ（Molecular Beam Epitaxy）に
よる非平衡反応に基づくヘテロエピタキシャル成長法に
よって行われていた。これに対して、近年、ＺｎＯをバ
ッファ層としてサファイア基板上に成膜した上にＧａＮ
単結晶を成長させる方法が開示され（例えば、Applied
physics letter Vol.61 (1992) p.2688 ）、ＧａＮ基板
の作製が可能になった。このＧａＮ基板上に同質のＧａ
Ｎ系単結晶薄膜を成長させることによって、上記サファ
イア基板上への直接的な結晶成長にくらべＧａＮ系単結
晶薄膜の品質は向上した。2. Description of the Related Art The demand for multicolor display in light-emitting displays and the like and the demand for higher data density in communication and recording have led to a strong demand for semiconductor devices capable of emitting light of short wavelengths from the blue to the ultraviolet wavelength region. ing. As a semiconductor material for this blue to ultraviolet light emitting device, III-
Among V-based compound semiconductors, GaN-based single crystals, which are nitrides having the widest band gap, have been receiving attention. GaN has a direct transition-type band structure and therefore can emit light with high efficiency, and has a large band gap at room temperature of about 3.4 eV, and emits blue to ultraviolet light, which is suitable for the requirements of the semiconductor device. Material. However, since GaN has a high crystal growth temperature and a high equilibrium vapor pressure of nitrogen near the crystal growth temperature, it is extremely difficult to produce a high-quality large single crystal from a melt. Therefore, a GaN-based single crystal is grown on a sapphire substrate or SiC having excellent heat resistance.
MOVPE (Metal Organic Vapor Phase)
Epitaxy) or heteroepitaxial growth based on non-equilibrium reaction by MBE (Molecular Beam Epitaxy). On the other hand, in recent years, a GaN film was formed on a sapphire substrate using ZnO as a buffer layer.
Methods for growing single crystals are disclosed (eg, Applied
physics letter Vol.61 (1992) p.2688), making GaN substrates possible. On this GaN substrate, homogeneous Ga
By growing the N-based single-crystal thin film, the quality of the GaN-based single-crystal thin film was improved as compared with the direct crystal growth on the sapphire substrate.
【０００３】[0003]
【発明が解決しようとする課題】ところが、上記ＺｎＯ
をバッファ層として用いる従来の方法では、サファイア
基板上へのＺｎＯの成膜がスパッタリング法によるもの
であるため、該ＺｎＯ層は高品質の単結晶とはならず、
この結晶構造の品質が次のＧａＮ単結晶層に影響するた
めに高品質なＧａＮ単結晶が得られないという問題があ
った。また、従来知られていたＧａＮ単結晶の結晶品質
は、最も高品質なものであっても、２結晶法Ｘ線ロッキ
ングカーブの半値全幅（full width at half-maximumof
the double-crystal X-ray rocking curve）が１００
ｓｅｃ程度、室温でのMobility は６００ｃｍ2 ／ＶＳ
程度であったが、結晶を成長させる方法がＭＯＶＰＥで
あるために膜厚が５μｍ程度しか得られず非常に薄いの
で、ＧａＮ単結晶をもとの基板から分離し、例えば半導
体発光素子の基板として、単独に用いることは困難であ
った。このため、ＧａＮ単結晶を利用する場合は、もと
の基板上に形成された状態のまま用いることを余儀なく
されていたのである。以下、本明細書では、「２結晶法
Ｘ線ロッキングカーブの半値全幅」を単に「半値全幅」
という。また、上記のようにＺｎＯバッファ層上に、Ｈ
ＶＰＥ（Hydride Vapor PhaseEpitaxy ）によって成長
させたＧａＮ単結晶は、基板としては十分な厚みのもの
が得られていたが、その品質は半値全幅が３００ｓｅｃ
以上の低品質のものであった。即ち、良好な品質と十分
な厚みとを同時に有するＧａＮ単結晶はなかったのであ
る。However, the above-mentioned ZnO
In the conventional method using as a buffer layer, the ZnO film is formed on a sapphire substrate by a sputtering method, so that the ZnO layer does not become a high-quality single crystal,
There is a problem that a high-quality GaN single crystal cannot be obtained because the quality of the crystal structure affects the next GaN single crystal layer. In addition, the crystal quality of a conventionally known GaN single crystal, even at the highest quality, is the full width at half-maximum of the X-ray rocking curve of the two-crystal method.
the double-crystal X-ray rocking curve) is 100
Mobility at room temperature is about 600cm 2 / VS
However, since the method for growing the crystal is MOVPE, the film thickness is only about 5 μm and is very thin. Therefore, the GaN single crystal is separated from the original substrate, and is used as a substrate for a semiconductor light emitting device, for example. , It was difficult to use it alone. For this reason, when a GaN single crystal is used, it must be used as it is formed on the original substrate. Hereinafter, in this specification, the “full width at half maximum of the two-crystal method X-ray rocking curve” is simply referred to as “full width at half maximum”.
That. Further, as described above, H
A GaN single crystal grown by VPE (Hydride Vapor Phase Epitaxy) had a sufficient thickness as a substrate, but its quality was such that the full width at half maximum was 300 sec.
These were of low quality. That is, there was no GaN single crystal having both good quality and sufficient thickness at the same time.
【０００４】本発明の目的は、高品質な単結晶で、か
つ、単独で基板として用いることが可能なほど十分な厚
みを有する、ＧａＮ単結晶を提供することである。本発
明の他の目的は、高品質な単結晶で、かつ、単独で基板
として用いることが可能なほど十分な厚みを有するＧａ
Ｎ単結晶の製造が可能な、ＧａＮ単結晶の製造方法を提
供することである。[0004] It is an object of the present invention to provide a GaN single crystal that is a high-quality single crystal and has a thickness sufficient to be used alone as a substrate. Another object of the present invention is to provide a single crystal of high quality and having a thickness sufficient to be able to be used alone as a substrate.
An object of the present invention is to provide a method for producing a GaN single crystal, capable of producing an N single crystal.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、ＧａＮ単
結晶が従来の製造方法による低品質の結晶構造であって
も、あるいはサファイア基板等のようなＧａＮ以外の結
晶であっても、これらを最初の結晶基板として、この上
にＧａＮ単結晶との格子整合性が良好な物質を薄膜成長
させてバッファ層とし、この上にＧａＮを結晶成長させ
ることによって、より高品質のＧａＮ単結晶が得られる
こと、および当該ＧａＮ単結晶を新たな基板とし、再び
この上にバッファ層・ＧａＮ単結晶を成長させるという
ように、バッファ層物質とＧａＮとを交互にエピタキシ
ャル成長させることを繰り返すに応じてＧａＮ単結晶が
より高品質化され、十分な厚みに形成し得ることを見出
し本発明を完成した。Means for Solving the Problems The present inventors have determined whether a GaN single crystal has a low-quality crystal structure by a conventional manufacturing method or a crystal other than GaN such as a sapphire substrate. Using these as the first crystal substrate, a material having good lattice matching with the GaN single crystal is grown thereon as a thin film to form a buffer layer, and GaN crystal is grown thereon, thereby obtaining a higher quality GaN single crystal. Is obtained, and the buffer layer material and GaN are alternately epitaxially grown such that the GaN single crystal is used as a new substrate and the buffer layer / GaN single crystal is grown thereon again. The present inventors have found that GaN single crystals can be formed with higher quality and can be formed to a sufficient thickness, and have completed the present invention.
【０００６】本発明のＧａＮ単結晶およびその製造方法
は次の特徴を有するものである。 (1) ２結晶法Ｘ線ロッキングカーブの半値全幅が５〜２
５０ｓｅｃであり、かつ、厚みが８０μｍ以上であっ
て、ＧａＮ系半導体結晶層を成長させるための基板とな
るＧａＮ単結晶。 (2) 少なくとも表面がＧａＮ単結晶である基板上にＧａ
Ｎ単結晶との格子整合性の良好な物質を薄膜成長させて
バッファ層とした上にＧａＮを結晶成長させてＧａＮ単
結晶を得る工程を有する、前記ＧａＮ系半導体結晶層を
成長させるための基板となるＧａＮ単結晶の製造方法。 (3) 少なくとも表面がＧａＮ単結晶である基板上にＧａ
Ｎ単結晶との格子整合性の良好な物質を薄膜成長させて
バッファ層とした上にＧａＮを結晶成長させてＧａＮ単
結晶を得る工程を１回の結晶成長サイクルとし、得られ
たＧａＮ単結晶上に上記結晶成長サイクルを少なくとも
１サイクル繰り返して積層物を形成させた後に各バッフ
ァ層を除去し、ＧａＮ単結晶を得ることを特徴とするＧ
ａＮ単結晶の製造方法。 (4) 少なくとも表面がＧａＮ単結晶である基板上にＧａ
Ｎ単結晶との格子整合性の良好な物質を薄膜成長させて
バッファ層とした上にＧａＮを結晶成長させてＧａＮ単
結晶を得る工程を１回の結晶成長サイクルとし、得られ
たＧａＮ単結晶を新たな基板として上記結晶成長サイク
ルを少なくとも１サイクル繰り返し、かつ１サイクル毎
にバッファ層を除去し、ＧａＮ単結晶を得ることを特徴
とするＧａＮ単結晶の製造方法。The GaN single crystal and the method for producing the same according to the present invention have the following features. (1) The full width at half maximum of the two-crystal method X-ray rocking curve is 5-2.
Is 50 sec, and there in a thickness of 80μm or more
Thus, it becomes a substrate for growing a GaN-based semiconductor crystal layer.
That GaN single crystal. (2) Ga on a substrate having at least a surface of GaN single crystal
Forming a buffer layer by growing a thin film of a substance having good lattice matching with the N single crystal to obtain GaN single crystal by growing GaN on the buffer layer;
A method for producing a GaN single crystal serving as a substrate for growth . (3) On a substrate having at least a surface made of GaN single crystal,
A process of growing a GaN single crystal by growing a GaN crystal on a thin film of a substance having good lattice matching with the N single crystal to form a buffer layer is defined as one crystal growth cycle. The above crystal growth cycle is repeated at least one cycle to form a laminate, and then each buffer layer is removed to obtain a GaN single crystal.
Manufacturing method of aN single crystal. (4) Ga on a substrate having at least a surface made of GaN single crystal
A process of growing a GaN single crystal by growing a GaN crystal on a thin film of a substance having good lattice matching with the N single crystal to form a buffer layer is defined as one crystal growth cycle. A GaN single crystal obtained by repeating the crystal growth cycle at least one cycle using a new substrate as a new substrate and removing the buffer layer every cycle.
【０００７】[0007]
【作用】本発明のＧａＮ単結晶は、基板上にバッファ層
の成膜とＧａＮの結晶成長とを交互に、また、サイクル
的に繰り返すことによって形成される。基板中に存在し
ている多くの転位、積層欠陥などは、ＧａＮの結晶成長
層内、バッファ層内、または基板とバッファ層との界
面、またはバッファ層とＧａＮ結晶成長層との界面で消
滅する。従って、該結晶成長サイクルを１回行なう毎
に、ＧａＮの単結晶構造の品質は向上し、これを限りな
く繰り返せば、成長条件で規定されるような単結晶構造
に漸近的に収束するものと思われる。本発明の製造方法
によって得られるＧａＮ単結晶は品質が良好であり、ま
た、必要ならば８０μｍ以上の厚みにまで形成すること
が可能であり、特に半導体発光素子の基板として好まし
いものとなる。The GaN single crystal of the present invention is formed by alternately repeating the film formation of the buffer layer and the crystal growth of GaN on the substrate, or by repeating the same in a cyclic manner. Many dislocations, stacking faults, etc. existing in the substrate disappear in the GaN crystal growth layer, in the buffer layer, at the interface between the substrate and the buffer layer, or at the interface between the buffer layer and the GaN crystal growth layer. . Therefore, each time the crystal growth cycle is performed, the quality of the GaN single crystal structure is improved, and if this is repeated indefinitely, the GaN single crystal structure asymptotically converges to the single crystal structure defined by the growth conditions. Seem. The GaN single crystal obtained by the production method of the present invention has good quality and can be formed to a thickness of 80 μm or more if necessary, and is particularly preferable as a substrate of a semiconductor light emitting device.
【０００８】[0008]
【実施例】以下、実施例を挙げて本発明をより詳細に説
明する。本発明のＧａＮ単結晶は、上記したように、そ
の半値全幅が５〜２５０ｓｅｃの値を示す高品質なもの
であり、かつ、単独で基板として用いることができる
程、充分な厚み８０μｍ以上を有するものである。本発
明では、ＧａＮ単結晶の品質を数値で表すための方法と
してＸ線回折法を用い、この方法によって示される半値
全幅の値をもってＧａＮ単結晶の品質とした。Ｘ線回折
法は、結晶に照射されたＸ線の回折を利用する方法であ
る。そのなかでも、本発明では、その測定精度を向上さ
せるために、２結晶を用いる方法によって測定をおこな
った。２結晶を用いるＸ線回折法は、試料の格子定数を
精密に評価し、その半値幅から結晶の完全性を評価する
方法である。本発明におけるＧａＮ単結晶の品質評価に
おいては、Ｘ線源から入射したＸ線を第１結晶により高
度に単色化して、第２結晶である試料のＧａＮ単結晶に
照射し、この試料から回折するＸ線のピークを中心とす
るＦＷＨＭ（full width athalf-maximum）を測定し
た。Ｘ線源にはＣｕｋα1 を用い、３０ｋＶ、１０ｍＡ
でＸ線を発生させた。単色化のための第１結晶には、Ｇ
ｅ（４００）を用いた。測定は、ＧａＮ（０００２）の
回折ピークについて行い、測定のステップ間隔は０．０
０２°で行うものとした。The present invention will be described below in more detail with reference to examples. As described above, the GaN single crystal of the present invention is a high-quality one whose full width at half maximum indicates a value of 5 to 250 sec, and has a sufficient thickness of 80 μm or more such that it can be used alone as a substrate. Things. In the present invention, an X-ray diffraction method is used as a method for expressing the quality of a GaN single crystal by a numerical value, and the value of the full width at half maximum indicated by this method is used as the quality of the GaN single crystal. The X-ray diffraction method is a method that utilizes the diffraction of X-rays applied to a crystal. Among them, in the present invention, in order to improve the measurement accuracy, the measurement was performed by a method using two crystals. The X-ray diffraction method using two crystals is a method of precisely evaluating the lattice constant of a sample and evaluating the integrity of the crystal from its half-value width. In the quality evaluation of the GaN single crystal in the present invention, the X-ray incident from the X-ray source is made highly monochromatic by the first crystal, irradiated to the GaN single crystal of the sample as the second crystal, and diffracted from this sample. The FWHM (full width at half-maximum) centered on the X-ray peak was measured. Using CuKa 1 is the X-ray source, 30 kV, 10 mA
Produced X-rays. The first crystal for monochromaticization has G
e (400) was used. The measurement is performed on the diffraction peak of GaN (0002), and the measurement step interval is 0.0
02 °.
【０００９】本発明によるＧａＮ単結晶の品質の実験値
については後述するものとし、次にこのような品質のＧ
ａＮ単結晶を得ることが可能な製造方法を説明する。図
１は本発明の製造方法によるＧａＮ単結晶の形成工程の
一例を模式的に示す図である。本発明のＧａＮ単結晶の
製造方法は、最も簡単には、同図工程１に示すように、
少なくとも表面がＧａＮ単結晶である最初の基板Ｐ0 上
にＧａＮ単結晶との格子整合性が良好な物質を堆積させ
てバッファ層Ｂ1 とした上にＧａＮを結晶成長させてＧ
ａＮ単結晶を得るものである。The experimental value of the quality of the GaN single crystal according to the present invention will be described later.
A manufacturing method capable of obtaining an aN single crystal will be described. FIG. 1 is a diagram schematically showing an example of a step of forming a GaN single crystal according to the manufacturing method of the present invention. The method for producing a GaN single crystal of the present invention is most simply described as shown in Step 1 in FIG.
A material having good lattice matching with the GaN single crystal is deposited on the first substrate P 0 having at least a surface of a GaN single crystal to form a buffer layer B 1, and GaN crystal is grown thereon.
An aN single crystal is obtained.
【００１０】本発明のＧａＮ単結晶の製造方法は、ま
た、同図工程２に示すように、工程１で形成された積層
体の基板Ｐ1 上にＧａＮ単結晶との格子整合性が良好な
物質を薄膜成長させてバッファ層Ｂ2 を形成した上にＧ
ａＮを結晶成長させＧａＮ単結晶よりなる基板Ｐ2 を形
成させる。この様な工程を、工程１を１回目と数えてサ
イクル的にｎ回繰り返すことによって最上層にＧａＮ単
結晶Ｐn が成長した後に、それまで累積した各バッファ
層を一度に除去し、ＧａＮ単結晶Ｐ1 〜Ｐn を分離して
多数枚のＧａＮ単結晶とする方法である。上記方法で
は、サイクル数を増やす毎に、得られるＧａＮの結晶品
質は向上するが、結晶品質の向上が平衡状態に達した後
は、むしろ多数枚の基板作製技術として有用なものとな
る。[0010] method of manufacturing a GaN single crystal of the present invention, and as shown in FIG step 2, a good lattice matching with GaN single crystal on the substrate P 1 of the laminate formed in step 1 The substance is grown on a thin film to form a buffer layer B 2 and then G
The aN to form the substrate P 2 of GaN single crystals by crystal growth. By repeating this process n times in a cycle by counting Step 1 as the first time, after the GaN single crystal Pn is grown on the uppermost layer, each buffer layer accumulated so far is removed at a time, and the GaN single crystal is removed. In this method, the crystals P 1 to P n are separated into a large number of GaN single crystals. In the above method, the crystal quality of the obtained GaN is improved each time the number of cycles is increased. However, after the improvement of the crystal quality reaches an equilibrium state, it becomes rather useful as a technique for manufacturing a large number of substrates.
【００１１】本発明のＧａＮ単結晶の製造方法は、さら
に、同図工程３に示すように、工程１のバッファ層Ｂ1
を除去してＧａＮ単結晶Ｐ0 ，Ｐ1 を分離し、ＧａＮ単
結晶の単独基板Ｐ1 を得、当該基板Ｐ1 上にＧａＮ単結
晶との格子整合性が良好な物質を薄膜成長させてバッフ
ァ層Ｂ2 を形成した上にＧａＮを結晶成長させ、バッフ
ァ層Ｂ2 を除去してＧａＮ単結晶Ｐ1 ，Ｐ2 を分離す
る。この様な工程を、工程１を１回目と数えてサイクル
的にｎ回繰り返すことによってＧａＮ単結晶Ｐnが得ら
れる。即ち、本方法は新たに得られるＧａＮ単結晶が結
晶成長する度に、その結晶成長の基礎となったバッファ
層を１サイクル毎に除去し、新たに得られるＧａＮ単結
晶を常にＧａＮ単独の単結晶とする方法である。この方
法においても上記工程２と同様に、結晶品質の向上が平
衡状態に達した後は、バッファ層を除去して分離される
２つのＧａＮ単結晶は、製品材料として利用する他に、
各々次のＧａＮ結晶成長サイクルの基板として再び利用
してもよい。[0011] method of manufacturing a GaN single crystal of the present invention, further, as shown in FIG. Step 3, the buffer layer B 1 of step 1
To separate the GaN single crystals P 0 and P 1 to obtain a single substrate P 1 of GaN single crystal, and a thin film of a substance having good lattice matching with the GaN single crystal is grown on the substrate P 1. the GaN is crystal grown on the formation of the buffer layer B 2, to separate the GaN single crystal P 1, P 2 to remove the buffer layer B 2. Such a process is repeated n times in a cycle, counting Step 1 as the first time, to obtain a GaN single crystal Pn . That is, every time a newly obtained GaN single crystal grows, the present method removes the buffer layer on which the crystal growth is based every cycle, and always replaces the newly obtained GaN single crystal with a single GaN single crystal. This is a method of forming crystals. In this method, similarly to the above-described step 2, after the improvement of the crystal quality reaches an equilibrium state, the two GaN single crystals separated by removing the buffer layer are used as product materials,
Each may be reused as a substrate for the next GaN crystal growth cycle.
【００１２】また、工程２，３に示した２つの方法を適
当に複合する方法として、結晶成長サイクルの任意の回
数ｋごとにバッファ層を除去する方法が考えられる。こ
の場合の任意の回数ｋは自由に選択してよい。As a method of appropriately combining the two methods shown in Steps 2 and 3, a method of removing the buffer layer at an arbitrary number k of crystal growth cycles can be considered. The arbitrary number k in this case may be freely selected.
【００１３】上記のように、本発明のＧａＮ単結晶の製
造方法は、結晶成長サイクルを繰り返すことによって、
ＧａＮの結晶構造が該結晶成長サイクルを１回行なう毎
に品質が向上し、所望の回数ｎ回目に、極めて高品質な
ＧａＮ単結晶Ｐn が得られるというものである。As described above, the method for producing a GaN single crystal of the present invention can be realized by repeating a crystal growth cycle.
The quality of the GaN crystal structure is improved each time the crystal growth cycle is performed, and an extremely high-quality GaN single crystal Pn can be obtained at a desired number n times.
【００１４】バッファ層の薄膜成長は、公知の成膜法や
結晶成長法が用いられるが、特にエピタキシャル成長可
能な成膜法が、得られるＧａＮ単結晶の品質向上に対し
て好ましい。また、バッファ層上へＧａＮを結晶成長さ
せる方法も、バッファ層の薄膜成長と同様に、エピタキ
シャル成長可能な成膜法が品質向上に対して好ましい。For the growth of the thin film of the buffer layer, a known film forming method or a crystal growing method is used. In particular, a film forming method capable of epitaxial growth is preferable for improving the quality of the obtained GaN single crystal. In addition, as for the method of crystal-growing GaN on the buffer layer, a film-forming method capable of epitaxial growth is preferable for quality improvement, like the thin-film growth of the buffer layer.
【００１５】エピタキシャル成長は、結晶基板上にこれ
と同一物質あるいは同一結晶構造の物質を、その結晶軸
の向きが基板の結晶軸の向きにそろった単結晶として成
長させる方法である。本発明においては、ＧａＮやバッ
ファ層となる物質をエピタキシャル成長させる成膜法が
最も好ましく、特にＶＰＥ（Vapor Phase Epitaxy ）、
ＨＶＰＥ、ＭＯＶＰＥ、ＭＢＥ、ＧＳ−ＭＢＥ（Gas So
urse ＭＢＥ）、ＣＢＥ（Chemical beam Epitaxy ）等
が挙げられる。The epitaxial growth is a method of growing the same substance or a substance having the same crystal structure on a crystal substrate as a single crystal whose crystal axis is aligned with the crystal axis of the substrate. In the present invention, a film formation method for epitaxially growing GaN or a substance to be a buffer layer is most preferable, and in particular, VPE (Vapor Phase Epitaxy),
HVPE, MOVPE, MBE, GS-MBE (Gas So
urse MBE), CBE (Chemical beam Epitaxy) and the like.
【００１６】上記結晶成長サイクルを繰り返す回数ｎ
は、特に限定されるものではなく、求めるＧａＮ結晶の
品質に応じて、また、必要とするＧａＮ結晶基板の枚数
に応じてサイクル回数を決定してよいが、通常の半導体
デバイス用のＧａＮ結晶基板として用いるには、２回〜
５回程度で十分な結晶品質となる。Number n of repeating the crystal growth cycle
The number of cycles is not particularly limited, and the number of cycles may be determined according to the quality of the GaN crystal required and the number of required GaN crystal substrates. Twice to use as
Sufficient crystal quality is obtained in about 5 times.
【００１７】上記、ＧａＮの結晶成長の基礎となったバ
ッファ層を除去する方法は、得られたＧａＮ単結晶を分
離しうる方法であればどのような方法であってもよい
が、酸等による化学的な除去方法が有効である。The method of removing the buffer layer on which the GaN crystal growth is based may be any method as long as the obtained GaN single crystal can be separated. Chemical removal methods are effective.
【００１８】上記バッファ層に用いられる物質は、Ｇａ
Ｎ単結晶との格子整合性が良好なものが用いられる。Ｇ
ａＮ単結晶と格子製合性の良好な物質とは、結晶格子に
おけるａ軸の格子定数が、ＧａＮ単結晶のそれに対して
±１０％以内、好ましくは±５％以内であるウルツァイ
ト型の結晶構造も持つものを言う。これを満足する物質
の好ましい例として、ＺｎＯが挙げられる。ＺｎＯのａ
軸の格子定数（単位格子の長さ）は３．２４９６Åであ
り、ＧａＮのａ軸の格子定数３．１８９Åに対して＋
１．９％と、非常に近似した格子定数を備えており、良
好なＧａＮの結晶成長が行い得るので望ましい。また、
ＺｎＯは酸によるエッチング除去性が良好であり、この
点でも、バッファ層に用いる物質として好適である。バ
ッファ層の厚みは、０．０１μｍ〜１００μｍ程度が好
ましい。The material used for the buffer layer is Ga
Those having good lattice matching with the N single crystal are used. G
The substance having good lattice compatibility with the aN single crystal is a wurtzite type crystal structure in which the lattice constant of the a-axis in the crystal lattice is within ± 10%, preferably ± 5% of that of the GaN single crystal. Say what you have. A preferable example of a material satisfying this is ZnO. A of ZnO
The lattice constant of the axis (the length of the unit cell) is 3.2496 °, and the lattice constant of the GaN a-axis of 3.189 ° is +2.8.
It has a very close lattice constant of 1.9%, which is desirable because good GaN crystal growth can be performed. Also,
ZnO has good etching removability with an acid, and in this respect, it is also suitable as a substance used for the buffer layer. The thickness of the buffer layer is preferably about 0.01 μm to 100 μm.
【００１９】最初の基板Ｐ0 は、少なくとも表面がＧａ
Ｎ単結晶であるものを用いる。即ち、全体が実質的にＧ
ａＮだけからなるＧａＮ単結晶の単独の基板、または、
ＧａＮ単結晶層をバッファ層形成側の表面に有するよう
な、表面だけがＧａＮ単結晶であるような基板である。
後者の場合、ＧａＮ単結晶層を担持する基材物質として
は、ＧａＮ単結晶の成長温度（１０００〜１１００℃）
に対する耐熱性が良好なものが望ましく、例えばサファ
イア結晶基板、Ｓｉ基板、水晶、ＺｎＯ基板、ＳｉＣ基
板などが例示される。これら基材物質上へのＧａＮ単結
晶層の形成は、ＭＯＶＰＥ法、ＭＢＥ法などによる非平
衡反応に基づくヘテロエピタキシャル成長法によって行
うことができる。The first substrate P 0 has at least a surface of Ga
An N single crystal is used. That is, the whole is substantially G
a single substrate of GaN single crystal consisting only of aN, or
The substrate has a GaN single crystal layer only on the surface on the buffer layer formation side, such as a GaN single crystal.
In the latter case, the base material supporting the GaN single crystal layer may be a GaN single crystal growth temperature (1000-1100 ° C.)
A sapphire crystal substrate, a Si substrate, a quartz crystal, a ZnO substrate, a SiC substrate, etc. are exemplified. The formation of a GaN single crystal layer on these substrate materials can be performed by a heteroepitaxial growth method based on a non-equilibrium reaction such as a MOVPE method or an MBE method.
【００２０】〔ＧａＮ単結晶の製造実験および品質確認
実験〕次に、本発明のＧａＮ単結晶の製造方法によって
実際にＧａＮ単結晶を製造し、その品質を確認した結果
を示す。 実験例１ 本実験例では、上記本発明のＧａＮ単結晶の製造方法に
おける結晶成長サイクルを繰り返す方法として、図１に
おける工程２に示すように、最初の基板Ｐ0 上にバッフ
ァ層およびＧａＮ単結晶を順次成長させて積層し、最後
に各バッファ層を一度に除去してＧａＮ単結晶を分離す
る方法とした。最初の基板Ｐ0 としては、サファイア結
晶基材上にＭＯＶＰＥ法によりＧａＮ単結晶層をエピタ
キシャル成長させた基板を用いた。バッファ層は厚みを
０．２μｍ、材料をＺｎＯとした。結晶成長サイクルは
５回繰り返すものとした。結晶成長サイクル各回に形成
されるＧａＮ単結晶Ｐ1 〜Ｐ5 の厚みは全て３００μｍ
を目標とした。最後に得られたＧａＮ単結晶Ｐ5 の半値
全幅を測定したところ、２９ｓｅｃであり、また、その
厚みは３０５μｍであった。[Manufacturing Experiment of GaN Single Crystal and Quality Confirmation Experiment] Next, the result of actually manufacturing a GaN single crystal by the method of manufacturing a GaN single crystal of the present invention and confirming the quality thereof will be described. In Experiment 1 In this experiment example, as a method of repeating the crystal growth cycle in the manufacturing method of the GaN single crystal of the present invention, as shown in step 2 in FIG. 1, the buffer layer and GaN single crystal on the first substrate P 0 Are sequentially grown and stacked, and finally, each buffer layer is removed at a time to separate a GaN single crystal. The first substrate P 0, using a substrate obtained by epitaxially growing a GaN single crystal layer by the MOVPE method on a sapphire crystal substrate. The buffer layer had a thickness of 0.2 μm and the material was ZnO. The crystal growth cycle was repeated five times. The thickness of each of the GaN single crystals P 1 to P 5 formed in each crystal growth cycle is 300 μm
Was targeted. Measurement of the finally obtained full width at half maximum of the GaN single crystal P 5, a 29Sec, also its thickness was 305 .mu.m.
【００２１】実験例２ 本実験例では、上記実験例１における結晶成長サイクル
を繰り返す方法に代えて、図１における工程３に示すよ
うに、ＧａＮ単結晶がエピタキシャル成長する度に、そ
の前のバッファ層を除去し、新たな基板を常に１枚のＧ
ａＮ単独の単結晶とした以外は、実験例１と全く同様の
ＧａＮ単結晶の作製を行った。最後に得られたＧａＮ単
結晶Ｐ5 の品質は、半値全幅が２８ｓｅｃであり、ま
た、その厚みは２８９μｍであった。EXPERIMENTAL EXAMPLE 2 In this experimental example, instead of the method of repeating the crystal growth cycle in Experimental Example 1, as shown in step 3 in FIG. Is removed, and a new substrate is always
A GaN single crystal was produced in exactly the same manner as in Experimental Example 1, except that a single crystal of aN alone was used. Quality finally obtained GaN single crystal P 5 is full width at half maximum is 28Sec, also its thickness was 289μm.
【００２２】実験例３ 本実験例では、上記実験例２における最初の基板とし
て、サファイア基板と、ＡｌＮ（窒化アルミニウム）の
バッファ層と、ＧａＮ単結晶とからなる３層の基板を用
いた以外は、実験例２と全く同様のＧａＮ単結晶の作製
を行った。３層の基板の製作工程を簡単に説明する。厚
さ３００μｍ、面積５ｃｍ×５ｃｍのサファイア結晶基
板上に、バッファ層としてＡｌＮをＭＯＶＰＥ法によっ
て厚み５００Åまでエピタキシャル成長させ、その状態
のままで材料ガスを切替え、同じＭＯＶＰＥ法によって
ＧａＮ単結晶を厚み２μｍまでエピタキシャル成長させ
て表層とし、サファイア結晶基板と、ＡｌＮバッファ層
と、ＧａＮ単結晶の表層とからなる総厚約３０２μｍの
三層構造の基板を得た。本実験によって最後に得られた
ＧａＮ単結晶Ｐ5 の品質は、半値全幅が２５ｓｅｃであ
り、また、その厚みは２９５μｍであった。Experimental Example 3 In this experimental example, a three-layer substrate composed of a sapphire substrate, an AlN (aluminum nitride) buffer layer, and a GaN single crystal was used as the first substrate in Experimental Example 2 above. A GaN single crystal was produced in exactly the same manner as in Experimental Example 2. The manufacturing process of a three-layer substrate will be briefly described. On a sapphire crystal substrate having a thickness of 300 μm and an area of 5 cm × 5 cm, AlN is epitaxially grown as a buffer layer to a thickness of 500 ° by MOVPE, and the material gas is changed in this state, and a GaN single crystal is grown to 2 μm by the same MOVPE. A three-layer substrate having a total thickness of about 302 μm, comprising a sapphire crystal substrate, an AlN buffer layer, and a GaN single crystal surface layer, was obtained by epitaxial growth to form a surface layer. Quality GaN single crystal P 5 obtained last by the present experiment, the full width at half maximum is 25 sec, also its thickness was 295μm.
【００２３】実験例４ 本実験例では、上記実験例２において、最初の基板Ｐ0
として実験例３と同様の３層の基板を用い、ＧａＮ単結
晶の結晶成長サイクルを繰り返す際の、各サイクルにお
けるバッファ層の材料として（ＢｅＯ）0.13（ＺｎＯ）
0.87 を用いた以外は、実験例２と全く同様のＧａＮ単
結晶の作製を行った。本実験によって最後に得られたＧ
ａＮ単結晶Ｐ5 の品質は、半値全幅が２８ｓｅｃであ
り、また、その厚みは３０１μｍであった。EXPERIMENTAL EXAMPLE 4 In this experimental example, the first substrate P 0 in Experimental Example 2 was used.
When the same three-layer substrate as in Experimental Example 3 is used, and the crystal growth cycle of the GaN single crystal is repeated, (BeO) 0.13 (ZnO) is used as the material of the buffer layer in each cycle.
Except that 0.87 was used, a GaN single crystal was produced in exactly the same manner as in Experimental Example 2. G finally obtained by this experiment
aN quality of the single crystal P 5 is full width at half maximum is 28Sec, also its thickness was 301μm.
【００２４】実験例５ 本実験例では、本発明によるＧａＮ単結晶の品質と比較
するために、従来の製造方法によるＧａＮ単結晶の品質
を調べた。厚さ３００μｍ、面積５ｃｍ×５ｃｍのサフ
ァイア結晶基板上に、スパッタリング法によってＺｎＯ
を材料とする厚さ０．６μｍのバッファ層を成膜し、そ
の上にＨＶＰＥによってＧａＮ単結晶を厚さ２５０μｍ
までエピタキシャル成長させた。このＧａＮ単結晶の品
質は、半値全幅が４２０ｓｅｃであった。Experimental Example 5 In this experimental example, the quality of a GaN single crystal by a conventional manufacturing method was examined in order to compare with the quality of a GaN single crystal according to the present invention. ZnO was formed on a sapphire crystal substrate having a thickness of 300 μm and an area of 5 cm × 5 cm by sputtering.
Is formed into a buffer layer having a thickness of 0.6 μm, and a GaN single crystal is formed thereon by HVPE to a thickness of 250 μm.
Until epitaxial growth. As for the quality of the GaN single crystal, the full width at half maximum was 420 sec.
【００２５】上記実験結果で明らかなように、本発明の
ＧａＮ単結晶の製造方法は、従来には無い、高品質なＧ
ａＮ単結晶を製造することが可能であり、かつ、ＧａＮ
単結晶を単独の基板として用いるのに十分な厚みに製造
することが可能であることが確認された。As is evident from the above experimental results, the method for producing a GaN single crystal of the present invention has a high quality G
aN single crystal can be produced and GaN
It was confirmed that a single crystal could be manufactured to a thickness sufficient to be used as a single substrate.
【００２６】本発明の製造方法によって得られる、この
ような高品質で厚いＧａＮ単結晶は、発光ダイオード
（ＬＥＤ）、レーザーダイオード（ＬＤ）、スーパール
ミネッセンスダイオード等の半導体発光素子、電子デバ
イス等の用途に好ましく用いられる。半導体発光素子に
おいては、本発明のＧａＮ単結晶を基板として用いるこ
とで、従来の赤色ＬＥＤ等と同じ電極部の構造を有する
ＬＥＤ、ＬＤ等の製造が可能となる。これらのなかでも
特に、青色発光するものは重要である。また、その半導
体発光素子の発光の効率はより高いものとなる。Such a high-quality and thick GaN single crystal obtained by the manufacturing method of the present invention can be used for semiconductor light-emitting devices such as light-emitting diodes (LEDs), laser diodes (LDs), superluminescence diodes, and electronic devices. It is preferably used. In a semiconductor light emitting device, by using the GaN single crystal of the present invention as a substrate, it becomes possible to manufacture LEDs, LDs and the like having the same electrode structure as a conventional red LED and the like. Of these, those that emit blue light are particularly important. In addition, the light emitting efficiency of the semiconductor light emitting device becomes higher.
【００２７】〔本発明によるＧａＮ単結晶を用いたＬＥ
Ｄの品質確認実験〕本発明の製造方法によって得られた
ＧａＮ単結晶を基板として用いたＬＥＤを実際に製造
し、その品質を確認した。また、従来品質のＧａＮ単結
晶、およびサファイア結晶を各々基板とするＬＥＤを製
作し、本発明のＧａＮ単結晶を基板とするＬＥＤの品質
と比較した。従来品質のＧａＮ単結晶としては、半値全
幅が３００ｓｅｃのものを用いた。ＬＥＤの品質は、初
期の輝度と寿命について評価した。寿命は、温度８５℃
湿度８５％の雰囲気中において２０ｍＡの電流によって
２０００時間連続発光させた後の輝度を測定し、その輝
度の初期の輝度に対する低下率を求め、低下率２％未満
をＡ、低下率２〜５未満％をＢ、低下率５〜１０％をＣ
と、３つのランクに分けた。ＬＥＤの構造は、本発明の
製造方法によって得られたＧａＮ単結晶を基板とし、該
基板上に、ｎ−ＡｌＧａＮクラッド層、アンドープのＩ
ｎＧａＮ活性層、ｐ−ＡｌＧａＮクラッド層を順次成長
させてなるダブルヘテロ接合型の構成とした。本発明に
よるＧａＮ単結晶の基板の品質は、半値全幅が３０ｓｅ
ｃ、１００ｓｅｃ、２５０ｓｅｃの３種類である。厚み
はすべて２８０μｍである。また、活性層のＩｎＧａＮ
の組成比は、Ｉｎ0.15Ｇａ0.85Ｎと、Ｉｎ0.25Ｇａ0.75
Ｎの２種類とし、各々の組成比のＩｎＧａＮについて、
発光素子を作成し実験を行った。この実験結果を次の表
１、２に示す。[LE using GaN single crystal according to the present invention]
D. Quality Confirmation Experiment] An LED using the GaN single crystal obtained by the production method of the present invention as a substrate was actually manufactured and its quality was confirmed. In addition, LEDs using conventional quality GaN single crystals and sapphire crystals as substrates were manufactured, and compared with the quality of LEDs using the GaN single crystals of the present invention as substrates. As a conventional quality GaN single crystal, one having a full width at half maximum of 300 sec was used. The quality of the LEDs was evaluated for initial brightness and lifetime. Life is 85 ° C
The luminance after continuously emitting light for 2000 hours with a current of 20 mA in an atmosphere of a humidity of 85% is measured, and a decrease rate of the luminance with respect to the initial luminance is obtained. % For B, 5% to 10% for C
And divided into three ranks. The structure of the LED is such that a GaN single crystal obtained by the manufacturing method of the present invention is used as a substrate, and an n-AlGaN cladding layer and an undoped I
A double heterojunction type structure in which an nGaN active layer and a p-AlGaN cladding layer were sequentially grown was adopted. The quality of the GaN single crystal substrate according to the present invention is such that the full width at half maximum is 30 seconds.
c, 100 sec, and 250 sec. All thicknesses are 280 μm. In addition, the active layer InGaN
The composition ratio of In 0.15 Ga 0.85 N and In 0.25 Ga 0.75
N and two types of InGaN with respective composition ratios:
A light emitting device was prepared and an experiment was performed. The experimental results are shown in Tables 1 and 2 below.
【００２８】[0028]
【表１】 [Table 1]
【００２９】[0029]
【表２】 [Table 2]
【００３０】表１、２に示すように、本発明による高品
質なＧａＮ単結晶を基板として用いたＬＥＤは、初期の
輝度と寿命の点で、従来のものより優れたＬＥＤである
ことがわかった。As shown in Tables 1 and 2, it was found that the LED using the high-quality GaN single crystal according to the present invention as a substrate was superior to the conventional LED in terms of initial luminance and life. Was.
【００３１】また、ＬＤに関しては、次の現象が確認で
きた。サファイア結晶を基板とする従来のＬＤでは、サ
ファイア結晶が、へき開面の形成が困難な物質であるた
めに基板面が好ましい鏡面状態とはならず、その基板面
に形成されるＧａＮ系化合物半導体層の面の状態は、基
板面の状態に従うため、ＬＤにとって好ましい反射面は
形成することができなかった。しかし、本発明によるＧ
ａＮ単結晶は高品質であり十分な厚みを有するため、Ｇ
ａＮ単結晶を基板として、そのへき開面を得ることが容
易になった。また、従来のＧａＮ系化合物半導体を用い
たＬＤでは、結晶品質が劣っているため、電流注入によ
る誘導放出が達成できなかったが、本発明による高品質
なＧａＮ単結晶を基板として用いたファブリ・ペロー型
共振器のストライプレーザーを構成し実験したところ、
室温において誘導放出が確認された。The following phenomena were confirmed for the LD. In a conventional LD using a sapphire crystal as a substrate, the sapphire crystal is a substance that is difficult to form a cleavage plane, so that the substrate surface does not have a desirable mirror state, and a GaN-based compound semiconductor layer formed on the substrate surface Since the state of the surface follows the state of the substrate surface, a favorable reflection surface for the LD could not be formed. However, G according to the invention
Since the aN single crystal is of high quality and has a sufficient thickness,
It became easy to obtain a cleaved surface using an aN single crystal as a substrate. Further, in the LD using the conventional GaN-based compound semiconductor, the crystal quality was inferior, so that the stimulated emission by current injection could not be achieved. However, a fabric using a high-quality GaN single crystal according to the present invention as a substrate. We constructed a Perot-type resonator stripe laser and performed experiments.
Stimulated release was observed at room temperature.
【００３２】[0032]
【発明の効果】以上詳述したように、本発明のＧａＮ単
結晶は、従来にはなかった結晶品質と充分な厚みを同時
に備えるものである。また、本発明の製造方法は、その
ような高品質で充分な厚みを同時に備えたＧａＮ単結晶
を好適に提供することができる。従って、高効率の青色
発光を呈するＬＥＤや、紫外線レーザーダイオード、ま
たは耐熱性の良好な半導体デバイスを得るために好適な
ＧａＮ単結晶の基板を提供することできる。また、本発
明の製造方法は、ＧａＮ単結晶の結晶品質の向上および
厚みの獲得だけでなく、高品質なＧａＮ単結晶を効率良
く多数枚製造することが可能であり、工業的にも極めて
重要な技術である。As described above in detail, the GaN single crystal of the present invention has both crystal quality and sufficient thickness which have not been obtained in the past. Further, the manufacturing method of the present invention can suitably provide a GaN single crystal having such high quality and sufficient thickness at the same time. Therefore, it is possible to provide a substrate of a GaN single crystal suitable for obtaining an LED that emits blue light with high efficiency, an ultraviolet laser diode, or a semiconductor device having good heat resistance. Further, the manufacturing method of the present invention not only improves the crystal quality and obtains the thickness of the GaN single crystal, but also enables efficient production of a large number of high-quality GaN single crystals, which is extremely important industrially. Technology.
【図１】本発明によるＧａＮ単結晶の製造方法の工程の
一例を示す模式図である。FIG. 1 is a schematic view showing an example of steps of a method for producing a GaN single crystal according to the present invention.
Ｐ0 最初の基板 Ｐ1 〜Ｐn ＧａＮ単結晶 Ｂ1 〜Ｂn バッファ層P 0 First substrate P 1 -P n GaN single crystal B 1 -B n buffer layer
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭51−50899（ＪＰ，Ａ) 特開 昭56−59700（ＪＰ，Ａ) 特開 昭53−104598（ＪＰ，Ａ) Ｔ．Ｄｅｔｃｈｐｒｏｈｍ ｅｔ ａ ｌ．，”Ｈｙｄｒｉｄｅ ｖａｐｏｒ ｐｈａｓｅ ｅｐｉｔａｘｉａｌ ｇｒ ｏｗｔｈ ｏｆ ａ ｈｉｇｈ ｑｕａ ｌｉｔｙ ＧａＮ ｆｉｌｍ ｕｓｉｎ ｇ ａ ＺｎＯ ｂｕｆｆｅｒ ｌａｙ ｅｒ”，Ａｐｐｌｉｅｄ Ｐｈｙｓｉｃ ｓ Ｌｅｔｔｅｒ，Ｖｏｌ．61，Ｎｏ. 22，Ｎｏｖ．30，1992，ｐ．2688−2690 (58)調査した分野(Int.Cl.7，ＤＢ名) C30B 1/00 - 35/00 H01L 33/00 ＥＰＡＴ（ＱＵＥＳＴＥＬ)──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-51-50899 (JP, A) JP-A-56-59700 (JP, A) JP-A-53-104598 (JP, A) Detchprohm et al. , "Hydride vapor phase epitaxial growth of a high quality GaN film usin g a ZnO buffer layer", Applied Physics Letters, Vol. 61, No. 22, Nov. 30, 1992, p. 2688-2690 (58) Field surveyed (Int. Cl. 7 , DB name) C30B 1/00-35/00 H01L 33/00 EPAT (QUESTEL)
Claims (4)
幅が５〜２５０ｓｅｃであり、かつ、厚みが８０μｍ以
上であって、ＧａＮ系半導体結晶層を成長させるための
基板となるＧａＮ単結晶。1. A two-crystal X-ray rocking curve having a full width at half maximum of 5 to 250 seconds and a thickness of 80 μm or more, which is used for growing a GaN-based semiconductor crystal layer.
GaN single crystal used as a substrate .
板上にＧａＮ単結晶との格子整合性の良好な物質を薄膜
成長させてバッファ層とした上にＧａＮを結晶成長させ
てＧａＮ単結晶を得る工程を有する、ＧａＮ系半導体結
晶層を成長させるための基板となるＧａＮ単結晶の製造
方法。2. A GaN single crystal is obtained by growing a thin film of a material having good lattice matching with the GaN single crystal on a substrate having at least a surface of a GaN single crystal to form a buffer layer and then growing GaN on the buffer layer. GaN-based semiconductor bonding process
A method for producing a GaN single crystal serving as a substrate for growing a crystal layer.
板上にＧａＮ単結晶との格子整合性の良好な物質を薄膜
成長させてバッファ層とした上にＧａＮを結晶成長させ
てＧａＮ単結晶を得る工程を１回の結晶成長サイクルと
し、得られたＧａＮ単結晶上に上記結晶成長サイクルを
少なくとも１サイクル繰り返して積層物を形成させた後
に各バッファ層を除去し、ＧａＮ単結晶を得ることを特
徴とするＧａＮ単結晶の製造方法。3. A GaN single crystal is obtained by growing a thin film of a substance having good lattice matching with the GaN single crystal on a substrate having at least a surface of a GaN single crystal to form a buffer layer and then growing GaN on the substrate. The process is a single crystal growth cycle, and the above crystal growth cycle is repeated at least one cycle on the obtained GaN single crystal to form a laminate, and then each buffer layer is removed to obtain a GaN single crystal. A method for producing a GaN single crystal.
板上にＧａＮ単結晶との格子整合性の良好な物質を薄膜
成長させてバッファ層とした上にＧａＮを結晶成長させ
てＧａＮ単結晶を得る工程を１回の結晶成長サイクルと
し、得られたＧａＮ単結晶を新たな基板として上記結晶
成長サイクルを少なくとも１サイクル繰り返し、かつ１
サイクル毎にバッファ層を除去し、ＧａＮ単結晶を得る
ことを特徴とするＧａＮ単結晶の製造方法。4. A GaN single crystal is obtained by growing a thin film of a material having good lattice matching with the GaN single crystal on a substrate having at least a surface of a GaN single crystal to form a buffer layer and then growing GaN on the buffer layer. The process is a single crystal growth cycle, and the obtained crystal growth cycle is repeated at least one cycle using the obtained GaN single crystal as a new substrate;
A method for producing a GaN single crystal, comprising removing a buffer layer every cycle to obtain a GaN single crystal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24296794A JP3184717B2 (en) | 1993-10-08 | 1994-10-06 | GaN single crystal and method for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25309893 | 1993-10-08 | ||
| JP5-253098 | 1993-10-08 | ||
| JP24296794A JP3184717B2 (en) | 1993-10-08 | 1994-10-06 | GaN single crystal and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07165498A JPH07165498A (en) | 1995-06-27 |
| JP3184717B2 true JP3184717B2 (en) | 2001-07-09 |
Family
ID=26536014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24296794A Expired - Lifetime JP3184717B2 (en) | 1993-10-08 | 1994-10-06 | GaN single crystal and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3184717B2 (en) |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0942459B1 (en) | 1997-04-11 | 2012-03-21 | Nichia Corporation | Method of growing nitride semiconductors |
| TW449937B (en) | 1999-02-26 | 2001-08-11 | Matsushita Electronics Corp | Semiconductor device and the manufacturing method thereof |
| JP4465745B2 (en) | 1999-07-23 | 2010-05-19 | ソニー株式会社 | Semiconductor laminated substrate, semiconductor crystal substrate, semiconductor element, and manufacturing method thereof |
| JP4618836B2 (en) * | 2000-01-04 | 2011-01-26 | シャープ株式会社 | Nitride-based compound semiconductor substrate and method for manufacturing the same |
| JP2002241198A (en) * | 2001-02-13 | 2002-08-28 | Hitachi Cable Ltd | GaN SINGLE CRYSTAL SUBSTRATE AND METHOD FOR PRODUCING THE SAME |
| JP3812368B2 (en) | 2001-06-06 | 2006-08-23 | 豊田合成株式会社 | Group III nitride compound semiconductor device and method for manufacturing the same |
| TWI277666B (en) | 2001-06-06 | 2007-04-01 | Ammono Sp Zoo | Process and apparatus for obtaining bulk mono-crystalline gallium-containing nitride |
| PL207400B1 (en) | 2001-06-06 | 2010-12-31 | Ammono Społka Z Ograniczoną Odpowiedzialnością | Method of and apparatus for obtaining voluminous, gallium containing, monocrystalline nitride |
| US6897138B2 (en) | 2001-06-25 | 2005-05-24 | Toyoda Gosei Co., Ltd. | Method and apparatus for producing group III nitride compound semiconductor |
| JP4035971B2 (en) | 2001-09-03 | 2008-01-23 | 豊田合成株式会社 | Manufacturing method of semiconductor crystal |
| US7750355B2 (en) | 2001-10-26 | 2010-07-06 | Ammono Sp. Z O.O. | Light emitting element structure using nitride bulk single crystal layer |
| CN1316070C (en) | 2001-10-26 | 2007-05-16 | 波兰商艾蒙诺公司 | Substrate for epitaxy |
| JP4416648B2 (en) | 2002-05-17 | 2010-02-17 | アンモノ・スプウカ・ジ・オグラニチョノン・オドポヴィエドニアウノシツィオン | Method for manufacturing light emitting device |
| TWI274735B (en) | 2002-05-17 | 2007-03-01 | Ammono Sp Zoo | Bulk single crystal production facility employing supercritical ammonia |
| JP3595829B2 (en) * | 2003-03-19 | 2004-12-02 | 株式会社東北テクノアーチ | GaN substrate manufacturing method |
| JP4600641B2 (en) | 2004-01-27 | 2010-12-15 | 日立電線株式会社 | Nitride semiconductor free-standing substrate and nitride semiconductor light emitting device using the same |
| JP4654611B2 (en) * | 2004-06-15 | 2011-03-23 | 日亜化学工業株式会社 | Method of growing nitride semiconductor layer |
| KR20070058465A (en) | 2004-08-06 | 2007-06-08 | 미쓰비시 가가꾸 가부시키가이샤 | Nitride semiconductor single crystal including ga, method for manufacturing the same, and substrate and device using the crystal |
| CN101248221B (en) | 2005-08-25 | 2012-06-06 | 东北技术使者株式会社 | Process for producing semiconductor substrate |
| KR100695118B1 (en) * | 2005-12-27 | 2007-03-14 | 삼성코닝 주식회사 | Fabrication method of multi-freestanding gan wafer |
| EP2045374A3 (en) | 2007-10-05 | 2011-02-16 | Sumitomo Electric Industries, Ltd. | Method of manufacturing a GaN substrate and a GaN epitaxial wafer |
| JP5291499B2 (en) * | 2009-03-10 | 2013-09-18 | 株式会社沖データ | Manufacturing method of semiconductor composite device |
| JP2011254068A (en) * | 2010-05-07 | 2011-12-15 | Sumitomo Chemical Co Ltd | Semiconductor substrate |
| WO2017221519A1 (en) * | 2016-06-20 | 2017-12-28 | ソニー株式会社 | Nitride semiconductor element, nitride semiconductor substrate, method for manufacturing nitride semiconductor element, and method for manufacturing nitride semiconductor substrate |
-
1994
- 1994-10-06 JP JP24296794A patent/JP3184717B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| Ｔ．Ｄｅｔｃｈｐｒｏｈｍ ｅｔ ａｌ．，"Ｈｙｄｒｉｄｅ ｖａｐｏｒ ｐｈａｓｅ ｅｐｉｔａｘｉａｌ ｇｒｏｗｔｈ ｏｆ ａ ｈｉｇｈ ｑｕａｌｉｔｙ ＧａＮ ｆｉｌｍ ｕｓｉｎｇ ａ ＺｎＯ ｂｕｆｆｅｒ ｌａｙｅｒ"，Ａｐｐｌｉｅｄ Ｐｈｙｓｉｃｓ Ｌｅｔｔｅｒ，Ｖｏｌ．６１，Ｎｏ．２２，Ｎｏｖ．３０，１９９２，ｐ．２６８８−２６９０ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07165498A (en) | 1995-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3184717B2 (en) | GaN single crystal and method for producing the same | |
| US5770887A (en) | GaN single crystal | |
| JP3749498B2 (en) | Crystal growth substrate and ZnO-based compound semiconductor device | |
| JP5023318B2 (en) | 3-5 nitride semiconductor multilayer substrate, 3-5 nitride semiconductor free-standing substrate manufacturing method, and semiconductor device | |
| JP4939014B2 (en) | Group III nitride semiconductor light emitting device and method for manufacturing group III nitride semiconductor light emitting device | |
| JPH10247626A (en) | Method of growing gallium nitride on spinel substrate | |
| WO2005015617A1 (en) | Semiconductor layer | |
| JPH07273367A (en) | Manufacture of semiconductor substrate and light-emitting device | |
| JPH11135882A (en) | Compound semiconductor substrate, manufacture thereof, and light-emitting element | |
| JPH11274560A (en) | Semiconductor element and manufacture thereof | |
| JPH11274082A (en) | Group iii nitride semiconductor and fabrication thereof, and group iii nitride semiconductor device | |
| JPH07273048A (en) | Manufacture method of compound semiconductor single crystal and single crystal substrate using such method | |
| JP2002241198A (en) | GaN SINGLE CRYSTAL SUBSTRATE AND METHOD FOR PRODUCING THE SAME | |
| JP3289682B2 (en) | Semiconductor light emitting device | |
| JPH07267796A (en) | Production of gallium nitride single crystal | |
| JP3463736B2 (en) | Semiconductor light emitting device and method of adjusting light emission intensity thereof | |
| JP2000114599A (en) | Semiconductor light emitting element | |
| JP2003309071A (en) | GaN SEMICONDUCTOR CRYSTAL BASE MATERIAL | |
| JPH09283799A (en) | Semiconductor light-emitting element | |
| JP2004014587A (en) | Nitride compound semiconductor epitaxial wafer and light emitting element | |
| JP4786587B2 (en) | Group III nitride semiconductor and method for manufacturing the same, substrate for manufacturing group III nitride semiconductor | |
| JPH0794784A (en) | Blue light-emitting device | |
| JP2000012979A (en) | Method for manufacturing nitride semiconductor substrate | |
| JP3749454B2 (en) | GaN single crystal manufacturing method | |
| JPH09237938A (en) | Iii-v group compound semiconductor device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090427 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090427 Year of fee payment: 8 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090427 Year of fee payment: 8 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090427 Year of fee payment: 8 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090427 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100427 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100427 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110427 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130427 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140427 Year of fee payment: 13 |
|
| EXPY | Cancellation because of completion of term |