JPH08203834A - Semiconductor thin film and manufacture thereof - Google Patents
Semiconductor thin film and manufacture thereofInfo
- Publication number
- JPH08203834A JPH08203834A JP909295A JP909295A JPH08203834A JP H08203834 A JPH08203834 A JP H08203834A JP 909295 A JP909295 A JP 909295A JP 909295 A JP909295 A JP 909295A JP H08203834 A JPH08203834 A JP H08203834A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- algan
- forming
- single 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.)
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- Semiconductor Lasers (AREA)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、緑・青色発光ダイオー
ドや光ディスク等情報処理装置用光源に用いることので
きる青色もしくは更に短波長の半導体レーザ素子の製造
方法に関するもので、特に窒化物系材料の薄膜形成に係
わるものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a blue or shorter wavelength semiconductor laser device which can be used as a light source for an information processing device such as a green / blue light emitting diode or an optical disk. It is related to thin film formation.
【０００２】[0002]
【従来の技術】１９８８年に６７０ｎｍ帯ＡｌＧａＩｎ
Ｐ系赤色半導体レーザが商品化されて以来、レーザプリ
ンター、光ディスク等の情報処理装置用光源として短波
長半導体レーザの開発が活発に行われている。当初６７
０〜６９０ｎｍが開発の中心であったが、バーコードリ
ーダの視認性の改善、光ディスクの高密度化等の要求に
ともなって、波長領域はＨｅ−Ｎｅガスレーザと同レベ
ルの６３０ｎｍ帯へと移行しつつある。さらに将来、記
憶容量の増大に伴って、赤色よりさらに短波長の青・緑
色から紫外域にわたる半導体レーザの実現が切望されて
おり、ｐ型導電型制御が可能となったことを契機にＩＩ
-ＶＩ族系半導体レーザの研究が急速に進展してきてい
る。一方、窒化ガリウム(ＧａＮ）は、約３．４eVの広
エネルギーギャップを持つ直接遷移型の化合物半導体で
青色から紫外領域にわたる発光素子として有望な材料で
あるがＧａＮバルク基板結晶が容易に作製できず、ま
た、ほかに適当な基板結晶がないことから半導体レーザ
としての開発はあまり進展していなかった。2. Description of the Related Art In 1988, 670 nm band AlGaIn
Since the commercialization of the P-based red semiconductor laser, short wavelength semiconductor lasers have been actively developed as a light source for information processing devices such as laser printers and optical discs. Initially 67
Although 0 to 690 nm was the focus of development, the wavelength range shifted to the 630 nm band, which is the same level as the He-Ne gas laser, due to demands for improved visibility of barcode readers and higher density of optical discs. It's starting. Furthermore, in the future, with the increase in storage capacity, there is a strong demand for the realization of semiconductor lasers that have wavelengths shorter than red, such as blue / green to the ultraviolet region, and the p-type conductivity type control became possible.
-Research on group VI semiconductor lasers has been rapidly progressing. On the other hand, gallium nitride (GaN) is a direct transition type compound semiconductor having a wide energy gap of about 3.4 eV and is a promising material as a light emitting device in the blue to ultraviolet region, but a GaN bulk substrate crystal cannot be easily manufactured. Moreover, since there is no other suitable substrate crystal, the development as a semiconductor laser has not made much progress.
【０００３】ＧａＮ薄膜の作製方法としては、αーＡｌ
2Ｏ3（サファイア）基板上にＭＯＶＰＥ法（有機金属気
相成長法）により気相成長する方法が一般的に用いられ
ている。これは、例えばトリメチルガリウムとアンモニ
アを１０５０℃程度に加熱した基板、例えば、サファイ
ア基板の表面上で分解、反応させ、ＧａＮ薄膜を成長し
ようとするものである。最近サファイアの（０００１）
Ｃ面を用い、低温で堆積したＧａＮやＡｌＮ緩衝層を介
して比較的良質のＧａＮ薄膜を形成できることが実証さ
れ、青色発光ダイオードとして商品化されまでに至っ
た。As a method for producing a GaN thin film, α-Al is used.
A method of vapor phase growth on a 2 O 3 (sapphire) substrate by MOVPE (metalorganic vapor phase epitaxy) is generally used. This is for growing a GaN thin film by decomposing and reacting trimethylgallium and ammonia on the surface of a substrate, for example, a sapphire substrate heated to about 1050 ° C. Recently Sapphire (0001)
It has been demonstrated that a relatively good quality GaN thin film can be formed using a C-plane and a GaN or AlN buffer layer deposited at low temperature, and has been commercialized as a blue light emitting diode.
【０００４】[0004]
【発明が解決しようとする課題】上述の従来技術によれ
ば、サファイアＣ面とＧａＮとの間には１３．８％とい
う極めて大きな格子不整合や大きな熱膨張係数の差があ
るため、成長した窒化膜にはピットやクラックが入りや
すく、均一で平坦性のよい窒化膜の成長が困難であっ
た。According to the above-mentioned conventional technique, there is an extremely large lattice mismatch of 13.8% between the sapphire C-plane and GaN, and a large difference in thermal expansion coefficient, so that growth has occurred. Pits and cracks were easily formed in the nitride film, and it was difficult to grow a uniform and flat nitride film.
【０００５】低温で堆積した緩衝層を介した場合におい
ては、格子不整合の緩和は効率的におこり平坦で鏡面性
の窒化膜の成長が可能であるが、依然として１０8ｃｍ
-2以上のミスフィット転位が存在し高品質な薄膜の形成
が困難であった。さらに従来技術によれば、サファイア
が基板として用いられていたため加工が困難でデバイス
の作製が容易でないという問題があった。When the buffer layer deposited at a low temperature is used, the lattice mismatch is effectively relaxed and a flat and mirror-like nitride film can be grown, but it is still 10 8 cm.
-There were more than 2 misfit dislocations and it was difficult to form high quality thin films. Further, according to the conventional technique, since sapphire is used as the substrate, there is a problem that processing is difficult and device fabrication is not easy.
【０００６】本発明は、転位が少なく平坦性のよいＡｌ
ＧａＩｎＮ薄膜の形成方法を提供することを目的とす
る。同時に、加工の容易な基板上への高品質なＡｌＧａ
ＩｎＮ薄膜の形成方法を提供することを目的とする。According to the present invention, Al having few dislocations and good flatness is provided.
It is an object to provide a method for forming a GaInN thin film. At the same time, high quality AlGa on the substrate that is easy to process
An object is to provide a method for forming an InN thin film.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成するため
に、請求項１記載のＡｌＧａＩｎＮ薄膜の形成方法は、
加熱された基板表面上にIII族構成元素を含む原料およ
び窒素を含む原料を供給して緩衝層を介してＡｌＧａＩ
ｎＮ薄膜を形成する方法において、前記基板上に第一の
ＡｌＧａＮ単結晶薄膜を形成した後にＡｌＧａＮからな
る緩衝層を形成する工程と、次いで第二のＡｌＧａＮ単
結晶薄膜を形成した後にＡｌＧａＩｎＮ単結晶薄膜を形
成する工程を少なくとも含むことを特徴とする。ここ
で、前記第一及び第二のＡｌＧａＮ単結晶薄膜は８００
℃以上の基板温度で形成し、前記ＡｌＧａＮからなる緩
衝層は８００℃以下の基板温度とすることが望ましい。In order to achieve the above object, a method for forming an AlGaInN thin film according to claim 1 is
A raw material containing a group III constituent element and a raw material containing nitrogen are supplied onto the surface of the heated substrate, and AlGaI is passed through the buffer layer.
In the method of forming an nN thin film, a step of forming a first AlGaN single crystal thin film on the substrate and then forming a buffer layer made of AlGaN, and then forming a second AlGaN single crystal thin film and then an AlGaInN single crystal thin film. It is characterized by including at least the process of forming. Here, the first and second AlGaN single crystal thin films are 800
It is desirable that the buffer layer is formed at a substrate temperature of not less than 0 ° C. and the buffer layer made of AlGaN has a substrate temperature of not more than 800 ° C.
【０００８】請求項２記載のＡｌＧａＩｎＮ薄膜の形成
方法は、加熱された基板表面上にIII族構成元素を含む
原料および窒素を含む原料を供給して緩衝層を介してＡ
ｌＧａＩｎＮ薄膜を形成する方法において、前記基板上
に第一のＡｌＧａＮ単結晶薄膜を形成した後にＡｌＧａ
Ｎからなる緩衝層を形成する工程と、次いで第二のＡｌ
ＧａＮ単結晶薄膜を形成した後にＡｌＧａＩｎＮ単結晶
薄膜を形成する工程と、前記第二のＡｌＧａＮ単結晶薄
膜中もしくは前記第二のＡｌＧａＮ単結晶薄膜上に複数
の組成の異なるＡｌＧａＩｎＮ層からなる歪超格子構造
を形成する工程とを少なくとも含むことをを特徴とす
る。ここで、前記第一及び第二のＡｌＧａＮ単結晶薄膜
は８００℃以上の基板温度で形成し、前記ＡｌＧａＮか
らなる緩衝層は８００℃以下の基板温度とすることが望
ましい。According to a second aspect of the present invention, there is provided a method of forming an AlGaInN thin film, in which a raw material containing a group III constituent element and a raw material containing nitrogen are supplied onto a heated substrate surface, and A is supplied via a buffer layer.
In the method of forming a 1GaInN thin film, after forming a first AlGaN single crystal thin film on the substrate, AlGaInN thin film is formed.
Forming a buffer layer of N, and then a second Al
A step of forming an AlGaInN single crystal thin film after forming a GaN single crystal thin film, and a strained superlattice composed of a plurality of AlGaInN layers having different compositions in or on the second AlGaN single crystal thin film And at least a step of forming a structure. Here, it is preferable that the first and second AlGaN single crystal thin films are formed at a substrate temperature of 800 ° C. or higher, and the buffer layer made of AlGaN is set to a substrate temperature of 800 ° C. or lower.
【０００９】以上の請求項において、基板を配置した加
熱体の回転速度は３００回転/分以上とすること、基板
はＳｉＣやＺｎＯであることが望ましい。In the above claims, it is desirable that the rotating speed of the heating element on which the substrate is arranged is 300 rpm or more, and the substrate is SiC or ZnO.
【００１０】[0010]
【作用】請求項１のＡｌＧａＩｎＮ薄膜の作製方法によ
れば、以下のような作用がある。According to the method of manufacturing the AlGaInN thin film of the first aspect, there are the following effects.
【００１１】ＡｌＧａＩｎＮとの格子不整合差や熱膨張
係数差がサファイア基板と比べ極めて小さいＳｉＣ、Ｚ
ｎＯ基板を用いることによって、臨界膜厚以下であれば
単結晶ＡｌＮ薄膜を平坦かつ均一に堆積できる。このＡ
ｌＮ薄膜上に低温で堆積する非単結晶ＡｌＮは同一元素
からなる単結晶上に堆積するので、その表面は平坦かつ
均一とすることが可能となる。SiC, Z having a lattice mismatch with AlGaInN and a difference in thermal expansion coefficient which are extremely smaller than those of the sapphire substrate.
By using the nO substrate, a single crystal AlN thin film can be flatly and uniformly deposited if the thickness is below the critical film thickness. This A
Since the non-single-crystal AlN deposited on the 1N thin film at low temperature is deposited on the single crystal composed of the same element, its surface can be made flat and uniform.
【００１２】さらには、単結晶層を介して非単結晶緩衝
層を低温で堆積しているので、基板からの不純物拡散は
著しく低減できる。従って、従来のサファイア基板上に
非単結晶緩衝層のみを介して堆積したＡｌＧａＩｎＮ層
に比べ、緩衝層界面から発生した欠陥の伝搬は著しく低
減され、上面に堆積したＡｌＧａＩｎＮ薄膜へのミスフ
ィット転位の伝搬を大幅に低減でき高品質なＡｌＧａＩ
ｎＮ薄膜の形成が可能である。Furthermore, since the non-single crystal buffer layer is deposited at a low temperature through the single crystal layer, the diffusion of impurities from the substrate can be significantly reduced. Therefore, as compared with the AlGaInN layer deposited on the conventional sapphire substrate via only the non-single-crystal buffer layer, the propagation of defects generated from the interface of the buffer layer is significantly reduced, and misfit dislocations to the AlGaInN thin film deposited on the upper surface are reduced. High quality AlGaI that can greatly reduce propagation
It is possible to form an nN thin film.
【００１３】更に、請求項２記載のＡｌＧａＩｎＮ薄膜
の作製方法によれば、以下のような付加的な作用があ
る。Further, according to the method of manufacturing an AlGaInN thin film according to the second aspect, there are the following additional effects.
【００１４】ＡｌＧａＩｎＮ薄膜の形成に先立ち歪Ａｌ
ＧａＩｎＮ超格子を配置するので、ミスフィット転位は
歪ＡｌＧａＩｎＮ超格子によって面内方向への運動成分
が大きくなるため、上面への伝搬を効率的に抑制でき高
品質なＡｌＧａＩｎＮ薄膜の形成が可能となる。Prior to the formation of the AlGaInN thin film, strained Al
Since the GaInN superlattice is arranged, the misfit dislocation has a large motion component in the in-plane direction due to the strained AlGaInN superlattice, so that the propagation to the upper surface can be efficiently suppressed, and a high-quality AlGaInN thin film can be formed. .
【００１５】また、本発明によれば、ＳｉＣなどの加工
の容易な基板上にも高品質なＡｌＧａＩｎＮ薄膜の形成
が可能である。Further, according to the present invention, it is possible to form a high-quality AlGaInN thin film on a substrate such as SiC which is easily processed.
【００１６】さらには、基板を高速回転させたので、比
較的低温で成長可能であり 、成長温度が高いことによ
るガス対流の抑制、Ｉｎの解離の抑制が可能となる。よ
って従来よりも低温で高品質なＡｌＧａＩｎＮ薄膜もし
くはＡｌＧａＩｎＮ多層膜の形成が可能となる。Further, since the substrate is rotated at a high speed, it is possible to grow at a relatively low temperature, and it is possible to suppress gas convection and dissociation of In due to the high growth temperature. Therefore, it is possible to form a high quality AlGaInN thin film or AlGaInN multilayer film at a lower temperature than in the past.
【００１７】[0017]
【実施例】以下、実施例で本発明を説明する。なお、以
下同一部分については同一符号を記す。EXAMPLES The present invention will be described below with reference to examples. Note that, hereinafter, the same portions will be denoted by the same reference numerals.
【００１８】ＡｌＧａＩｎＮ薄膜の製造には、図１に概
略的に示すＭＯＶＰＥ装置を用いた。ここで、石英製反
応管１の内部には石英製ガス導入管２が取り付けられて
いる。石英製ガス導入管からはIII族構成元素を含む原
料および窒素を含む原料を同時に供給できる構造となっ
ている。石英製反応管１の外周には高周波加熱用コイル
３が設置され、また、内部にはＳｉＣコートされたグラ
ファイト製サセプター４が設置されている。グラファイ
ト製サセプター４はモーターによって１０００回転/分
程度に回転可能なサセプター支持棒５により支持されて
いる。グラファイト製サセプター４上面には、石英製ト
レー６上に搭載された基板７が設置できる構成となって
いる。また、石英製反応管１の底部には真空ポンプに接
続された排気口８が設けられていて、石英製反応管１内
の圧力調整及びガスの排気ができる。The MOVPE apparatus schematically shown in FIG. 1 was used to manufacture the AlGaInN thin film. Here, a quartz gas introduction tube 2 is attached inside the quartz reaction tube 1. From the quartz gas introduction pipe, the raw material containing the group III constituent element and the raw material containing nitrogen can be simultaneously supplied. A high-frequency heating coil 3 is installed on the outer circumference of the quartz reaction tube 1, and a SiC-coated graphite susceptor 4 is installed inside. The graphite susceptor 4 is supported by a susceptor support rod 5 which is rotatable by a motor at about 1000 revolutions / minute. On the upper surface of the graphite susceptor 4, the substrate 7 mounted on the quartz tray 6 can be installed. An exhaust port 8 connected to a vacuum pump is provided at the bottom of the quartz reaction tube 1 so that the pressure inside the quartz reaction tube 1 can be adjusted and the gas can be exhausted.
【００１９】（実施例１）図２に本発明の第一の実施例
のＡｌxＧａyＩｎzＮ薄膜（ｘ＋ｙ＋ｚ＝１、０≦≦ｘ
≦１、０≦ｙ≦１、０≦ｚ≦１、以下、ＡｌＧａＩｎＮ
と称す。）の形成方法により作製したＡｌＧａＩｎＮ薄
膜の断面構造図を示す。図１のＭＯＶＰＥ装置を用いた
ＡｌＧａＩｎＮ薄膜の形成方法について、順を追って説
明する。(Embodiment 1) FIG. 2 shows an AlxGayInzN thin film (x + y + z = 1, 0 ≦≦ x of the first embodiment of the present invention.
≦ 1, 0 ≦ y ≦ 1, 0 ≦ z ≦ 1, hereinafter, AlGaInN
Called. FIG. 3 is a cross-sectional structural view of an AlGaInN thin film manufactured by the method described in (1). A method of forming an AlGaInN thin film using the MOVPE apparatus of FIG. 1 will be described step by step.
【００２０】６Ｈ-ＳｉＣ基板１１を脱脂洗浄した後、
石英製トレー６上に結晶成長基板として配置し、石英製
反応管１内に導入した。石英製反応管１内に水素ガスを
導入し、石英製反応管１内圧力を１／１０気圧に設定し
た後、グラファイト製サセプター４を１０００回転/分
で回転させた。次いで、水素ガス中でグラファイト製サ
セプター４を１1００℃まで昇温し、６Ｈ-ＳｉＣ基板１
１表面の清浄化を行った。After degreasing and cleaning the 6H-SiC substrate 11,
It was placed as a crystal growth substrate on a quartz tray 6 and introduced into the quartz reaction tube 1. Hydrogen gas was introduced into the quartz reaction tube 1 to set the internal pressure of the quartz reaction tube 1 to 1/10 atmospheric pressure, and then the graphite susceptor 4 was rotated at 1000 rpm. Then, the temperature of the graphite susceptor 4 is raised to 110 ° C. in hydrogen gas, and the 6H-SiC substrate 1 is heated.
1 The surface was cleaned.
【００２１】その後、基板温度を９００℃まで降温し、
石英製ガス導入管２から６Ｈ-ＳｉＣ基板１１面上にＶ
族原料としてアンモニアガスを導入した後、１０秒後に
III族原料としてトリメチルアルミニウムを供給して膜
厚１０ｎｍの単結晶ＡｌＮ層１２を堆積した。このＡｌ
Ｎ層１２は１０ｎｍ程度であるので、欠陥が入ることの
ない高品質の膜となっている。またこの層は、これから
堆積させる層とＳｉＣ基板とのなじみをよくするはたら
きもある。ＳｉＣ基板はＡｌＧａＩｎＮ層と格子定数は
近いが、Ａｌを含んでいないなどの構成元素のちがいが
あるからである。Thereafter, the substrate temperature is lowered to 900 ° C.,
From the quartz gas inlet tube 2 to V on the 6H-SiC substrate 11 surface
10 seconds after introducing ammonia gas as a group raw material
Trimethyl aluminum was supplied as a Group III material to deposit a single crystal AlN layer 12 having a film thickness of 10 nm. This Al
Since the N layer 12 has a thickness of about 10 nm, it is a high quality film with no defects. This layer also serves to improve the compatibility between the layer to be deposited and the SiC substrate. This is because the SiC substrate has a lattice constant close to that of the AlGaInN layer, but there is a difference in constituent elements such as not containing Al.
【００２２】その後、トリメチルアルミニウムの供給を
一旦停止し、基板温度を６００℃まで降温した後、石英
製ガス導入管２からIII族原料としてトリメチルアルミ
ニウムを再度供給して膜厚２０ｎｍの非単結晶ＡｌＮ層
１３を堆積した。これを緩衝層として用いた。ＡｌＮ層
１２は臨界膜厚以内であって、膜厚もうすいため、欠陥
がはいることはないが、このＡｌＮ１３は非単結晶とな
っている。ここで非単結晶とは、完全な単結晶ではない
ことを意味し、多結晶や非晶質も含まれる。Thereafter, the supply of trimethylaluminum is once stopped, the substrate temperature is lowered to 600 ° C., and then trimethylaluminum as a group III raw material is supplied again from the quartz gas introduction tube 2 to supply non-single-crystal AlN having a film thickness of 20 nm. Layer 13 was deposited. This was used as a buffer layer. Since the AlN layer 12 is within the critical film thickness and the film thickness is already thin, no defects are present, but the AlN 13 is a non-single crystal. Here, the term "non-single crystal" means not a perfect single crystal, and includes polycrystal and amorphous.
【００２３】次いで、基板温度を１０００℃に昇温した
後、III族原料としてトリメチルアルミニウムとトリメ
チルガリウムを供給して膜厚３μｍのＡｌＧａＮ層１４
を堆積した。組成は、Ａｌ0.1Ｇａ0.9Ｎである。３μｍ
の成長によってＡｌＧａＮ層１４表面は平坦となった。Next, after raising the substrate temperature to 1000 ° C., trimethylaluminum and trimethylgallium are supplied as a group III raw material to form an AlGaN layer 14 having a film thickness of 3 μm.
Was deposited. The composition is Al0.1Ga0.9N. 3 μm
The surface of the AlGaN layer 14 became flat due to the growth of.
【００２４】更に、基板温度を９００℃に降温した後、
トリメチルガリウム、トリメチルアルミニウムとトリメ
チルインジウムを同時に供給して膜厚３μｍのＡｌＧａ
ＩｎＮ層１５を堆積した。組成はＡｌ0.8Ｇａ0.05Ｉｎ
0.15Ｎである。Further, after lowering the substrate temperature to 900 ° C.,
Trimethylgallium, trimethylaluminum and trimethylindium are supplied simultaneously to form an AlGa film having a thickness of 3 μm.
InN layer 15 was deposited. The composition is Al0.8Ga0.05In
It is 0.15N.
【００２５】最後にトリメチルガリウム、トリメチルア
ルミニウムとトリメチルインジウムの供給を停止した
後、基板温度を降温して３００℃以下の温度になったと
ころでアンモニアの供給を停止した。基板の温度を室温
まで降下させた後、石英製反応管１内より基板を取り出
した。Finally, after the supply of trimethylgallium, trimethylaluminum and trimethylindium was stopped, the temperature of the substrate was lowered and the supply of ammonia was stopped when the temperature reached 300 ° C. or lower. After the temperature of the substrate was lowered to room temperature, the substrate was taken out from the quartz reaction tube 1.
【００２６】本実施例においては、基板上に６μｍ以上
の厚膜を堆積したにもかかわらず、クラックの発生もな
く表面平坦であり、ホール効果によるとキャリア濃度は
１０ 15ｃｍ-3と極めて欠陥の少ない四元混晶層が得られ
た。In this embodiment, 6 μm or more is formed on the substrate.
Despite depositing a thick film of
The surface is flat and the carrier concentration is
10 Fifteencm-3And a quaternary mixed crystal layer with extremely few defects was obtained.
Was.
【００２７】また、グラファイト製サセプター４を１０
回転/分で回転させた場合は、結晶表面は凸凹で四元混
晶層のＩｎ組成が０．０６であったのに対し、本実施例
の場合、Ｉｎ組成は０．１５となり、１０００回転/分
の高速回転によりＩｎの取り込まれ率が増大することを
確認した。Further, the graphite susceptor 4 is replaced by 10
In the case of rotating at a speed of rotation / minute, the crystal surface was uneven and the In composition of the quaternary mixed crystal layer was 0.06, whereas in the present example, the In composition was 0.15 and 1000 rotations were performed. It was confirmed that the In incorporation rate increased with the high-speed rotation of / min.
【００２８】本実施例によれば、従来のサファイア基板
上に非単結晶層のみを介して堆積したＡｌＧａＩｎＮ層
に比べ、緩衝層界面から発生した欠陥の伝搬は著しく低
減された。According to this embodiment, the propagation of defects generated from the interface of the buffer layer was significantly reduced as compared with the conventional AlGaInN layer deposited on the sapphire substrate via only the non-single crystal layer.
【００２９】このように基板上に非常に品質のよいＡｌ
ＧａＩｎＮ層を堆積できる理由は、ＡｌＧａＩｎＮ層１
５に格子定数の近いＳｉＣ基板１１を用いた上に、この
基板１１上に、非単結晶ＡｌＮ層１３と同じ構成元素で
あるうすい単結晶ＡｌＮ層１２を堆積したので、非単結
晶ＡｌＮ層１３は厚みや結晶構造のばらつきが少ない層
を堆積できるからである。この単結晶ＡｌＮ層１２と非
単結晶層１３とを介してＡｌＧａＩｎＮ層を成長させれ
ば、かならずしもＳｉＣ基板を用いなくてもよい。た
だ、ＳｉＣ基板はサファイア基板に比べて格段に取扱が
容易である。As described above, Al of very high quality is formed on the substrate.
The reason why the GaInN layer can be deposited is that the AlGaInN layer 1
5, a thin single crystal AlN layer 12 having the same constituent elements as the non-single crystal AlN layer 13 was deposited on the SiC substrate 11 having a lattice constant close to that of the non-single crystal AlN layer 13. Is because it is possible to deposit a layer with little variation in thickness and crystal structure. If the AlGaInN layer is grown through the single crystal AlN layer 12 and the non-single crystal layer 13, it is not always necessary to use the SiC substrate. However, the SiC substrate is much easier to handle than the sapphire substrate.
【００３０】またここではＳｉＣ基板上に組成がＡｌＮ
からなる単結晶ＡｌＮ層１２および非単結晶ＡｌＮ層１
３を用いているが、この組成にＧａが含まれていてもよ
く、いわゆるＡｌxＧａ1-xＮ層（０≦ｘ≦１）であって
もよい。Further, here, the composition is AlN on the SiC substrate.
Single-crystal AlN layer 12 and non-single-crystal AlN layer 1
However, Ga may be contained in this composition, and a so-called AlxGa1-xN layer (0≤x≤1) may be used.
【００３１】なお、本実施例では、品質のよいＡｌＧａ
ＩｎＮ層１５の成長のために、非単結晶ＡｌＮ層１３の
上に、Ａｌ0.1Ｇａ0.9Ｎ層１４を用いているが、この層
がない場合であってもかまわない。In this embodiment, high quality AlGa is used.
In order to grow the InN layer 15, the Al0.1Ga0.9N layer 14 is used on the non-single-crystal AlN layer 13, but this layer may be omitted.
【００３２】（実施例２）図３に本発明の第二の実施例
のＡｌＧａＩｎＮ薄膜の形成方法により作製したＡｌＧ
ａＩｎＮ薄膜の断面構造図を示す。実施例１との違い
は、ＡｌＧａＩｎＮ層１５とＡｌＧａＮ層１４との間に
ＡｌＧａＮ／ＧａＩｎＮ歪超格子１８を用いていること
である。図１のＭＯＶＰＥ装置を用いたＡｌＧａＩｎＮ
薄膜の製造方法について、順を追って説明する。(Embodiment 2) FIG. 3 shows an AlG produced by the method of forming an AlGaInN thin film according to the second embodiment of the present invention.
The cross-section figure of an aInN thin film is shown. The difference from Example 1 is that an AlGaN / GaInN strained superlattice 18 is used between the AlGaInN layer 15 and the AlGaN layer 14. AlGaInN using the MOVPE device of FIG.
A method of manufacturing a thin film will be described step by step.
【００３３】６Ｈ-ＳｉＣ基板１１を脱脂洗浄した後、
石英製トレー６上に結晶成長基板として配置し、石英製
反応管１内に導入した。石英製反応管１内に水素ガスを
導入し、石英製反応管１内圧力を１／１０気圧に設定し
た後、グラファイト製サセプター４を１０００回転/分
で回転させた。次いで、水素ガス中でグラファイト製サ
セプター４を１1００℃まで昇温し、６Ｈ-ＳｉＣ基板１
１表面の清浄化を行った。After degreasing and cleaning the 6H-SiC substrate 11,
It was placed as a crystal growth substrate on a quartz tray 6 and introduced into the quartz reaction tube 1. Hydrogen gas was introduced into the quartz reaction tube 1 to set the internal pressure of the quartz reaction tube 1 to 1/10 atmospheric pressure, and then the graphite susceptor 4 was rotated at 1000 rpm. Then, the temperature of the graphite susceptor 4 is raised to 110 ° C. in hydrogen gas, and the 6H-SiC substrate 1 is heated.
1 The surface was cleaned.
【００３４】その後、基板温度を９００℃まで降温し、
石英製ガス導入管２から６Ｈ-ＳｉＣ基板１１面上にＶ
族原料としてアンモニアガスを導入した後、１０秒後に
III族原料としてトリメチルアルミニウムを供給して膜
厚１０ｎｍの単結晶ＡｌＮ層１２を堆積した。Thereafter, the substrate temperature is lowered to 900 ° C.,
From the quartz gas inlet tube 2 to V on the 6H-SiC substrate 11 surface
10 seconds after introducing ammonia gas as a group raw material
Trimethyl aluminum was supplied as a Group III material to deposit a single crystal AlN layer 12 having a film thickness of 10 nm.
【００３５】その後、トリメチルアルミニウムの供給を
一旦停止し、基板温度を６００℃まで降温した後、石英
製ガス導入管２からIII族原料としてトリメチルアルミ
ニウムを再度供給して膜厚２０ｎｍの非単結晶ＡｌＮ層
１３を堆積した。これを緩衝層として用いた。Then, the supply of trimethylaluminum is temporarily stopped, the substrate temperature is lowered to 600 ° C., and trimethylaluminum as a group III raw material is supplied again from the quartz gas introduction tube 2 to supply a non-single-crystal AlN film having a thickness of 20 nm. Layer 13 was deposited. This was used as a buffer layer.
【００３６】次いで、基板温度を１０００℃に昇温した
後、III族原料としてトリメチルアルミニウムとトリメ
チルガリウムを供給して膜厚３μｍのＡｌＧａＮ層１４
を堆積した。組成はＡｌ0.1Ｇａ0.9Ｎである。３μｍの
成長によってＡｌＧａＮ層１４表面は平坦となった。Next, after raising the substrate temperature to 1000 ° C., trimethylaluminum and trimethylgallium are supplied as a group III raw material to form an AlGaN layer 14 having a film thickness of 3 μm.
Was deposited. The composition is Al0.1Ga0.9N. The growth of 3 μm flattens the surface of the AlGaN layer 14.
【００３７】その後、基板温度を９００℃に降温した
後、トリメチルガリウム、トリメチルアルミニウムとト
リメチルインジウムを供給して膜厚２ｎｍのＡｌＧａＮ
層１６と膜厚２ｎｍのＧａＩｎＮ層１７を連続して４０
周期堆積し、ＡｌＧａＮ/ＡｌＩｎＮ歪超格子１８を形
成した。組成はＡｌ0.9Ｇａ0.1Ｎ、Ａｌ0.7Ｉｎ0.3Ｎで
ある。Then, after the substrate temperature is lowered to 900 ° C., trimethylgallium, trimethylaluminum and trimethylindium are supplied to supply AlGaN having a film thickness of 2 nm.
The layer 16 and the GaInN layer 17 having a film thickness of 2 nm are consecutively 40
Cyclic deposition was performed to form an AlGaN / AlInN strained superlattice 18. The composition is Al0.9Ga0.1N, Al0.7In0.3N.
【００３８】更に、トリメチルガリウム、トリメチルア
ルミニウムとトリメチルインジウムを同時に供給して膜
厚３μｍのＡｌＧａＩｎＮ層１５を堆積した。組成はＡ
ｌ0.8Ｇａ0.05Ｉｎ0.15Ｎである。Further, trimethylgallium, trimethylaluminum and trimethylindium were simultaneously supplied to deposit an AlGaInN layer 15 having a film thickness of 3 μm. The composition is A
l0.8Ga0.05In0.15N.
【００３９】最後にトリメチルガリウム、トリメチルア
ルミニウムとトリメチルインジウムの供給を停止した
後、基板温度を降温し３００℃以下の温度になったとこ
ろでアンモニアの供給を停止した。基板の温度を室温ま
で降下させた後、石英製反応管１内より基板を取り出し
た。Finally, after the supply of trimethylgallium, trimethylaluminum and trimethylindium was stopped, the substrate temperature was lowered and when the temperature reached 300 ° C. or lower, the supply of ammonia was stopped. After the temperature of the substrate was lowered to room temperature, the substrate was taken out from the quartz reaction tube 1.
【００４０】本実施例においては、基板上に６μｍ以上
の厚膜を堆積したにもかかわらず、クラックの発生もな
く表面平坦であり、ホール効果によるとキャリア濃度は
１０ 15ｃｍ-3と極めて欠陥の少ない四元混晶層が得られ
た。In this embodiment, 6 μm or more on the substrate
Despite depositing a thick film of
The surface is flat and the carrier concentration is
10 Fifteencm-3And a quaternary mixed crystal layer with extremely few defects was obtained.
Was.
【００４１】また、グラファイト製サセプター４を１０
回転/分で回転させた場合は、結晶表面は凸凹で四元混
晶層のＩｎ組成が０．０６であったのに対し、本実施例
の場合、Ｉｎ組成は０．１５となり、１０００回転/分
の高速回転によりＩｎの取り込まれ率が増大することを
確認した。Further, the graphite susceptor 4 is replaced by 10
In the case of rotating at a speed of rotation / minute, the crystal surface was uneven and the In composition of the quaternary mixed crystal layer was 0.06, whereas in the present example, the In composition was 0.15 and 1000 rotations were performed. It was confirmed that the In incorporation rate increased with the high-speed rotation of / min.
【００４２】本実施例によれば、従来のサファイア基板
上に非単結晶層のみを介して堆積したＡｌＧａＩｎＮ層
に比べ、緩衝層界面から発生した欠陥の伝搬は著しく低
減されただけでなく、歪超格子１８を配置したので、ミ
スフィット転位がＡｌＧａＮ層１４から上面へ伝搬する
のを効率的に抑制でき、ＡｌＧａＩｎＮ層１５の欠陥密
度を実施例１の場合に比べてさらに２桁程度が低減され
た。According to the present embodiment, the propagation of defects generated from the interface of the buffer layer is significantly reduced and the strain is not only significantly reduced as compared with the conventional AlGaInN layer deposited on the sapphire substrate via only the non-single crystal layer. Since the superlattice 18 is arranged, propagation of misfit dislocations from the AlGaN layer 14 to the upper surface can be efficiently suppressed, and the defect density of the AlGaInN layer 15 is further reduced by about two digits as compared with the case of the first embodiment. It was
【００４３】この形成方法は、サファイア基板を用いた
場合には全く効果は認められず、ＳｉＣ基板の場合に極
めて有効であった。This forming method had no effect when a sapphire substrate was used, and was extremely effective when using a SiC substrate.
【００４４】なお、本発明は上述した実施例に限定され
るものではない。また、用いる基板は上述の基板には限
定されない。ただ、ＳｉＣ基板やＺｎＯ基板は、ＡｌＧ
ａＩｎＮ層との格子定数の差がサファイア基板よりも格
段に小さく、また取扱いも容易である。結晶成長に用い
た原料や薄膜組成も上述の限りではない。ＡｌＧａＩｎ
Ｎ多層膜の組成や構成も限定されるものでない。The present invention is not limited to the above embodiment. The substrate used is not limited to the above-mentioned substrate. However, SiC and ZnO substrates are AlG
The difference in lattice constant from the aInN layer is significantly smaller than that of the sapphire substrate, and the handling is easy. The raw materials and the thin film composition used for crystal growth are not limited to the above. AlGaIn
The composition and structure of the N multilayer film are not limited.
【００４５】さらには、本発明を用いた発光素子として
の多層薄膜形成にも適用できるのは言うまでもない。Further, it goes without saying that the present invention can be applied to the formation of a multilayer thin film as a light emitting device using the present invention.
【００４６】[0046]
【発明の効果】このように本発明によれば、単結晶Ａｌ
Ｎ薄膜上に非単結晶ＡｌＮを形成し格子歪みを緩和した
後にＡｌＧａＮ単結晶薄膜を形成すると欠陥の発生が抑
制され、上面に堆積したＡｌＧａＩｎＮ薄膜への転位の
伝搬を大幅に低減できる構成とするため、高品質なＡｌ
ＧａＩｎＮ薄膜を形成できる。As described above, according to the present invention, single crystal Al
When non-single crystal AlN is formed on the N thin film to relax the lattice strain and then the AlGaN single crystal thin film is formed, the generation of defects is suppressed, and the propagation of dislocations to the AlGaInN thin film deposited on the upper surface can be significantly reduced. Therefore, high quality Al
A GaInN thin film can be formed.
【００４７】また、ＡｌＧａＩｎＮ薄膜の形成に先立ち
歪ＡｌＧａＩｎＮ超格子を配置するので、基板や緩衝層
界面から発生した転位は面内方向への運動成分が大きく
なるため、上面への伝搬を効率的に抑制でき高品質なＡ
ｌＧａＩｎＮ薄膜を形成できる。Further, since the strained AlGaInN superlattice is arranged prior to the formation of the AlGaInN thin film, the dislocation generated from the interface of the substrate and the buffer layer has a large motion component in the in-plane direction, so that the propagation to the upper surface is efficiently performed. High quality A that can be suppressed
An lGaInN thin film can be formed.
【００４８】したがって、発光効率の高い青色発光ダイ
オードや情報処理装置用光源などに用いることのできる
青色半導体レーザ素子製造に極めて有用である。Therefore, it is extremely useful for manufacturing a blue semiconductor laser device which can be used for a blue light emitting diode having a high luminous efficiency, a light source for an information processing device and the like.
【図１】本発明の実施例の形成方法を説明するＭＯＶＰ
Ｅ装置の概略図FIG. 1 is a MOVP illustrating a forming method according to an embodiment of the present invention.
Schematic of E device
【図２】本発明の第一の実施例のＡｌＧａＩｎＮ薄膜の
形成方法によるＡｌＧａＩｎＮ薄膜の断面構造図FIG. 2 is a sectional structural view of an AlGaInN thin film formed by the method of forming an AlGaInN thin film according to the first embodiment of the present invention.
【図３】本発明の第二の実施例のＡｌＧａＩｎＮ層膜の
形成方法によるＡｌＧａＩｎＮ層膜の断面構造図FIG. 3 is a sectional structural view of an AlGaInN layer film formed by the method of forming an AlGaInN layer film according to the second embodiment of the present invention.
１ 石英製反応管 ２ 石英製ガス導入管 ３ 高周波加熱用コイル ４ グラファイト製サセプター ５ サセプター支持棒 ６ 石英製トレー ７ 基板 ８ 排気口 １１ ６Ｈ-ＳｉＣ基板 １２ 単結晶ＡｌＮ層 １３ 非単結晶ＡｌＮ層 １４ ＡｌＧａＮ層 １５ ＡｌＧａＩｎＮ層 １６ ＡｌＧａＮ層 １７ ＧａＩｎＮ層 １８ ＡｌＧａＮ/ＡｌＩｎＮ歪超格子 1 Quartz reaction tube 2 Quartz gas introduction tube 3 High frequency heating coil 4 Graphite susceptor 5 Susceptor support rod 6 Quartz tray 7 Substrate 8 Exhaust port 11 6H-SiC substrate 12 Single crystal AlN layer 13 Non-single crystal AlN layer 14 AlGaN layer 15 AlGaInN layer 16 AlGaN layer 17 GaInN layer 18 AlGaN / AlInN strained superlattice
Claims (7)
含む原料および窒素を含む原料を供給して緩衝層を介し
てＡｌＧａＩｎＮ薄膜を形成する方法であって、 前記基板上に第一のＡｌＧａＮ単結晶薄膜を形成した後
に、ＡｌＧａＮからなる緩衝層を形成する工程と、 次いで第二のＡｌＧａＮ単結晶薄膜を形成した後に、Ａ
ｌＧａＩｎＮ単結晶薄膜を形成する工程と、を含むこと
を特徴とするＡｌＧａＩｎＮ半導体薄膜の製造方法。1. A method for forming an AlGaInN thin film through a buffer layer by supplying a raw material containing a group III constituent element and a raw material containing nitrogen onto a heated substrate surface, the method comprising: A step of forming a buffer layer made of AlGaN after forming the AlGaN single crystal thin film, and then forming a second AlGaN single crystal thin film, and
and a step of forming a 1GaInN single crystal thin film, the method comprising the steps of:
含む原料および窒素を含む原料を供給して緩衝層を介し
てＡｌＧａＩｎＮ薄膜を形成する方法であって、 前記基板上に第一のＡｌＧａＮ単結晶薄膜を形成した後
に、ＡｌＧａＮからなる緩衝層を形成する工程と、 次いで第二のＡｌＧａＮ単結晶薄膜を形成した後に、前
記第二のＡｌＧａＮ単結晶薄膜中もしくは前記第二のＡ
ｌＧａＮ単結晶薄膜上に、複数の組成の異なるＡｌＧａ
ＩｎＮ層からなる歪超格子構造を形成する工程と、を含
むことを特徴とするＡｌＧａＩｎＮ半導体薄膜の製造方
法。2. A method for forming an AlGaInN thin film through a buffer layer by supplying a raw material containing a group III constituent element and a raw material containing nitrogen onto a heated substrate surface, the method comprising: A step of forming a buffer layer made of AlGaN after forming the AlGaN single crystal thin film, and then forming a second AlGaN single crystal thin film, and then in the second AlGaN single crystal thin film or in the second A
A plurality of AlGa having different compositions are formed on the lGaN single crystal thin film.
And a step of forming a strained superlattice structure made of an InN layer, the manufacturing method of an AlGaInN semiconductor thin film.
は、８００℃以上の基板温度で形成し、ＡｌＧａＮから
なる緩衝層は８００℃以下の基板温度で形成することを
特徴とする請求項第１または２に記載のＡｌＧａＩｎＮ
半導体薄膜の製造方法。3. The first and second AlGaN single crystal thin films are formed at a substrate temperature of 800 ° C. or higher, and the AlGaN buffer layer is formed at a substrate temperature of 800 ° C. or lower. The first or second AlGaInN
Method for manufacturing semiconductor thin film.
法であって、基板を配置した加熱体の回転速度を３００
回転/分以上とすることを特徴とする請求項１または２
に記載のＡｌＧａＩｎＮ半導体薄膜の製造方法。4. The method for forming is a vapor phase growth method using an organic metal, wherein the rotation speed of the heating body on which the substrate is arranged is 300.
Rotation / minute or more, The 1 or 2 characterized by the above-mentioned.
The method for manufacturing an AlGaInN semiconductor thin film according to item 4.
徴とする請求項１または２に記載のＡｌＧａＩｎＮ半導
体薄膜の製造方法。5. The method for manufacturing an AlGaInN semiconductor thin film according to claim 1, wherein the substrate is SiC or ZnO.
る緩衝層と、 前記ＡｌＧａＮからなる緩衝層上に形成したＡｌＧａＩ
ｎＮ層と、を備えたことを特徴とする半導体薄膜構造。6. A single crystal AlGaN layer, a buffer layer made of AlGaN formed on the single crystal AlGaN layer, and an AlGaI formed on the buffer layer made of AlGaN.
A semiconductor thin film structure comprising: an nN layer.
６に記載の半導体薄膜構造を堆積したことを特徴とする
半導体発光素子。7. A semiconductor light emitting device, comprising the semiconductor thin film structure according to claim 6 deposited on a SiC substrate or a ZnO substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP909295A JPH08203834A (en) | 1995-01-24 | 1995-01-24 | Semiconductor thin film and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP909295A JPH08203834A (en) | 1995-01-24 | 1995-01-24 | Semiconductor thin film and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08203834A true JPH08203834A (en) | 1996-08-09 |
Family
ID=11710981
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP909295A Pending JPH08203834A (en) | 1995-01-24 | 1995-01-24 | Semiconductor thin film and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08203834A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6420283B1 (en) | 1997-10-28 | 2002-07-16 | Sharp Kabushiki Kaisha | methods for producing compound semiconductor substrates and light emitting elements |
| JP2004006556A (en) * | 2001-06-08 | 2004-01-08 | Toyoda Gosei Co Ltd | Manufacturing method of group iii nitride compound semiconductor element |
| US6677619B1 (en) | 1997-01-09 | 2004-01-13 | Nichia Chemical Industries, Ltd. | Nitride semiconductor device |
| JP2004200384A (en) * | 2002-12-18 | 2004-07-15 | Ngk Insulators Ltd | Substrate for epitaxial growth |
| US6872967B2 (en) | 2000-03-24 | 2005-03-29 | Sanyo Electric Co., Ltd. | Nitride-based semiconductor device and manufacturing method thereof |
| US6984840B2 (en) * | 1998-05-18 | 2006-01-10 | Fujitsu Limited | Optical semiconductor device having an epitaxial layer of III-V compound semiconductor material containing N as a group V element |
| US7554132B2 (en) | 2005-09-27 | 2009-06-30 | Toyoda Gosei, Co., Ltd. | Electronic device containing group-III element based nitride semiconductors |
| US20110095335A1 (en) * | 2008-07-03 | 2011-04-28 | Panasonic Corporation | Nitride semiconductor device |
| US8134168B2 (en) | 2003-10-14 | 2012-03-13 | Showa Denko K.K. | Group-III nitride semiconductor device |
| JP2016029741A (en) * | 2015-11-05 | 2016-03-03 | 住友化学株式会社 | Method for manufacturing nitride semiconductor epitaxial wafer for transistors |
| CN109244203A (en) * | 2018-09-12 | 2019-01-18 | 华灿光电(苏州）有限公司 | A kind of epitaxial wafer of light emitting diode and preparation method thereof |
-
1995
- 1995-01-24 JP JP909295A patent/JPH08203834A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8541794B2 (en) | 1997-01-09 | 2013-09-24 | Nichia Chemical Industries, Ltd. | Nitride semiconductor light-emitting devices |
| US6677619B1 (en) | 1997-01-09 | 2004-01-13 | Nichia Chemical Industries, Ltd. | Nitride semiconductor device |
| US7615804B2 (en) | 1997-01-09 | 2009-11-10 | Nichia Chemical Industries, Ltd. | Superlattice nitride semiconductor LD device |
| US6849864B2 (en) | 1997-01-09 | 2005-02-01 | Nichia Chemical Industries, Ltd. | Nitride semiconductor device |
| US7211822B2 (en) | 1997-01-09 | 2007-05-01 | Nichia Chemical Industries, Ltd. | Nitride semiconductor device |
| US6420283B1 (en) | 1997-10-28 | 2002-07-16 | Sharp Kabushiki Kaisha | methods for producing compound semiconductor substrates and light emitting elements |
| US6984840B2 (en) * | 1998-05-18 | 2006-01-10 | Fujitsu Limited | Optical semiconductor device having an epitaxial layer of III-V compound semiconductor material containing N as a group V element |
| US6872967B2 (en) | 2000-03-24 | 2005-03-29 | Sanyo Electric Co., Ltd. | Nitride-based semiconductor device and manufacturing method thereof |
| JP2004006556A (en) * | 2001-06-08 | 2004-01-08 | Toyoda Gosei Co Ltd | Manufacturing method of group iii nitride compound semiconductor element |
| JP2004200384A (en) * | 2002-12-18 | 2004-07-15 | Ngk Insulators Ltd | Substrate for epitaxial growth |
| US8134168B2 (en) | 2003-10-14 | 2012-03-13 | Showa Denko K.K. | Group-III nitride semiconductor device |
| US7554132B2 (en) | 2005-09-27 | 2009-06-30 | Toyoda Gosei, Co., Ltd. | Electronic device containing group-III element based nitride semiconductors |
| US20110095335A1 (en) * | 2008-07-03 | 2011-04-28 | Panasonic Corporation | Nitride semiconductor device |
| JP2016029741A (en) * | 2015-11-05 | 2016-03-03 | 住友化学株式会社 | Method for manufacturing nitride semiconductor epitaxial wafer for transistors |
| CN109244203A (en) * | 2018-09-12 | 2019-01-18 | 华灿光电(苏州）有限公司 | A kind of epitaxial wafer of light emitting diode and preparation method thereof |
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