KR20040036382A - METHOD FOR MANUFACTURING GaN SUBSTRATE - Google Patents

METHOD FOR MANUFACTURING GaN SUBSTRATE Download PDF

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KR20040036382A
KR20040036382A KR1020020065388A KR20020065388A KR20040036382A KR 20040036382 A KR20040036382 A KR 20040036382A KR 1020020065388 A KR1020020065388 A KR 1020020065388A KR 20020065388 A KR20020065388 A KR 20020065388A KR 20040036382 A KR20040036382 A KR 20040036382A
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gallium nitride
substrate
nitride layer
grown
layer
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이석우
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엘지전자 주식회사
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02367Substrates
    • H01L21/0237Materials
    • H01L21/02387Group 13/15 materials
    • H01L21/02389Nitrides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02656Special treatments
    • H01L21/02664Aftertreatments
    • H01L21/02667Crystallisation or recrystallisation of non-monocrystalline semiconductor materials, e.g. regrowth
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304Mechanical treatment, e.g. grinding, polishing, cutting
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30604Chemical etching
    • H01L21/30612Etching of AIIIBV compounds
    • H01L21/30621Vapour phase etching

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

PURPOSE: A method for manufacturing a GaN substrate is provided to be capable of improving the quality of the GaN substrate using a two-step GaN layer growing process. CONSTITUTION: The first GaN layer(11) is grown on a hetero substrate(10). Surface defects of the first GaN layer are removed by partially performing a dry etching process on the first GaN layer. The second GaN layer(14) is re-grown on the first GaN layer. Preferably, the dry etching process is performed by supplying HCl into a chamber for growing the GaN layers. Preferably, the dry etching process and the second GaN layer growing process are capable of being repeatedly performed on the resultant structure. Preferably, the hetero substrate is separated from the GaN layers by carrying out a laser lift-off process or a mechanical polishing process.

Description

질화갈륨 기판 제조방법{Method for manufacturing GaN substrate}Gallium nitride substrate manufacturing method {Method for manufacturing GaN substrate}

본 발명은 질화갈륨 기판 제조 방법에 관한 것으로, 보다 상세하게는 이종 기판에 1차로 질화갈륨층을 성장시키고, 이 질화갈륨층을 건식식각한 후, 2차로 질화갈륨층을 성장시킴으로써, 전위나 크랙 등의 결함밀도가 상당히 감소된 고품질의 질화갈륨 기판을 제조할 수 있는 질화갈륨 기판 제조 방법에 관한 것이다.The present invention relates to a method for producing a gallium nitride substrate, and more particularly, a gallium nitride layer is first grown on a dissimilar substrate, and the gallium nitride layer is dry-etched, followed by a second growth of a gallium nitride layer, thereby dissolving a potential or crack. The present invention relates to a gallium nitride substrate manufacturing method capable of producing a high quality gallium nitride substrate having significantly reduced defect density.

일반적으로 III-V족 질화물 화합물 반도체는 자외선(Ultraviolet)에서 적색에 이르는 발광다이오드(Light Emitting Diode, LED), 레이저 다이오드, 광검출기 등의 광소자와 넓은 밴드갭(Bandgap)을 이용한 고온 및 고출력 전자 소자 등에 이용되고 있다.In general, group III-V nitride compound semiconductors are high-temperature and high-power electronics using optical devices such as light emitting diodes (LEDs), laser diodes, and photodetectors ranging from ultraviolet to red, and wide bandgaps. It is used for an element.

그러한 소자들은 III-V족 질화물 화합물 반도체의 단결정 박막 즉, 에피 박막층으로 구성되는데, 우수한 에피 박막을 얻기 위해서는 결함이 적은 동종의 단결정 물질 기판으로 제조가 되어야 한다.Such devices are composed of a single crystal thin film of an III-V nitride compound semiconductor, that is, an epi thin film layer. In order to obtain an excellent epi thin film, it must be manufactured with a homogeneous single crystal material substrate having few defects.

그러나 아직까지 질화갈륨(GaN)의 단결정 성장이 어려워 2인치 이상의 대면적 단결정 기판을 제조하기가 어려운 실정이다.However, gallium nitride (GaN) single crystal growth is still difficult to manufacture a large area single crystal substrate of more than 2 inches.

따라서, 현재까지 질화물 화합물 반도체를 이용한 소자는 대부분 사파이어나 실리콘카바이드(SiC) 등의 이종 기판 위에 성장되고 있다.Therefore, until now, devices using nitride compound semiconductors have been mostly grown on dissimilar substrates such as sapphire and silicon carbide (SiC).

그러나, 이종기판은 질화물 화합물 반도체와의 격자 상수 및 열팽창 계수의 차이가 커서, 이종기판에 성장되는 질화갈륨 에피 박막 내부에 전위(Dislocation), 크랙(Crack) 등의 결함이 상당수 존재하게 된다.However, the dissimilar substrate has a large difference in lattice constant and thermal expansion coefficient with the nitride compound semiconductor, and a large number of defects such as dislocations and cracks exist in the gallium nitride epitaxial film grown on the dissimilar substrate.

이런 결함들을 갖는 기판으로 소자를 제조할 경우, 결함들이 누설전류의 통로가 되거나, 비발광 부위로 작용하여 소자의 성능을 저하시키게 된다.When the device is manufactured from a substrate having such defects, the defects become a passage of leakage current or act as a non-light emitting portion, thereby degrading the performance of the device.

도 1은 종래기술에 따라 이종 기판의 상부에 성장된 질화갈륨층의 모식 단면도로써, 사파이어나 실리콘카바이드(SiC) 등의 이종 기판(10)의 상부에 성장된 질화갈륨층에는 이종 기판(10)과 성장되는 질화갈륨의 격자 상수와 열팽창 계수의 차이로 인하여 전위(12)와 같은 결함이 형성된다.1 is a schematic cross-sectional view of a gallium nitride layer grown on top of a heterogeneous substrate according to the related art, and the heterogeneous substrate 10 is formed on a gallium nitride layer grown on a heterogeneous substrate 10 such as sapphire or silicon carbide (SiC). Defects such as dislocations 12 are formed due to the difference between the lattice constant and the coefficient of thermal expansion of gallium nitride overgrown.

전술된 문제점을 해결하기 위하여, 최근까지 선택영역 에피성장(SelectiveArea Epitaxy Growth)법, 즉, 측면 에피성장(Lateral Epitaxial Overgrowth)법으로 질화갈륨 기판을 제조하고 있고, 다른 한편으로는 더욱 특성이 우수한 질화갈륨 기판을 개발하려는 노력이 계속되고 있다.In order to solve the above-mentioned problem, until recently, gallium nitride substrates have been manufactured by the Selective Area Epitaxy Growth method, that is, the Lateral Epitaxial Overgrowth method, and on the other hand, the nitrided material having better characteristics Efforts to develop gallium substrates continue.

한편, 현재의 프리 스탠팅(Free-Standing) 질화갈륨 기판을 형성하는 방법은 이종기판에 질화갈륨 후막을 성장 후, 레이저 리프트 오프(Laser Lift-Off)방법으로 질화갈륨을 이종기판에서 분리하거나 기계적으로 연마를 해서 이종기판을 갈아내어 분리하는 방법이 이용되고 있다.On the other hand, the current method of forming a free-standing gallium nitride substrate is to grow a gallium nitride thick film on a dissimilar substrate, and then to separate the gallium nitride from the dissimilar substrate by laser lift-off method or mechanical A method of grinding and separating heterogeneous substrates by polishing with a metal is used.

그러므로, 질화갈륨 성장 시 발생되는 격자 상수 및 열팽창 계수의 차이에 의한 결함은 프리스탠딩을 수행한 후에도 질화갈륨 기판에 그대로 잔존하여, 이를 이용하여 제조된 소자에 악영향을 인가하게 된다.Therefore, defects due to differences in lattice constants and thermal expansion coefficients generated during gallium nitride growth remain on the gallium nitride substrate even after freestanding, thereby adversely affecting devices manufactured using the same.

따라서, 결함밀도가 감소되는 질화갈륨 기판의 제조방법이 요구되는 것이다.Therefore, there is a need for a method of manufacturing a gallium nitride substrate in which defect density is reduced.

이에 본 발명은 상기한 바와 같은 문제점을 해결하기 위하여 안출된 것으로,Accordingly, the present invention has been made to solve the above problems,

본 발명은 이종 기판에 1차로 질화갈륨층을 성장시키고, 이 질화갈륨층을 건식식각한 후, 2차로 질화갈륨층을 성장시킴으로써, 전위나 크랙 등의 결함밀도가 상당히 감소된 고품질의 질화갈륨 기판을 제조할 수 있는 질화갈륨 기판의 제조방법을 제공하는 데 그 목적이 있다.The present invention is a high quality gallium nitride substrate in which a gallium nitride layer is first grown on a heterogeneous substrate, the gallium nitride layer is dry etched, and a second gallium nitride layer is grown, thereby significantly reducing defect densities such as dislocations and cracks. It is an object of the present invention to provide a method for producing a gallium nitride substrate which can be prepared.

상기한 본 발명의 목적을 달성하기 위한 바람직한 양태(樣態)는, 이종 기판의 상부에 질화갈륨층을 성장시키는 제 1 단계와;A preferred aspect for achieving the above object of the present invention comprises a first step of growing a gallium nitride layer on top of a heterogeneous substrate;

상기 질화갈륨층의 일부를 건식식각하여 상기 질화갈륨층의 표면의 결함을제거하는 제 2 단계와;Dry etching a portion of the gallium nitride layer to remove defects on the surface of the gallium nitride layer;

상기 식각된 질화갈륨층의 상부에 질화갈륨층을 재성장시키는 제 3 단계로 이루어진 것을 특징으로 하는 질화갈륨 기판 제조 방법이 제공된다.A gallium nitride substrate manufacturing method comprising a third step of regrowing a gallium nitride layer on the etched gallium nitride layer is provided.

도 1은 종래기술에 따라 이종 기판의 상부에 성장된 질화갈륨층의 모식 단면도이다.1 is a schematic cross-sectional view of a gallium nitride layer grown on top of a heterogeneous substrate according to the prior art.

도 2a 내지 2c는 본 발명에 따른 질화갈륨 기판 제조 공정 모식 단면도이다.2A to 2C are schematic cross-sectional views of a gallium nitride substrate manufacturing process according to the present invention.

도 3은 본 발명에 따라 도 2b와 2c의 공정을 반복적으로 수행하여 이종기판 상부에 형성된 질화갈륨층의 모식 단면도이다.FIG. 3 is a schematic cross-sectional view of a gallium nitride layer formed on a dissimilar substrate by repeatedly performing the processes of FIGS. 2B and 2C according to the present invention.

<도면의 주요부분에 대한 부호의 설명><Description of the symbols for the main parts of the drawings>

10 : 이종기판 11,14,15 : 질화갈륨층10: dissimilar substrate 11,14,15: gallium nitride layer

12,12a,12c : 전위(Dislocation) 13,13a,13b,13c : 식각된 버퍼층12,12a, 12c: Dislocation 13,13a, 13b, 13c: Etched buffer layer

이하, 첨부된 도면을 참조하여 본 발명의 바람직한 실시예를 설명하면 다음과 같다.Hereinafter, exemplary embodiments of the present invention will be described with reference to the accompanying drawings.

도 2a 내지 2c는 본 발명에 따른 질화갈륨 기판 제조 공정 모식 단면도로써, 먼저, 사파이어나 실리콘카바이드(SiC) 등의 이종 기판(10)의 상부에 질화갈륨층(11)을 성장시킨다.(도 2a)2A to 2C are schematic cross-sectional views of a gallium nitride substrate manufacturing process according to the present invention. First, a gallium nitride layer 11 is grown on a dissimilar substrate 10 such as sapphire or silicon carbide (SiC). )

그 후, 상기 질화갈륨층(11)의 일부를 건식식각하여 식각된 버퍼층(13)을 형성한다.(도 2b)Thereafter, a part of the gallium nitride layer 11 is dry etched to form an etched buffer layer 13 (FIG. 2B).

여기서, 상기 건식식각은 상기 질화갈륨층(11)이 성장되는 챔버내에서 염산(HCl)등의 가스를 주입해 500℃ ~ 1100℃ 정도의 온도에서 1 ~ 30분 정도 상기 질화갈륨층(11)의 표면을 식각한다.The dry etching is performed by injecting a gas such as hydrochloric acid (HCl) into the chamber in which the gallium nitride layer 11 is grown, and the gallium nitride layer 11 at a temperature of about 500 ° C to 1100 ° C for about 1 to 30 minutes. Etch the surface.

이렇게 식각되면 도 2b와 같은 모양으로 결함이 있는 부분에 에치핏(Etch Pit)이 생기게 된다.When etched in this way, an etching pit is formed in a defective part in a shape as shown in FIG. 2B.

마지막으로, 상기 식각된 버퍼층(13)의 상부에 질화갈륨층(14)을 성장시킨다.(도 2c)Finally, the gallium nitride layer 14 is grown on the etched buffer layer 13 (FIG. 2C).

여기서, 상기 식각된 버퍼층(13)의 상부에 성장되는 질화갈륨층(14)은 상기 버퍼층(13)과 동종물질이기 때문에, 크랙 및 전위 밀도가 감소한다.Here, since the gallium nitride layer 14 grown on the etched buffer layer 13 is the same material as the buffer layer 13, the crack and dislocation density decrease.

더불어, 전술된 도 2a 내지 2c 공정을 수행하여 상기 식각된 버퍼층(13)의 상부에 질화갈륨층(14)을 성장시킨 후, 레이저 리프트 오프(Laser Lift-Off) 공정을 수행하여 이종기판(10)에서 질화갈륨층을 분리한다.2A to 2C, the gallium nitride layer 14 is grown on the etched buffer layer 13, and then a laser lift-off process is performed to dissimilar the substrate 10. The gallium nitride layer is separated from

또는, 기계적으로 연마해서 이종기판(10)을 갈아냄으로써, 프리스탠딩 질화갈륨 기판을 제조할 수 있다.Alternatively, the freestanding gallium nitride substrate can be manufactured by grinding the dissimilar substrate 10 by mechanical polishing.

도 3은 본 발명에 따라 도 2b와 2c의 공정을 반복적으로 수행하여 이종기판 상부에 형성된 질화갈륨층의 모식 단면도로써, 전술된 건식식각과 질화갈륨층 성장을 반복 수행하면 최종적으로 결함밀도가 가장 감소된 질화갈륨층(15)이 형성된다.FIG. 3 is a schematic cross-sectional view of a gallium nitride layer formed on a dissimilar substrate by repeatedly performing the processes of FIGS. 2B and 2C according to the present invention. Reduced gallium nitride layer 15 is formed.

즉, 이종기판(10)의 상부에 1차 질화갈륨층을 형성하고 건식식각하여 제 1 식각된 버퍼층(13a)을 형성하고, 그 제 1 식각된 버퍼층(13a)의 상부에 2차 질화갈륨층을 형성하고 건식식각하여 제 2 식각된 버퍼층(13b)을 형성하고, 제 2 식각된 버퍼층(13b)의 상부에 3차 질화갈륨층을 형성하고 건식식각하여 제 3 식각된 버퍼층(13c)을 형성한다.That is, a primary gallium nitride layer is formed on the hetero substrate 10 and dry-etched to form a first etched buffer layer 13a, and a secondary gallium nitride layer on the first etched buffer layer 13a. Form and dry etch to form a second etched buffer layer 13b, and form a tertiary gallium nitride layer on top of the second etched buffer layer 13b and dry etch to form a third etched buffer layer 13c. do.

그 후에, 질화갈륨층(15)을 성장하면, 제 1 식각된 버퍼층(13a)에 형성된 결함밀도(12a)보다 제 3 식각된 버퍼층(13b)에 형성된 결함밀도(12c)가 작으므로, 최종적인 질화갈륨층(15)은 결함밀도가 더욱 감소된다.Thereafter, when the gallium nitride layer 15 is grown, the defect density 12c formed in the third etched buffer layer 13b is smaller than the defect density 12a formed in the first etched buffer layer 13a. The gallium nitride layer 15 is further reduced in defect density.

따라서, 본 발명은 질화갈륨으로 이루어진 식각된 버퍼층(13)의 상부에 질화갈륨을 재성장시킴으로써, 재성장되는 질화갈륨층에는 이종 기판(10)과 성장되는 질화갈륨의 격자 상수와 열팽창 계수의 차이로 인하여 발생되는 전위(dislocation)와 크랙(Crack) 등의 결함을 제거할 수 있다.Therefore, the present invention re-grows gallium nitride on the etched buffer layer 13 made of gallium nitride, so that the regrown gallium nitride layer has a difference between lattice constants and thermal expansion coefficients of the heterogeneous substrate 10 and the grown gallium nitride. Defects such as dislocations and cracks generated can be eliminated.

이상에서 상세히 설명한 바와 같이 본 발명은 이종 기판에 1차로 질화갈륨층을 성장시키고, 이 질화갈륨층을 건식식각한 후, 2차로 질화갈륨층을 성장시킴으로써, 고품질의 질화갈륨 기판을 제조할 수 있는 효과가 발생한다.As described in detail above, the present invention can produce a high quality gallium nitride substrate by first growing a gallium nitride layer on a dissimilar substrate, dry etching the gallium nitride layer, and secondly growing a gallium nitride layer. Effect occurs.

더불어, 이러한 방법으로 만들어진 기판을 이용해 우수한 광소자 및 전자소자를 만들 수 있는 효과가 발생된다.In addition, there is an effect that can make excellent optical devices and electronic devices using the substrate made in this way.

본 발명은 구체적인 예에 대해서만 상세히 설명되었지만 본 발명의 기술사상 범위 내에서 다양한 변형 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속함은 당연한 것이다.Although the invention has been described in detail only with respect to specific examples, it will be apparent to those skilled in the art that various modifications and variations are possible within the spirit of the invention, and such modifications and variations belong to the appended claims.

Claims (4)

이종 기판의 상부에 질화갈륨층을 성장시키는 제 1 단계와;A first step of growing a gallium nitride layer on top of the dissimilar substrate; 상기 질화갈륨층의 일부를 건식식각하여 상기 질화갈륨층의 표면의 결함을 제거하는 제 2 단계와;Dry etching a portion of the gallium nitride layer to remove defects on the surface of the gallium nitride layer; 상기 식각된 질화갈륨층의 상부에 질화갈륨층을 재성장시키는 제 3 단계로 구성된 질화갈륨 기판 제조 방법.And a third step of regrowing the gallium nitride layer on the etched gallium nitride layer. 제 1 항에 있어서,The method of claim 1, 상기 제 2 단계의 건식식각은,The dry etching of the second step, 상기 질화갈륨층이 성장되는 챔버내에서 염산(HCl)을 주입하여 식각하는 것을 특징으로 하는 질화갈륨 기판 제조 방법.The gallium nitride substrate manufacturing method characterized in that the etching by implanting hydrochloric acid (HCl) in the chamber in which the gallium nitride layer is grown. 제 1 항에 있어서,The method of claim 1, 상기 제 2 단계와 제 3 단계를 반복적으로 수행하는 것을 특징으로 하는 질화갈륨 기판 제조 방법.Method of manufacturing a gallium nitride substrate, characterized in that to perform the second step and the third step repeatedly. 제 1 항에 있어서,The method of claim 1, 상기 제 3 단계후에,After the third step, 레이저 리프트 오프(Laser Lift-Off) 공정 또는 기계적인 연마공정으로 상기이종기판을 상기 질화갈륨층으로부터 분리하는 공정이 더 구비된 것을 특징으로 하는 질화갈륨 기판 제조 방법.The gallium nitride substrate manufacturing method further comprises the step of separating the dissimilar substrate from the gallium nitride layer by a laser lift-off process or a mechanical polishing process.
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KR100764427B1 (en) * 2006-07-27 2007-10-05 삼성전기주식회사 Manufacturing method of nitride single crystal thick film

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JP2001039800A (en) * 1999-05-21 2001-02-13 Nichia Chem Ind Ltd Growing method of nitride semiconductor and nitride semiconductor element
JP2001181096A (en) * 1999-12-24 2001-07-03 Toyoda Gosei Co Ltd Method for producing iii group nitride compound semiconductor and iii group nitride compound semiconductor element
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KR100735488B1 (en) * 2006-02-03 2007-07-04 삼성전기주식회사 Method for forming the gan type led device
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