JP2006225232A - Method for producing silicon carbide single crystal, silicon carbide single crystal ingot, silicon carbide single crystal substrate, silicon carbide epitaxial wafer and thin film epitaxial wafer - Google Patents
Method for producing silicon carbide single crystal, silicon carbide single crystal ingot, silicon carbide single crystal substrate, silicon carbide epitaxial wafer and thin film epitaxial wafer Download PDFInfo
- Publication number
- JP2006225232A JP2006225232A JP2005044305A JP2005044305A JP2006225232A JP 2006225232 A JP2006225232 A JP 2006225232A JP 2005044305 A JP2005044305 A JP 2005044305A JP 2005044305 A JP2005044305 A JP 2005044305A JP 2006225232 A JP2006225232 A JP 2006225232A
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- silicon carbide
- carbide single
- growth
- crystal
- 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.)
- Granted
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 319
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 149
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 47
- 239000000758 substrate Substances 0.000 title claims description 20
- 239000010409 thin film Substances 0.000 title claims description 19
- 238000000034 method Methods 0.000 claims abstract description 31
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 7
- 229910002601 GaN Inorganic materials 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 4
- NWAIGJYBQQYSPW-UHFFFAOYSA-N azanylidyneindigane Chemical compound [In]#N NWAIGJYBQQYSPW-UHFFFAOYSA-N 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 31
- 235000012431 wafers Nutrition 0.000 description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 21
- 229910002804 graphite Inorganic materials 0.000 description 21
- 239000010439 graphite Substances 0.000 description 21
- 239000002994 raw material Substances 0.000 description 21
- 239000007789 gas Substances 0.000 description 10
- 239000010453 quartz Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 238000003754 machining Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000000859 sublimation Methods 0.000 description 4
- 230000008022 sublimation Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000004430 X-ray Raman scattering Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
本発明は、炭化珪素単結晶の製造方法、炭化珪素単結晶インゴット、炭化珪素単結晶基板、炭化珪素エピタキシャルウェハ、および薄膜エピタキシャルウェハに関し、特に、電子デバイスの基板ウェハとなる良質で大型の単結晶インゴットが得られる炭化珪素単結晶の製造方法と、この製造方法を用いたて製造された炭化珪素単結晶インゴット、炭化珪素単結晶基板、炭化珪素エピタキシャルウェハ、および薄膜エピタキシャルウェハに関するものである。 The present invention relates to a method for manufacturing a silicon carbide single crystal, a silicon carbide single crystal ingot, a silicon carbide single crystal substrate, a silicon carbide epitaxial wafer, and a thin film epitaxial wafer. The present invention relates to a method for producing a silicon carbide single crystal from which an ingot is obtained, and a silicon carbide single crystal ingot, a silicon carbide single crystal substrate, a silicon carbide epitaxial wafer, and a thin film epitaxial wafer produced by using this production method.
炭化珪素(SiC)は、耐熱性及び機械的強度に優れ、放射線に強い等の物理的、化学的性質から、耐環境性半導体材料として注目されている。また、近年、青色から紫外にかけての短波長光デバイス、高周波・高耐圧電子デバイス等の基板ウェハとしてSiC単結晶ウェハの需要が高まっている。しかしながら、大面積を有する高品質のSiC単結晶を、工業的規模で安定に供給し得る結晶成長技術は、未だ確立されていない。それゆえ、SiCは、上述のような多くの利点及び可能性を有する半導体材料にもかかわらず、その実用化が阻まれていた。 Silicon carbide (SiC) is attracting attention as an environmentally resistant semiconductor material because of its physical and chemical properties such as excellent heat resistance and mechanical strength and resistance to radiation. In recent years, the demand for SiC single crystal wafers as substrate wafers for short-wavelength optical devices from blue to ultraviolet, high-frequency / high-voltage electronic devices, and the like has increased. However, a crystal growth technique that can stably supply a high-quality SiC single crystal having a large area on an industrial scale has not yet been established. Therefore, practical use of SiC has been hindered despite the semiconductor material having many advantages and possibilities as described above.
従来、研究室程度の規模では、例えば、昇華再結晶法(レーリー法)でSiC単結晶を成長させ、半導体素子の作製が可能なサイズのSiC単結晶を得ていた。しかしながら、この方法では、得られた単結晶の面積が小さく、その寸法及び形状を高精度に制御することは困難である。また、SiCが有する結晶多形及び不純物キャリア濃度の制御も容易ではない。また、化学気相成長法(CVD法)を用いて、珪素(Si)等の異種基板上にヘテロエピタキシャル成長させることにより、立方晶のSiC単結晶を成長させることも行われている。この方法では、大面積の単結晶は得られるが、基板との格子不整合が約20%あることにより、積層欠陥等の結晶欠陥が入り易く、高品質のSiC単結晶を得ることは難しい。 Conventionally, on a laboratory scale scale, for example, a SiC single crystal was grown by a sublimation recrystallization method (Rayleigh method) to obtain a SiC single crystal of a size capable of producing a semiconductor element. However, with this method, the area of the obtained single crystal is small, and it is difficult to control its size and shape with high accuracy. Moreover, it is not easy to control the crystal polymorphism and impurity carrier concentration of SiC. In addition, a cubic SiC single crystal is grown by heteroepitaxial growth on a heterogeneous substrate such as silicon (Si) using a chemical vapor deposition method (CVD method). In this method, a single crystal having a large area can be obtained. However, since the lattice mismatch with the substrate is about 20%, crystal defects such as stacking faults are likely to occur, and it is difficult to obtain a high-quality SiC single crystal.
これらの問題点を解決するために、SiC単結晶ウェハを種結晶として用いて昇華再結晶を行う改良型のレーリー法が提案され(非特許文献1)、多くの研究機関で実施されている。この方法では、種結晶を用いているため結晶の核形成過程が制御でき、また、不活性ガスにより雰囲気圧力を100Pa〜15kPa程度に制御することにより、結晶の成長速度等を再現性良くコントロールできる。 In order to solve these problems, an improved Rayleigh method in which sublimation recrystallization is performed using a SiC single crystal wafer as a seed crystal has been proposed (Non-Patent Document 1) and has been implemented in many research institutions. In this method, since the seed crystal is used, the nucleation process of the crystal can be controlled, and by controlling the atmospheric pressure to about 100 Pa to 15 kPa with an inert gas, the growth rate of the crystal can be controlled with good reproducibility. .
図1を用いて、改良レーリー法の原理を説明する。種結晶101となるSiC単結晶と、原料102となるSiC結晶粉末は、坩堝103(通常黒鉛製)の中に収納され、アルゴン等の不活性ガス雰囲気中(133〜13.3kPa)、2000〜2400℃に加熱される。坩堝103は坩堝蓋104によってふさがれている。結晶成長に際しては、原料102の粉末に比べ、種結晶101がやや低温になるように、温度勾配が設定される。原料102は、昇華後、濃度勾配(温度勾配により形成される)により種結晶方向へ拡散、輸送される。単結晶成長は、種結晶101に到着した原料ガスが種結晶101上で再結晶化することにより実現されて成長結晶105ができる。 The principle of the improved Rayleigh method will be described with reference to FIG. The SiC single crystal serving as the seed crystal 101 and the SiC crystal powder serving as the raw material 102 are housed in a crucible 103 (usually made of graphite), in an inert gas atmosphere such as argon (133 to 13.3 kPa), 2000 to 2000 Heat to 2400 ° C. The crucible 103 is blocked by a crucible lid 104. During crystal growth, the temperature gradient is set so that the seed crystal 101 is slightly cooler than the powder of the raw material 102. After sublimation, the raw material 102 is diffused and transported in the seed crystal direction by a concentration gradient (formed by a temperature gradient). Single crystal growth is realized by recrystallizing the source gas that has arrived at the seed crystal 101 on the seed crystal 101, thereby forming a growth crystal 105.
成長させた単結晶の抵抗率は、この成長過程において、不活性ガスからなる雰囲気中に不純物ガスを添加する、あるいは、SiC原料粉末中に不純物元素あるいはその化合物を混合することにより、制御可能である。SiC単結晶中の置換型不純物としては、代表的なものに、窒素(n型)、ホウ素(p型)、アルミニウム(p型)がある。改良レーリー法を用いれば、SiC単結晶の結晶多形(6H型、4H型、15R型等)及び形状、キャリア型及び濃度を制御しながら、SiC単結晶を成長させることができる。 The resistivity of the grown single crystal can be controlled in this growth process by adding an impurity gas in an atmosphere of an inert gas or mixing an impurity element or a compound thereof in the SiC raw material powder. is there. Typical substitutional impurities in the SiC single crystal include nitrogen (n-type), boron (p-type), and aluminum (p-type). By using the modified Rayleigh method, it is possible to grow a SiC single crystal while controlling the crystal polymorphism (6H type, 4H type, 15R type, etc.), shape, carrier type and concentration of the SiC single crystal.
上記SiC単結晶は、主要な面方位として{0001}面(c面)と、{0001}面に垂直な{11−20}面(a面)及び{1−100}面(m面)を有している。従来よりSiC単結晶を得る方法としては、{0001}面もしくは{0001}面からオフ角度10°以内の面を種結晶成長面として用いて、改良レーリー法によりSiC単結晶を成長させる、いわゆるc面成長が用いられてきた。その結果、現在、口径2インチ(50.8mm)から3インチ(76.2mm)のSiC単結晶ウェハが製造され、エピタキシャル薄膜成長、デバイス作製に供されている。 The SiC single crystal has {0001} plane (c plane) as a main plane orientation, {11-20} plane (a plane) and {1-100} plane (m plane) perpendicular to the {0001} plane. Have. Conventionally, as a method for obtaining a SiC single crystal, a SiC single crystal is grown by an improved Rayleigh method using a {0001} plane or a plane within an off angle of 10 ° from the {0001} plane as a seed crystal growth plane. Planar growth has been used. As a result, SiC single crystal wafers having a diameter of 2 inches (50.8 mm) to 3 inches (76.2 mm) are currently manufactured and used for epitaxial thin film growth and device fabrication.
しかしながら、これらのSiC単結晶ウェハには、成長方向(結晶c軸方向)に貫通するマイクロパイプ欠陥が1〜100cm−2程度、転位欠陥が104〜105cm−2程度含まれており、高性能のデバイス製造を妨げていた。また、これらマイクロパイプ欠陥、転位欠陥は、その大部分が結晶成長の成長開始時に導入されることが、非特許文献2記載されている。 However, these SiC single crystal wafer, growing direction micropipe defects penetrating in the (crystalline c-axis direction) is 1 to 100 cm -2 about dislocation defects included degree 10 4 ~10 5 cm -2, This hindered the production of high-performance devices. Non-Patent Document 2 describes that most of these micropipe defects and dislocation defects are introduced at the start of crystal growth.
c軸方向にほぼ平行に伝播するマイクロパイプ欠陥及び貫通転位欠陥は、{0001}面からの傾きが60〜120°(好ましくは90°)の面、例えば、a面あるいはm面を種結晶として用いて、<0001>方向、即ち、c軸方向とほぼ垂直方向にSiC単結晶を成長させることにより、完全に防止できることが、特許文献1に開示されている。 Micropipe defects and threading dislocation defects that propagate almost parallel to the c-axis direction have a 60-120 ° (preferably 90 °) inclination from the {0001} plane, for example, the a-plane or m-plane as a seed crystal. Patent Document 1 discloses that it can be completely prevented by growing a SiC single crystal in the <0001> direction, that is, in a direction substantially perpendicular to the c-axis direction.
しかしながら、この方法では、マイクロパイプ欠陥及びc軸方向に貫通する転位欠陥は完全に抑制できるものの、c軸に垂直方向に存在する基底面転位は残存し、また、新たに積層欠陥が発生すると言う問題が生じることが、非特許文献3に開示されている。 However, in this method, although micropipe defects and dislocation defects penetrating in the c-axis direction can be completely suppressed, basal plane dislocations existing in a direction perpendicular to the c-axis remain, and new stacking faults are generated. It is disclosed in Non-Patent Document 3 that a problem occurs.
一方、特許文献2には、N回(Nは、N≧3の自然数)の成長工程を有し、n=1である第1成長工程においては、{1−100}面からオフ角±20°以下の面、又は、{11−20}面からオフ角±20°以下の面を第1成長面とした第1種結晶を用いて、上記第1成長面に直交する方向にSiC単結晶を成長させ第1成長結晶を作製し、n=2、3、…、(N−1)回目(N≧3の自然数)である中間成長工程においては、第(n−1)成長面より45〜90°傾き、且つ、{0001}面より60〜90°傾いた面を第n成長面とした第n種結晶を第(n−1)成長結晶より作製し、この第n種結晶の第n成長面に直交する方向に第n成長結晶を作製し、n=Nである最終成長工程においては、第(N−1)成長結晶の{0001}面よりオフ角度±20°以下の面を最終成長面とした最終種結晶を第(N−1)成長結晶より作製し、この最終種結晶の最終成長面に直交する方向にバルク状のSiC単結晶を作製しすることにより、マイクロパイプ、らせん転位、刃状転位、及び積層欠陥をほとんど含まない高品質なSiC単結晶の製造方法が記載されている。
しかしながら、先に述べた特許文献2に記載されている方法では、単結晶の成長方向がc軸方向({0001}面の垂直方向)から大きく傾いた方向(傾角:60°以上)となっているために、大口径の{0001}面ウェハを得ようとした場合には、ほぼその口径に相当する長さまで結晶を成長することが必要となる。そのため、結晶成長に要する時間が長時間化し、結晶製造の生産性が低下する。さらに、SiC単結晶成長においては、原料や坩堝の経時変化等により、最適成長条件を長時間に亘って維持するのは一般に難しい。その結果、長尺結晶の高品質化は困難なものとなる。したがって、特許文献2に記載されている方法では、結晶成長の長時間化に伴って、結晶成長の歩留まりが低下し、結晶製造コストが著しく増加してしまっていた。 However, in the method described in Patent Document 2 described above, the growth direction of the single crystal is a direction (tilt angle: 60 ° or more) greatly inclined from the c-axis direction (vertical direction of the {0001} plane). Therefore, when an attempt is made to obtain a {0001} plane wafer having a large diameter, it is necessary to grow the crystal to a length substantially corresponding to the diameter. For this reason, the time required for crystal growth becomes longer, and the productivity of crystal production decreases. Furthermore, in SiC single crystal growth, it is generally difficult to maintain optimum growth conditions for a long time due to changes in the raw materials and crucibles over time. As a result, it is difficult to improve the quality of long crystals. Therefore, in the method described in Patent Document 2, the yield of crystal growth is reduced and the crystal production cost is remarkably increased as the crystal growth is prolonged.
本発明は、上記事情に鑑みてなされたものであり、マイクロパイプ欠陥、転位欠陥の少ない良質の大口径{0001}面ウェハを、再現性良く低コストで製造し得るためのSiC単結晶の製造方法及び炭化珪素単結晶インゴットを提供するものである。また、他の目的は、これら炭化珪素単結晶の製造方法によって得られた炭化珪素単結晶インゴットから炭化珪素単結晶基板、炭化珪素エピタキシャルウェハ、および薄膜エピタキシャルウェハを提供することである。 The present invention has been made in view of the above circumstances, and manufacture of a SiC single crystal for manufacturing a high-quality large-diameter {0001} plane wafer with few micropipe defects and dislocation defects at a low cost with good reproducibility. A method and a silicon carbide single crystal ingot are provided. Another object is to provide a silicon carbide single crystal substrate, a silicon carbide epitaxial wafer, and a thin film epitaxial wafer from the silicon carbide single crystal ingot obtained by the silicon carbide single crystal manufacturing method.
本発明は、以下のように構成される。 The present invention is configured as follows.
(1)SiC単結晶よりなる種結晶上にSiC単結晶を成長させてバルク状のSiC単結晶インゴットを製造する製造方法において、該製造方法はN回(Nは、N≧2の自然数)の成長工程を含み、各成長工程を第n成長工程(nは自然数であって1から始まりNで終わる序数)として表した場合、{0001}面から20°以上90°未満傾斜した傾斜面を成長面上に有するSiC単結晶育成用種結晶を用いてSiC単結晶インゴットを成長させ、その成長した単結晶インゴットから再び{0001}面から20°以上90°未満傾斜した傾斜面を成長面上に有するSiC単結晶育成用種結晶を切り出し、SiC単結晶成長をN回繰返すSiC単結晶インゴットの製造方法であって、前記第(n−1)成長工程で使用した種結晶の傾斜面の傾斜方向と第n成長工程で使用する種結晶の傾斜面の傾斜方向との{0001}面内における角度差が45°以上135°以下であるSiC単結晶インゴットの製造方法。 (1) In a manufacturing method for manufacturing a bulk SiC single crystal ingot by growing a SiC single crystal on a seed crystal made of SiC single crystal, the manufacturing method is N times (N is a natural number of N ≧ 2). When each growth process is expressed as an nth growth process (n is an ordinal number starting from 1 and ending with N) including a growth process, an inclined surface inclined by 20 ° or more and less than 90 ° from the {0001} plane is grown. An SiC single crystal ingot is grown using the SiC single crystal growth seed crystal on the surface, and an inclined surface inclined again by 20 ° or more and less than 90 ° from the {0001} plane from the grown single crystal ingot is formed on the growth surface. A method for producing a SiC single crystal ingot in which a SiC single crystal growth seed crystal is cut out and SiC single crystal growth is repeated N times, and the inclination of the inclined surface of the seed crystal used in the (n-1) th growth step is Direction as the manufacturing method of the {0001} SiC single crystal ingot angle difference is 45 ° or more 135 ° or less in the plane of the inclined direction of the inclined plane of the seed crystal used at the n-th growth step.
(2)前記種結晶の傾斜面と{0001}面の間の角度が45°以上90°未満である(1)に記載のSiC単結晶インゴットの製造方法。 (2) The method for producing a SiC single crystal ingot according to (1), wherein an angle between the inclined plane of the seed crystal and the {0001} plane is 45 ° or more and less than 90 °.
(3)前記第(n−1)成長工程で使用した種結晶の傾斜面の傾斜方向と第n成長工程で使用する種結晶の傾斜面の傾斜方向との{0001}面内における角度差が60°以上120°以下である(1)に記載のSiC単結晶インゴットの製造方法。 (3) The angle difference in the {0001} plane between the inclination direction of the inclined surface of the seed crystal used in the (n-1) th growth step and the inclination direction of the inclined surface of the seed crystal used in the nth growth step is The method for producing a SiC single crystal ingot according to (1), which is 60 ° or more and 120 ° or less.
(4)前記第1成長工程で使用する種結晶の傾斜面の傾斜方向が{0001}面内において<1−100>方向を中心に−15°以上15°以内にある(1)に記載のSiC単結晶インゴットの製造方法。 (4) The inclination direction of the inclined surface of the seed crystal used in the first growth step is in the range of −15 ° to 15 ° around the <1-100> direction in the {0001} plane. A method for producing a SiC single crystal ingot.
(5)前記第1成長工程で使用する種結晶の傾斜面の傾斜方向が{0001}面内において<11−20>方向を中心に−15°以上15°以内にある(1)に記載のSiC単結晶インゴットの製造方法。 (5) The inclination direction of the inclined surface of the seed crystal used in the first growth step is in the range of −15 ° to 15 ° with respect to the <11-20> direction in the {0001} plane. A method for producing a SiC single crystal ingot.
(6)前記(1)〜(5)のいずれか一つに記載の製造方法により得られたSiC単結晶インゴットであって、該インゴットの口径が50mm以上300mm以下であることを特徴とするSiC単結晶インゴット。 (6) A SiC single crystal ingot obtained by the production method according to any one of (1) to (5) above, wherein the diameter of the ingot is 50 mm or more and 300 mm or less. Single crystal ingot.
(7)前記(6)に記載のSiC単結晶インゴットであって、該インゴットから切り出した{0001}面8°オフウェハ上で計測される転位に起因したエッチピット密度の合計が1×104cm−2以下であることを特徴とするSiC単結晶インゴット。 (7) The SiC single crystal ingot according to (6), wherein the total etch pit density caused by dislocations measured on a {0001} plane 8 ° off-wafer cut out from the ingot is 1 × 10 4 cm -SiC single crystal ingot characterized by being -2 or less.
(8)前記(6)又は(7)に記載のSiC単結晶インゴットを切断、研磨してなるSiC単結晶基板。 (8) A SiC single crystal substrate obtained by cutting and polishing the SiC single crystal ingot according to (6) or (7).
(9)前記(8)に記載のSiC単結晶基板に、SiC薄膜をエピタキシャル成長してなるSiCエピタキシャルウェハ。 (9) A SiC epitaxial wafer obtained by epitaxially growing a SiC thin film on the SiC single crystal substrate according to (8).
(10)前記(8)に記載のSiC単結晶基板に、窒化ガリウム(GaN)、窒化アルミニウム(AlN)、窒化インジウム(InN)又はこれらの混晶をエピタキシャル成長してなる薄膜エピタキシャルウェハ。
である。
(10) A thin film epitaxial wafer obtained by epitaxially growing gallium nitride (GaN), aluminum nitride (AlN), indium nitride (InN) or a mixed crystal thereof on the SiC single crystal substrate according to (8).
It is.
本発明の製造方法を用いれば、転位欠陥が少ない良質のSiC単結晶を再現性良く低コストで成長させることができる。このようなSiC単結晶から切り出したウェハ及びエピタキシャルウェハを用いれば、光学的特性の優れた青色発光素子、電気的特性の優れた高周波・高耐圧電子デバイスを製作することができる。 By using the production method of the present invention, a high-quality SiC single crystal with few dislocation defects can be grown with good reproducibility at low cost. By using a wafer and an epitaxial wafer cut out from such a SiC single crystal, it is possible to manufacture a blue light-emitting element with excellent optical characteristics and a high-frequency / high-voltage electronic device with excellent electrical characteristics.
本発明のSiC単結晶の製造方法は、N回(Nは、N≧2の自然数)の成長工程を含み、各成長工程を第n成長工程(nは自然数であって、1から始まりNで終わる序数)として表した場合、{0001}面から20°以上90°未満傾斜した傾斜面を成長面上に有するSiC単結晶育成用種結晶を用いてSiC単結晶インゴットを成長し、その成長した単結晶インゴットから再び{0001}面から20°以上90°未満傾斜した傾斜面を成長面上に有するSiC単結晶育成用種結晶を切り出し、SiC単結晶成長をN回繰返すSiC単結晶インゴットの製造方法であって、第(n−1)成長工程で使用した種結晶の傾斜面の傾斜方向と第n成長工程で使用する種結晶の傾斜面の傾斜方向との{0001}面内における角度差を45°以上135°以下とすることにより、転位欠陥を低減し、さらに大口径の{0001}面ウェハを低コストで得ることができる。 The method for producing a SiC single crystal of the present invention includes N growth steps (N is a natural number of N ≧ 2), and each growth step is divided into an nth growth step (n is a natural number, starting from 1, N In a case where the SiC single crystal ingot is grown using a seed crystal for growing an SiC single crystal having an inclined surface on the growth surface that is inclined by 20 ° or more and less than 90 ° from the {0001} plane. Production of a SiC single crystal ingot, in which a SiC single crystal growth seed crystal having an inclined surface inclined from the {0001} plane by 20 ° or more and less than 90 ° on the growth surface is cut out from the single crystal ingot and the SiC single crystal growth is repeated N times. An angular difference in the {0001} plane between the inclination direction of the inclined surface of the seed crystal used in the (n-1) th growth step and the inclination direction of the inclined surface of the seed crystal used in the nth growth step. 45 ° or more 13 By setting it to 5 ° or less, dislocation defects can be reduced, and a large-diameter {0001} plane wafer can be obtained at low cost.
なお、本発明において、{0001}、{1−100}、及び{11−20}は、いわゆる結晶面の面指数を表している。上記面指数において、「−」記号は通常数字の上に付されるが、本明細書及び図面においては書類作成の便宜上のため数字の左側に付した。また、<0001>、<1−100>、及び<11−20>は、結晶内の方向を表し、「−」記号の取扱いについては、上記面指数と同様である。 In the present invention, {0001}, {1-100}, and {11-20} represent plane indices of so-called crystal planes. In the above surface index, the “-” symbol is usually added on the number, but in the present specification and drawings, it is added on the left side of the number for the convenience of document preparation. Further, <0001>, <1-100>, and <11-20> represent directions in the crystal, and the handling of the “−” symbol is the same as the above-described plane index.
図2を用いて、本発明の効果を説明する。本発明のSiC単結晶の製造方法は、図2(a)及び図2(b)に模式的に示された{0001}面から20°以上90°未満傾斜した面を成長面上に有する種結晶上に、SiC単結晶を成長させることを特徴とする。図2(a)は、傾斜面を成長面上に有する種結晶を上方(結晶成長方向である<0001>方向)から見た図であり、図2(b)は、同じ種結晶を側方(この場合、<1−100>あるいは<11−20>方向)から見た図である。 The effect of the present invention will be described with reference to FIG. The SiC single crystal production method of the present invention is a seed having a growth surface with a plane inclined at 20 ° or more and less than 90 ° from the {0001} plane schematically shown in FIGS. 2 (a) and 2 (b). A SiC single crystal is grown on the crystal. 2A is a view of a seed crystal having an inclined surface on the growth surface as viewed from above (the <0001> direction which is the crystal growth direction), and FIG. 2B is a side view of the same seed crystal. It is the figure seen from (in this case <1-100> or <11-20> direction).
この図の場合、種結晶の中心から左右対称に傾斜面を有し、それぞれの傾角は、{0001}面に対し、±α°(20≦α≦90)となっている。但し、傾斜面の形態は、以下に述べる効果を発現するものであれば、図2(a)及び図2(b)に示された形態に限定されるものではない。例えば、図3に示されるような傾斜面の形態でも、同様な効果が期待できる。 In the case of this figure, there are inclined surfaces symmetrically from the center of the seed crystal, and each inclination angle is ± α ° (20 ≦ α ≦ 90) with respect to the {0001} plane. However, the form of the inclined surface is not limited to the form shown in FIGS. 2A and 2B as long as the effects described below are exhibited. For example, the same effect can be expected even in the form of an inclined surface as shown in FIG.
図2(a)に示した傾斜面を成長面上に有したSiC単結晶を種結晶として用いた場合、結晶成長の初期の段階では、傾斜面にほぼ垂直方向に結晶が成長する。即ち、結晶の成長方向は、<0001>方向からα°傾いた方向となり、その結果、αが60°以上90°未満の場合には、非特許文献2に示されているように、種結晶中に存在していたマイクロパイプ、貫通転位欠陥は、成長結晶には引き継がれず、また、新たな発生も完全に抑制される(図2(c)参照)。また、αが20°以上60°未満の場合にも、マイクロパイプ、貫通転位が、完全ではないものの、かなりの割合で結晶成長中に消失、あるいは、基底面積層欠陥あるいは基底面転位に変換されることを、発明者らは数多くの実験から見出した。 When the SiC single crystal having the inclined surface shown in FIG. 2A on the growth surface is used as a seed crystal, the crystal grows in a direction substantially perpendicular to the inclined surface in the initial stage of crystal growth. That is, the crystal growth direction is inclined by α ° from the <0001> direction. As a result, when α is 60 ° or more and less than 90 °, as shown in Non-Patent Document 2, The micropipe and threading dislocation defects that existed therein are not carried over to the grown crystal, and new generation is completely suppressed (see FIG. 2C). Even when α is 20 ° or more and less than 60 °, the micropipes and threading dislocations are not perfect, but disappear at a significant rate during crystal growth, or are converted into base area layer defects or basal plane dislocations. The inventors found out from numerous experiments.
その後の成長においては、結晶成長が進むにつれて、結晶成長方向が、徐々に<0001>方向に傾いて行き(即ち、傾斜面と{0001}面との間の傾角が小さくなって行き)、最終的には、傾斜面上ではc軸と5°〜10°程度の傾きを持って成長が進行する。非特許文献3に示されているように、結晶成長初期にマイクロパイプ、貫通転位が抑制された領域には、{0001}面積層欠陥が発生するが(図2(c)参照)、結晶成長方向がc軸から20°以内となる、成長中盤から後半にかけて成長した結晶部位には、積層欠陥は発生しない。また、成長初期に発生した積層欠陥は、{0001}面内の面欠陥であるため、c軸からの傾角が小さくなる成長中盤から後半に成長した結晶部位には引き継がれることはない。 In the subsequent growth, as the crystal growth proceeds, the crystal growth direction gradually inclines in the <0001> direction (that is, the inclination angle between the inclined surface and the {0001} surface decreases), and finally Specifically, the growth proceeds with an inclination of about 5 ° to 10 ° with respect to the c-axis on the inclined surface. As shown in Non-Patent Document 3, a {0001} area layer defect occurs in a region where micropipes and threading dislocations are suppressed in the initial stage of crystal growth (see FIG. 2C). Stacking faults do not occur in crystal parts grown from the middle of the growth to the latter half, the direction of which is within 20 ° from the c-axis. Further, since the stacking fault generated in the early stage of growth is a plane defect in the {0001} plane, it is not carried over to the crystal part grown in the latter half from the middle growth stage where the tilt angle from the c-axis becomes small.
一方、種結晶中に存在する基底面転位の中、傾斜面を横切るように存在するものは、結晶成長の開始に伴って、成長結晶中に引き継がれる(図2(c)参照)。発明者らは、その際、これらの基底面転位が傾斜面方向に配向することを見出した。即ち、種結晶に存在していた基底面転位は、種結晶中では基底面内ほぼランダムな方向に分布しているが、傾斜面を有した種結晶上にSiC単結晶を成長した場合には、基底面転位は、傾斜面方向(例えば、傾斜面の{0001}面内における傾斜方向が<11−20>方向の場合には、<11−20>方向)に配向した状態で成長結晶に引き継がれる。 On the other hand, among the basal plane dislocations present in the seed crystal, those existing across the inclined surface are inherited in the grown crystal as the crystal growth starts (see FIG. 2C). The inventors have found that these basal plane dislocations are oriented in the direction of the inclined plane. That is, the basal plane dislocations existing in the seed crystal are distributed in a nearly random direction in the basal plane in the seed crystal, but when a SiC single crystal is grown on the seed crystal having an inclined surface. The basal plane dislocations are formed in the grown crystal in the state of being oriented in the inclined plane direction (for example, the <11-20> direction when the inclined direction in the {0001} plane of the inclined plane is the <11-20> direction). Taken over.
マイクロパイプ、貫通転位、基底面転位は、種結晶に存在したものが引き継がれるだけでなく、結晶成長中にも発生する。発生の原因は種々考えられるが、大きなものの一つに下地結晶の結晶品質がある。即ち、結晶成長中に発生するマイクロパイプ、転位欠陥の量は、下地結晶の結晶品質に大きく影響され、下地結晶の結晶品質が向上すると、その発生量が低下する。発明者らは、数多くの実験から、特に下地結晶の転位密度が減少した時に、この効果が強く現れ、下地結晶の転位密度の低減に伴って、結晶成長中の欠陥発生量が減少することを見出した。 Micropipes, threading dislocations, and basal plane dislocations occur not only in the seed crystal but also during crystal growth. There are various causes for the occurrence, but one of the major ones is the crystal quality of the base crystal. That is, the amount of micropipes and dislocation defects generated during crystal growth is greatly influenced by the crystal quality of the base crystal, and the amount of generation decreases as the crystal quality of the base crystal improves. The inventors have shown from a number of experiments that this effect is particularly apparent when the dislocation density of the underlying crystal is reduced, and that the amount of defects generated during crystal growth decreases as the dislocation density of the underlying crystal decreases. I found it.
本発明のSiC単結晶インゴットの製造方法は、N回(Nは、N≧2の自然数)の成長工程を含み、各成長工程を第n成長工程(nは自然数であって、1から始まりNで終わる序数)として表した場合、第(n−1)成長工程で、図2(a)及び図2(b)に例示された種結晶上にSiC単結晶インゴットを成長し、その成長した単結晶インゴットから再び{0001}面から20°以上90°未満傾斜した傾斜面を成長面上に有するSiC単結晶育成用種結晶を切り出し、第n成長工程の種結晶として用いる。その際、第(n−1)成長工程で使用した種結晶の傾斜面の傾斜方向と第n成長工程で使用する種結晶の傾斜面の傾斜方向との{0001}面内における角度差を45°以上135°以下とすることを特徴とする。 The method for producing a SiC single crystal ingot according to the present invention includes N growth steps (N is a natural number of N ≧ 2), and each growth step includes an n-th growth step (n is a natural number, starting from 1 and N Ordinal number ending in) in the (n-1) th growth step, a SiC single crystal ingot is grown on the seed crystal illustrated in FIGS. 2A and 2B, and the grown single unit From the crystal ingot, a SiC single crystal growth seed crystal having an inclined surface inclined from the {0001} plane by 20 ° or more and less than 90 ° on the growth surface is cut out and used as a seed crystal for the n-th growth step. At that time, the angle difference in the {0001} plane between the inclination direction of the inclined surface of the seed crystal used in the (n-1) th growth step and the inclination direction of the inclined surface of the seed crystal used in the nth growth step is 45. It is characterized by being not less than 135 ° and not more than 135 °.
この傾斜面方向を回転させる効果について、次に述べる。第(n−1)成長工程で使用する種結晶の傾斜面を、例えば、<11−20>方向に45°傾斜したものとした場合、種結晶中に存在していた基底面転位は、成長結晶の下部において、<11−20>方向に配向した状態で成長結晶中に引き継がれる。また、結晶成長中に発生した基底面転位も、傾斜面(傾角5°〜10°)の効果により、成長結晶の各部位で常に<11−20>方向に配向した形で、成長結晶中に存在することになる。今、このような成長結晶から、<1−100>方向に45°傾斜した傾斜面を成長面上に有する種結晶を切り出し、第n成長工程で使用したとすると、種結晶(第n種結晶)中に存在する基底面転位は、前述したように<11−20>方向に、即ち、第n種結晶の傾斜面方向と90°異なる方向に配向している。このように傾斜面方向とほぼ垂直方向に配向した基底面転位は、傾斜面を横切ることがなく、種結晶から成長結晶に引き継がれることは極めて少なくなる。例えば、傾斜面の{0001}面からの傾角が45°の場合、第n種結晶中に存在する基底面転位(傾斜面方向とほぼ垂直方向に配向)の約1/10〜1/5が第n成長結晶に引き継がれる。したがって、このような種結晶上に成長したSiC単結晶では、種結晶から引き継がれる基底面転位の密度が極めて低く、結果として、下地結晶の結晶品質が大幅に改善され、結晶成長中の転位発生も大幅に低減される。 The effect of rotating the inclined surface direction will be described next. When the inclined surface of the seed crystal used in the (n-1) th growth step is inclined by 45 ° in the <11-20> direction, for example, the basal plane dislocations existing in the seed crystal are grown. In the lower part of the crystal, it is taken over in the grown crystal in a state oriented in the <11-20> direction. In addition, basal plane dislocations generated during crystal growth are also always oriented in the <11-20> direction at each part of the grown crystal due to the effect of the inclined surface (inclination angle 5 ° to 10 °). Will exist. Now, assuming that a seed crystal having an inclined surface inclined by 45 ° in the <1-100> direction on the growth surface is cut out from such a grown crystal and used in the n-th growth step, the seed crystal (n-th seed crystal) The basal plane dislocations present in are oriented in the <11-20> direction as described above, that is, in a direction different from the inclined plane direction of the n-th seed crystal by 90 °. Thus, the basal plane dislocation oriented in the direction substantially perpendicular to the inclined plane direction does not cross the inclined plane, and is very rarely transferred from the seed crystal to the grown crystal. For example, when the tilt angle of the tilted surface from the {0001} plane is 45 °, about 1/10 to 1/5 of the basal plane dislocation (orientated in a direction substantially perpendicular to the tilted surface direction) existing in the nth seed crystal is Takes over to the nth grown crystal. Therefore, in the SiC single crystal grown on such a seed crystal, the density of the basal plane dislocation inherited from the seed crystal is extremely low. As a result, the crystal quality of the underlying crystal is greatly improved, and dislocation occurs during crystal growth. Is also greatly reduced.
種結晶成長面上の傾斜面の形態としては、図2のような対称形で、全面が傾斜面で覆われたものが、欠陥低減の観点から好ましいが、上記のような欠陥の伝播様式が実現できれば、非対称形態あるいは一部のみが傾斜面で覆われた形態でも構わない。 As the form of the inclined surface on the seed crystal growth surface, a symmetrical shape as shown in FIG. 2 and the entire surface covered with the inclined surface are preferable from the viewpoint of defect reduction. As long as it can be realized, an asymmetrical form or a form in which only a part is covered with an inclined surface may be used.
したがって、種結晶の成長面上の傾斜面と{0001}面の間の角度(傾角α)としては、20°以上90°未満、好ましくは45°以上90°未満が望ましい。傾角が20°未満になった場合には、結晶成長様式が従来の(0001)面上のものとほぼ同一となってしまい、本発明で述べたマイクロパイプ、貫通転位欠陥の抑制、低減効果が得難い。また、90°以上の場合には、傾斜面が結晶成長方向と平行あるいは逆方向となってしまい結晶成長が困難となる。 Therefore, the angle (tilt angle α) between the inclined surface on the growth surface of the seed crystal and the {0001} plane is preferably 20 ° or more and less than 90 °, preferably 45 ° or more and less than 90 °. When the tilt angle is less than 20 °, the crystal growth mode is almost the same as that on the conventional (0001) plane, and the micropipe and threading dislocation defect suppression and reduction effects described in the present invention are effective. It is hard to get. On the other hand, when the angle is 90 ° or more, the inclined surface becomes parallel or opposite to the crystal growth direction, and crystal growth becomes difficult.
第(n−1)種結晶の傾斜面方向と第n種結晶の傾斜面方向との{0001}面内における角度差としては、45°以上135°以下、好ましくは60°以上120°以下が望ましい。傾斜面方向の角度差が45°未満になった場合には、第(n−1)成長工程で配向した基底面転位を第n成長工程で引き継いでしまう確率が高くなってしまう。また、135°超の場合にも、同様に基底面転位を引き継いでしまう確率が高くなるので好ましくない。 The angle difference in the {0001} plane between the inclined plane direction of the (n-1) th seed crystal and the inclined plane direction of the nth seed crystal is 45 ° to 135 °, preferably 60 ° to 120 °. desirable. When the angle difference in the inclined plane direction is less than 45 °, the probability that the basal plane dislocations oriented in the (n−1) th growth step will be inherited in the nth growth step is increased. Further, when the angle exceeds 135 °, the probability of taking over the basal plane dislocation is increased, which is not preferable.
種結晶への傾斜面の作製方法については、種々の方法が考えられるが、一番簡便な方法は、機械加工(例えば、ダイヤモンドブレードによる切削)による方法である。ブレードの先端形状、幅等を選択し、さらに、ブレードによる切削を三次元的に制御して行うことにより、種結晶成長面上に種々の形態の傾斜面を作製することができる。 Various methods are conceivable for the method of forming the inclined surface on the seed crystal, but the simplest method is a method by machining (for example, cutting with a diamond blade). By selecting the tip shape, width, and the like of the blade, and further performing cutting with the blade in a three-dimensional manner, various types of inclined surfaces can be produced on the seed crystal growth surface.
本発明のSiC単結晶の製造方法は、大口径のSiC単結晶の製造に用いられる。図1に示されるように、種結晶101は、SiC原料粉末102と共に坩堝103内に収納され、アルゴン等の不活性ガス雰囲気中、2000〜2400℃に加熱される。この際、原料粉末に比べ、種結晶がやや低温になるように、温度勾配が設定される。原料102は、昇華後、この温度勾配により種結晶101方向へ拡散、輸送される。単結晶成長は、種結晶101に到着した原料ガスが種結晶上で再結晶化することにより実現される。 The method for producing a SiC single crystal according to the present invention is used for producing a large-diameter SiC single crystal. As shown in FIG. 1, seed crystal 101 is housed in crucible 103 together with SiC raw material powder 102 and heated to 2000 to 2400 ° C. in an inert gas atmosphere such as argon. At this time, the temperature gradient is set so that the seed crystal has a slightly lower temperature than the raw material powder. After sublimation, the raw material 102 is diffused and transported toward the seed crystal 101 by this temperature gradient. Single crystal growth is realized by recrystallization of the source gas that has arrived at the seed crystal 101 on the seed crystal.
種結晶101の口径としては、40〜300mmが望ましい。従来から改良レーリー法によるSiC単結晶成長では、種結晶と同口径か少し大きな口径の結晶が製造できる。したがって、本発明においても種結晶の口径が40〜300mmあれば、一回の成長で口径50〜300mm程度のSiC単結晶インゴットを製造することが可能となる。 The diameter of the seed crystal 101 is preferably 40 to 300 mm. Conventionally, in SiC single crystal growth by the modified Rayleigh method, a crystal having the same diameter as the seed crystal or a slightly larger diameter can be produced. Therefore, in the present invention, if the diameter of the seed crystal is 40 to 300 mm, an SiC single crystal ingot having a diameter of about 50 to 300 mm can be manufactured by one growth.
そして、本発明では既に説明したようにしてN回結晶成長を繰り返し実行することで、良質のSiC単結晶を再現性良く成長させることができる。なお、繰り返しの回数Nは、多く繰り返すほど欠陥の少ないSiC単結晶の成長が望めるが、製造コストも考慮し、少なくとも2回以上行えば繰り返さなかったものよりも良質なSiC単結晶ができ、より好ましくは4〜6回繰り返すことで、さらに欠陥が少なく良質のSiC単結晶を製造することができる。 In the present invention, a high-quality SiC single crystal can be grown with good reproducibility by repeatedly executing crystal growth N times as already described. The number of repetitions N can be expected to grow SiC single crystals with fewer defects as the number of repetitions is increased. However, considering the manufacturing cost, a SiC single crystal with higher quality than that which has not been repeated can be obtained if it is performed at least twice. Preferably, by repeating 4 to 6 times, it is possible to produce a high-quality SiC single crystal with fewer defects.
本発明のSiC単結晶基板は、50mm以上300mm以下の口径を有しているので、この基板を用いて各種デバイスを製造する際、工業的に確立されている従来の半導体(Si、GaAs等)基板用の製造ラインを使用することができ、量産に適している。また、この基板の転位密度が{0001}面8°オフウェハ上のエッチピット密度換算で1×104cm−2以下と低いため、特に、大電流、高出力のデバイス製造に適している。さらに、このSiC単結晶ウェハ上にCVD法等によりエピタキシャル薄膜を成長して作製されるSiC単結晶エピタキシャルウェハ、あるいはGaN、AlN、InN及びこららの混晶薄膜エピタキシャルウェハは、その基板となるSiC単結晶ウェハの転位密度が小さいために、良好な特性(耐電圧、エピタキシャル薄膜の表面モフォロジー等)を有するようになる。 Since the SiC single crystal substrate of the present invention has a diameter of 50 mm or more and 300 mm or less, a conventional semiconductor (Si, GaAs, etc.) established industrially when manufacturing various devices using this substrate. A production line for substrates can be used, which is suitable for mass production. Further, since the dislocation density of this substrate is as low as 1 × 10 4 cm −2 or less in terms of etch pit density on the {0001} plane 8 ° off-wafer, it is particularly suitable for manufacturing a large current and high output device. Furthermore, an SiC single crystal epitaxial wafer produced by growing an epitaxial thin film on this SiC single crystal wafer by a CVD method or the like, or a mixed crystal thin film epitaxial wafer of GaN, AlN, InN, and these is used as an SiC substrate. Since the dislocation density of the single crystal wafer is small, it has good characteristics (withstand voltage, surface morphology of the epitaxial thin film, etc.).
以下に、本発明の実施例を述べる。 Examples of the present invention will be described below.
図4は、本発明を実施するための単結晶成長装置を示す図面である。この製造装置は、種結晶を用いた改良型レーリー法によって、SiC単結晶を成長させる装置の一例である。 FIG. 4 is a drawing showing a single crystal growth apparatus for carrying out the present invention. This manufacturing apparatus is an example of an apparatus for growing a SiC single crystal by an improved Rayleigh method using a seed crystal.
まず、この単結晶成長装置について簡単に説明する。結晶成長は、種結晶として用いた傾斜面を成長面上に有するSiC単結晶1の上に原料であるSiC粉末2を昇華再結晶化させることにより行われる。種結晶のSiC単結晶1は、黒鉛製坩堝3の蓋4の内面に取り付けられる。原料のSiC粉末2は、黒鉛製坩堝3の内部に充填されている。このような黒鉛製坩堝3は、二重石英管5の内部に、黒鉛の支持棒6により設置される。黒鉛製坩堝3の周囲には、熱シールドのための黒鉛製フェルト7が設置されている。二重石英管5は、真空排気装置により高真空排気(10−3Pa以下)することができ、かつ、内部雰囲気をArガスにより圧力制御することができる。また、二重石英管5の外周には、ワークコイル8が設置されており、高周波電流を流すことにより黒鉛製坩堝3を加熱し、原料及び種結晶を所望の温度に加熱することができる。坩堝温度の計測は、坩堝上部及び下部を覆うフェルトの中央部に直径2〜4mmの光路を設け、坩堝上部及び下部からの光を取り出し、二色温度計を用いて行う。坩堝下部の温度を原料温度、坩堝上部の温度を種結晶温度とする。 First, this single crystal growth apparatus will be briefly described. Crystal growth is performed by sublimating and recrystallizing SiC powder 2 as a raw material on SiC single crystal 1 having an inclined surface used as a seed crystal on the growth surface. The seed crystal SiC single crystal 1 is attached to the inner surface of the lid 4 of the graphite crucible 3. The raw material SiC powder 2 is filled in a graphite crucible 3. Such a graphite crucible 3 is installed inside a double quartz tube 5 by a support rod 6 made of graphite. Around the graphite crucible 3, a graphite felt 7 for heat shielding is installed. The double quartz tube 5 can be highly evacuated (10 −3 Pa or less) by a vacuum evacuation apparatus, and the internal atmosphere can be pressure controlled by Ar gas. In addition, a work coil 8 is provided on the outer periphery of the double quartz tube 5, and the graphite crucible 3 can be heated by flowing a high-frequency current to heat the raw material and the seed crystal to a desired temperature. The temperature of the crucible is measured using a two-color thermometer by providing an optical path having a diameter of 2 to 4 mm at the center of the felt covering the upper and lower parts of the crucible, taking out light from the upper and lower parts of the crucible. The temperature at the bottom of the crucible is the raw material temperature, and the temperature at the top of the crucible is the seed crystal temperature.
次に、この結晶成長装置を用いたSiC単結晶の製造について、実施例を説明する。まず、予め成長しておいたSiC単結晶インゴットから、口径50mm、高さ30mmの{0001}面を主面とした4H型のSiC単結晶片を種結晶として、また、口径50mm、厚さ1mmの{0001}面8°オフウェハをエッチピット密度計測用ウェハとして用意した。 Next, an example will be described for the production of a SiC single crystal using this crystal growth apparatus. First, from a previously grown SiC single crystal ingot, a 4H-type SiC single crystal piece having a {0001} face having a diameter of 50 mm and a height of 30 mm as a main surface is used as a seed crystal, and the diameter is 50 mm and the thickness is 1 mm. {0001} plane 8 ° off wafer was prepared as an etch pit density measurement wafer.
次に、このSiC単結晶インゴット中のマイクロパイプ欠陥と貫通転位密度、及び基底面転位密度を計測する目的で、上記{0001}面8°オフウェハのエッチピット観察を行った。その結果、マイクロパイプ欠陥、貫通転位、基底面転位に起因したエッチピット密度として、それぞれ10.2cm−2、2.2×104cm−2、5.3×103cm−2と言う値を得た。 Next, for the purpose of measuring the micropipe defects, threading dislocation density, and basal plane dislocation density in the SiC single crystal ingot, etch pit observation of the {0001} plane 8 ° off-wafer was performed. As a result, etch pit densities caused by micropipe defects, threading dislocations, and basal plane dislocations are 10.2 cm −2 , 2.2 × 10 4 cm −2 , and 5.3 × 10 3 cm −2 , respectively. Got.
欠陥密度評価後、種結晶1の(000−1)C面に機械加工を施し、<11−20>方向に45°傾斜した傾斜面を付与した。傾斜面は中心線から左右対称に付与した。また、この機械加工により種結晶の成長面に形成された加工損傷層は、薬液によるエッチングにより除去した。 After the defect density evaluation, the (000-1) C surface of the seed crystal 1 was machined to give an inclined surface inclined by 45 ° in the <11-20> direction. The inclined surface was provided symmetrically from the center line. Further, the processing damaged layer formed on the growth surface of the seed crystal by this machining was removed by etching with a chemical solution.
このようにして作製した傾斜面付SiC単結晶種結晶を、黒鉛製坩堝3の蓋4の内面に取り付けた。黒鉛製坩堝3の内部には、原料2を充填した。 The sloped SiC single crystal seed crystal thus produced was attached to the inner surface of the lid 4 of the graphite crucible 3. The raw material 2 was filled in the graphite crucible 3.
次いで、原料を充填した黒鉛製坩堝3を、種結晶を取り付けた蓋4で閉じ、黒鉛製フェルト7で被覆した後、黒鉛製支持棒6の上に乗せ、二重石英管5の内部に設置した。そして、石英管の内部を真空排気した後、ワークコイルに電流を流し、原料温度を2000℃まで上げた。その後、雰囲気ガスとして窒素を10%含むArガスを流入させ、石英管内圧力を約80kPaに保ちながら、原料温度を目標温度である2400℃まで上昇させた。成長圧力である1.3kPaには約30分かけて減圧し、その後、約50時間成長を続けた。この際の坩堝内の温度勾配は15℃/cmで、成長速度は平均で約0.70mm/時であった。得られた結晶の口径は51.5mmで、高さは35mm程度であった。 Next, the graphite crucible 3 filled with the raw material is closed with a lid 4 fitted with a seed crystal, covered with a graphite felt 7, placed on a graphite support rod 6, and installed inside the double quartz tube 5. did. And after evacuating the inside of a quartz tube, the electric current was sent through the work coil and the raw material temperature was raised to 2000 degreeC. Thereafter, Ar gas containing 10% nitrogen was introduced as the atmospheric gas, and the raw material temperature was raised to the target temperature of 2400 ° C. while maintaining the pressure in the quartz tube at about 80 kPa. The growth pressure was reduced to 1.3 kPa over about 30 minutes, and then the growth was continued for about 50 hours. At this time, the temperature gradient in the crucible was 15 ° C./cm, and the average growth rate was about 0.70 mm / hour. The diameter of the obtained crystal was 51.5 mm, and the height was about 35 mm.
こうして得られたSiC単結晶をX線回折及びラマン散乱により分析したところ、4H型のSiC単結晶インゴットが成長したことを確認できた。 When the SiC single crystal thus obtained was analyzed by X-ray diffraction and Raman scattering, it was confirmed that a 4H type SiC single crystal ingot had grown.
次に、この単結晶インゴットから再び種結晶として、口径50mm、高さ30mmの{0001}面を主面とした4H型のSiC単結晶片を用意した。 Next, a 4H-type SiC single crystal piece having a {0001} plane with a diameter of 50 mm and a height of 30 mm as a main surface was prepared again from this single crystal ingot as a seed crystal.
そして、再びこの種結晶の(000−1)C面に機械加工を施し、{0001}面から45°傾斜した傾斜面を成長面上に付与した。この際、傾斜面の傾斜方向を、前成長工程の種結晶の傾斜面方向とは垂直方向である<1−100>方向とした。傾斜面は中心線から左右対称に付与した。また、この機械加工により種結晶の成長面に形成された加工損傷層は、薬液によるエッチングにより除去した。 Then, machining was again performed on the (000-1) C plane of the seed crystal, and an inclined plane inclined by 45 ° from the {0001} plane was provided on the growth plane. At this time, the inclination direction of the inclined surface was set to the <1-100> direction which is perpendicular to the inclined surface direction of the seed crystal in the pre-growth step. The inclined surface was provided symmetrically from the center line. Further, the processing damaged layer formed on the growth surface of the seed crystal by this machining was removed by etching with a chemical solution.
このようにして作製した傾斜面付SiC単結晶種結晶を、新たに用意した黒鉛製坩堝3の蓋4の内面に取り付けた。黒鉛製坩堝3の内部には、原料2を充填した。 The sloped SiC single crystal seed crystal produced in this manner was attached to the inner surface of the lid 4 of a newly prepared graphite crucible 3. The raw material 2 was filled in the graphite crucible 3.
次いで、原料を充填した黒鉛製坩堝3を、種結晶を取り付けた蓋4で閉じ、黒鉛製フェルト7で被覆した後、黒鉛製支持棒6の上に乗せ、二重石英管5の内部に設置した。そして、石英管の内部を真空排気した後、ワークコイルに電流を流し、原料温度を2000℃まで上げた。その後、雰囲気ガスとして窒素を10%含むArガスを流入させ、石英管内圧力を約80kPaに保ちながら、原料温度を目標温度である2400℃まで上昇させた。成長圧力である1.3kPaには約30分かけて減圧し、その後、約50時間成長を続けた。この際の坩堝内の温度勾配は15℃/cmで、成長速度は約0.66mm/時であった。得られた結晶の口径は51.5mmで、高さは33mm程度であった。 Next, the graphite crucible 3 filled with the raw material is closed with a lid 4 fitted with a seed crystal, covered with a graphite felt 7, placed on a graphite support rod 6, and installed inside the double quartz tube 5. did. And after evacuating the inside of a quartz tube, the electric current was sent through the work coil and the raw material temperature was raised to 2000 degreeC. Thereafter, Ar gas containing 10% nitrogen was introduced as the atmospheric gas, and the raw material temperature was raised to the target temperature of 2400 ° C. while maintaining the pressure in the quartz tube at about 80 kPa. The growth pressure was reduced to 1.3 kPa over about 30 minutes, and then the growth was continued for about 50 hours. At this time, the temperature gradient in the crucible was 15 ° C./cm, and the growth rate was about 0.66 mm / hour. The diameter of the obtained crystal was 51.5 mm, and the height was about 33 mm.
こうして得られたSiC単結晶を再びX線回折及びラマン散乱により分析したところ、4H型のSiC単結晶が成長したことを確認できた。また、成長結晶中に存在するマイクロパイプ欠陥と貫通転位欠陥密度、及び基底面転位密度を評価する目的で、成長した単結晶インゴットの成長後半部分から{0001}面8°オフウェハを切り出し、研磨した。その後、約530℃の溶融KOHでウェハ表面をエッチングし、顕微鏡によりマイクロパイプ欠陥、貫通転位、基底面転位に対応するエッチピットの密度を調べたところ、それぞれウェハ全面の平均で3.1cm−2、0.6×104cm−2、1.2×103cm−2と言う値を得た。 When the SiC single crystal thus obtained was analyzed again by X-ray diffraction and Raman scattering, it was confirmed that a 4H type SiC single crystal had grown. In addition, in order to evaluate the micropipe defect and threading dislocation defect density and the basal plane dislocation density existing in the grown crystal, a {0001} plane 8 ° off-wafer was cut out and polished from the latter half of the grown single crystal ingot. . Thereafter, the wafer surface is etched with molten KOH at about 530 ° C., micropipe defects by a microscope, threading dislocations, was examined and the density of the etch pits corresponding to basal plane dislocations, 3.1 cm -2 at an average of the entire surface of the wafer, respectively , 0.6 × 10 4 cm −2 and 1.2 × 10 3 cm −2 were obtained.
さらに、上記SiC単結晶の成長後半の部位から、口径51mmの{0001}面SiC単結晶ウェハを切出し、鏡面ウェハとした。基板の面方位は(0001)Si面で[11−20]方向に8°オフとした。 Further, a {0001} plane SiC single crystal wafer having a diameter of 51 mm was cut out from the latter half of the SiC single crystal growth to obtain a mirror wafer. The plane orientation of the substrate was 8 ° off in the [11-20] direction on the (0001) Si plane.
このSiC単結晶ウェハを基板として用いて、SiCのエピタキシャル成長を行った。SiCエピタキシャル薄膜の成長条件は、成長温度1500℃、シラン(SiH4)、プロパン(C3H8)、水素(H2)の流量が、それぞれ5.0×10−9m3/sec、3.3×10−9m3/sec、5.0×10−5m3/secであった。成長圧力は大気圧とした。成長時間は2時間で、膜厚としては約5μm成長した。 Using this SiC single crystal wafer as a substrate, SiC was epitaxially grown. The growth conditions of the SiC epitaxial thin film are as follows: the growth temperature is 1500 ° C., and the flow rates of silane (SiH 4 ), propane (C 3 H 8 ), and hydrogen (H 2 ) are 5.0 × 10 −9 m 3 / sec, 3 was .3 × 10 -9 m 3 /sec,5.0×10 -5 m 3 / sec. The growth pressure was atmospheric pressure. The growth time was 2 hours, and the film thickness was about 5 μm.
エピタキシャル薄膜成長後、ノマルスキー光学顕微鏡により、得られたエピタキシャル薄膜の表面モフォロジーを観察したところ、ウェハ全面に渡って非常に平坦で、ピット等の表面欠陥が少ない良好な表面モフォロジーを有するSiCエピタキシャル薄膜が成長されているのが分かった。 After the epitaxial thin film growth, the surface morphology of the obtained epitaxial thin film was observed with a Nomarski optical microscope. As a result, a SiC epitaxial thin film having a good surface morphology that was very flat over the entire wafer surface and had few surface defects such as pits was obtained. I found it growing up.
また、上記SiC単結晶から同様にして、オフ角度が0°の(0001)Si面SiC単結晶ウェハを切り出し、鏡面研磨した後、その上にGaN薄膜を有機金属化学気相成長(MOCVD)法によりエピタキシャル成長させた。成長条件は、成長温度1050℃、トリメチルガリウム(TMG)、アンモニア(NH3)、シラン(SiH4)をそれぞれ、54×10−6モル/min、4リットル/min、22×10−11モル/min流した。また、成長圧力は大気圧とした。成長時間は60分間で、n型のGaNを3μmの膜厚で成長させた。 Similarly, a (0001) Si-face SiC single crystal wafer having an off angle of 0 ° is cut out from the SiC single crystal and mirror-polished, and then a GaN thin film is grown thereon by metal organic chemical vapor deposition (MOCVD). By epitaxial growth. The growth conditions were growth temperature of 1050 ° C., trimethylgallium (TMG), ammonia (NH 3 ), and silane (SiH 4 ) of 54 × 10 −6 mol / min, 4 liter / min, and 22 × 10 −11 mol / min, respectively. Min flowed. The growth pressure was atmospheric pressure. The growth time was 60 minutes, and n-type GaN was grown to a thickness of 3 μm.
得られたGaN薄膜の表面状態を調べる目的で、成長表面をノマルスキー光学顕微鏡により観察した。ウェハ全面に渡って非常に平坦なモフォロジーが得られ、全面に渡って高品質なGaN薄膜が形成されているのが分かった。 For the purpose of examining the surface state of the obtained GaN thin film, the growth surface was observed with a Nomarski optical microscope. It was found that a very flat morphology was obtained over the entire wafer surface, and a high-quality GaN thin film was formed over the entire surface.
1…種結晶(SiC単結晶)
2…SiC粉末原料
3…黒鉛製坩堝
4…黒鉛製坩堝蓋
5…二重石英管
6…支持棒
7…黒鉛製フェルト
8…ワークコイル
9…Arガス配管
10…Arガス用マスフローコントローラ
11…真空排気装置
1 ... Seed crystal (SiC single crystal)
2 ... SiC powder raw material 3 ... Graphite crucible 4 ... Graphite crucible lid 5 ... Double quartz tube 6 ... Support rod 7 ... Graphite felt 8 ... Work coil 9 ... Ar gas pipe 10 ... Ar gas mass flow controller 11 ... Vacuum Exhaust system
Claims (10)
該製造方法はN回(Nは、N≧2の自然数)の成長工程を含み、各成長工程を第n成長工程(nは自然数であって1から始まりNで終わる序数)として表した場合、{0001}面から20°以上90°未満傾斜した傾斜面を成長面上に有する炭化珪素単結晶育成用種結晶を用いて炭化珪素単結晶インゴットを成長させ、その成長した単結晶インゴットから再び{0001}面から20°以上90°未満傾斜した傾斜面を成長面上に有する炭化珪素単結晶育成用種結晶を切り出し、炭化珪素単結晶成長をN回繰返す炭化珪素単結晶インゴットの製造方法であって、第(n−1)成長工程で使用した種結晶の傾斜面の傾斜方向と第n成長工程で使用する種結晶の傾斜面の傾斜方向との{0001}面内における角度差が45°以上135°以下である炭化珪素単結晶インゴットの製造方法。 In a production method for producing a bulk silicon carbide single crystal ingot by growing a silicon carbide single crystal on a seed crystal composed of a silicon carbide single crystal,
The manufacturing method includes N growth steps (N is a natural number of N ≧ 2), and each growth step is expressed as an nth growth step (n is a natural number and starts with 1 and ends with N). A silicon carbide single crystal ingot is grown using a seed crystal for growing a silicon carbide single crystal having a tilted surface inclined from the {0001} plane by 20 ° or more and less than 90 ° on the growth surface, and from the grown single crystal ingot, { A silicon carbide single crystal ingot manufacturing method in which a silicon carbide single crystal growth seed crystal having an inclined surface inclined from the 0001} plane by 20 ° or more and less than 90 ° on the growth surface is cut out and the silicon carbide single crystal growth is repeated N times. The angle difference in the {0001} plane between the inclination direction of the inclined surface of the seed crystal used in the (n-1) th growth step and the inclination direction of the inclined surface of the seed crystal used in the nth growth step is 45 °. More than 135 degrees Method of manufacturing a silicon carbide single crystal ingot.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005044305A JP4603386B2 (en) | 2005-02-21 | 2005-02-21 | Method for producing silicon carbide single crystal |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005044305A JP4603386B2 (en) | 2005-02-21 | 2005-02-21 | Method for producing silicon carbide single crystal |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2006225232A true JP2006225232A (en) | 2006-08-31 |
JP4603386B2 JP4603386B2 (en) | 2010-12-22 |
Family
ID=36986921
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2005044305A Active JP4603386B2 (en) | 2005-02-21 | 2005-02-21 | Method for producing silicon carbide single crystal |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4603386B2 (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009102187A (en) * | 2007-10-22 | 2009-05-14 | Nippon Steel Corp | Crucible for growth of silicon carbide single crystal, method of manufacturing silicon carbide single crystal using the same, and silicon carbide single crystal ingot |
JP2010126380A (en) * | 2008-11-26 | 2010-06-10 | Bridgestone Corp | Production method of silicon carbide single crystal |
JP2012046377A (en) * | 2010-08-26 | 2012-03-08 | Toyota Central R&D Labs Inc | METHOD FOR MANUFACTURING SiC SINGLE CRYSTAL |
US20120132132A1 (en) * | 2010-11-29 | 2012-05-31 | Toyota Jidosha Kabushiki Kaisha | Manufacturing method of silicon carbide single crystal |
JP2012153543A (en) * | 2011-01-21 | 2012-08-16 | Central Research Institute Of Electric Power Industry | Method for producing silicon carbide single crystal, silicon carbide single crystal wafer, method for producing silicon carbide semiconductor element, and silicon carbide semiconductor element |
JP2012153544A (en) * | 2011-01-21 | 2012-08-16 | Central Research Institute Of Electric Power Industry | Method for producing silicon carbide single crystal, silicon carbide single crystal wafer, method for producing silicon carbide semiconductor element, and silicon carbide semiconductor element |
JP2012240859A (en) * | 2011-05-16 | 2012-12-10 | Toyota Central R&D Labs Inc | SiC SINGLE CRYSTAL, SiC WAFER, AND SEMICONDUCTOR DEVICE |
JP2014031313A (en) * | 2013-09-26 | 2014-02-20 | Denso Corp | Single crystal substrate made of silicon carbide, and single crystal epitaxial wafer made of silicon carbide |
WO2014076893A1 (en) | 2012-11-19 | 2014-05-22 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Seed crystal for sic single-crystal growth, sic single crystal, and method of manufacturing the sic single crystal |
WO2014129137A1 (en) | 2013-02-20 | 2014-08-28 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Sic single crystal, sic wafer, sic substrate, and sic device |
WO2019088221A1 (en) * | 2017-11-01 | 2019-05-09 | セントラル硝子株式会社 | Method for producing silicon carbide single crystal |
CN110088363A (en) * | 2016-12-26 | 2019-08-02 | 昭和电工株式会社 | The manufacturing method of SiC ingot |
WO2019176446A1 (en) * | 2018-03-15 | 2019-09-19 | 信越半導体株式会社 | Production method of silicon carbide single crystal |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1045499A (en) * | 1996-07-31 | 1998-02-17 | Nippon Steel Corp | Production of silicon carbide single crystal and seed crystal used therefor |
JP2001002499A (en) * | 1999-06-17 | 2001-01-09 | Denso Corp | Seed crystal, production of silicon carbide single crystal using the same, silicon carbide single crystal body and device for producing single crystal |
JP2003321298A (en) * | 2002-04-30 | 2003-11-11 | Toyota Central Res & Dev Lab Inc | SiC SINGLE CRYSTAL AND METHOD FOR PRODUCING THE SAME, SiC WAFER WITH EPITAXIAL FILM AND METHOD FOR PRODUCING THE SAME, AND SiC ELECTRONIC DEVICE |
JP2005041710A (en) * | 2003-07-23 | 2005-02-17 | Nippon Steel Corp | Silicon carbide single crystal, silicon carbide single crystal wafer, and method for manufacturing silicon carbide single crystal |
-
2005
- 2005-02-21 JP JP2005044305A patent/JP4603386B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1045499A (en) * | 1996-07-31 | 1998-02-17 | Nippon Steel Corp | Production of silicon carbide single crystal and seed crystal used therefor |
JP2001002499A (en) * | 1999-06-17 | 2001-01-09 | Denso Corp | Seed crystal, production of silicon carbide single crystal using the same, silicon carbide single crystal body and device for producing single crystal |
JP2003321298A (en) * | 2002-04-30 | 2003-11-11 | Toyota Central Res & Dev Lab Inc | SiC SINGLE CRYSTAL AND METHOD FOR PRODUCING THE SAME, SiC WAFER WITH EPITAXIAL FILM AND METHOD FOR PRODUCING THE SAME, AND SiC ELECTRONIC DEVICE |
JP2005041710A (en) * | 2003-07-23 | 2005-02-17 | Nippon Steel Corp | Silicon carbide single crystal, silicon carbide single crystal wafer, and method for manufacturing silicon carbide single crystal |
Cited By (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009102187A (en) * | 2007-10-22 | 2009-05-14 | Nippon Steel Corp | Crucible for growth of silicon carbide single crystal, method of manufacturing silicon carbide single crystal using the same, and silicon carbide single crystal ingot |
JP2010126380A (en) * | 2008-11-26 | 2010-06-10 | Bridgestone Corp | Production method of silicon carbide single crystal |
JP2012046377A (en) * | 2010-08-26 | 2012-03-08 | Toyota Central R&D Labs Inc | METHOD FOR MANUFACTURING SiC SINGLE CRYSTAL |
US20120060751A1 (en) * | 2010-08-26 | 2012-03-15 | Denso Corporation | Manufacturing method of silicon carbide single crystal |
US8936682B2 (en) | 2010-08-26 | 2015-01-20 | Denso Corporation | Method of manufacturing homogeneous silicon carbide single crystal with low potential of generating defects |
US20120132132A1 (en) * | 2010-11-29 | 2012-05-31 | Toyota Jidosha Kabushiki Kaisha | Manufacturing method of silicon carbide single crystal |
JP2012116676A (en) * | 2010-11-29 | 2012-06-21 | Toyota Central R&D Labs Inc | Method of manufacturing silicon carbide single crystal |
US9051663B2 (en) * | 2010-11-29 | 2015-06-09 | Denso Corporation | Manufacturing method of silicon carbide single crystal |
JP2012153543A (en) * | 2011-01-21 | 2012-08-16 | Central Research Institute Of Electric Power Industry | Method for producing silicon carbide single crystal, silicon carbide single crystal wafer, method for producing silicon carbide semiconductor element, and silicon carbide semiconductor element |
JP2012153544A (en) * | 2011-01-21 | 2012-08-16 | Central Research Institute Of Electric Power Industry | Method for producing silicon carbide single crystal, silicon carbide single crystal wafer, method for producing silicon carbide semiconductor element, and silicon carbide semiconductor element |
JP2012240859A (en) * | 2011-05-16 | 2012-12-10 | Toyota Central R&D Labs Inc | SiC SINGLE CRYSTAL, SiC WAFER, AND SEMICONDUCTOR DEVICE |
KR101713006B1 (en) | 2011-05-16 | 2017-03-07 | 도요타지도샤가부시키가이샤 | Sic single crystal, sic wafer, and semiconductor device |
KR20140022074A (en) * | 2011-05-16 | 2014-02-21 | 도요타지도샤가부시키가이샤 | Sic single crystal, sic wafer, and semiconductor device |
US9166008B2 (en) | 2011-05-16 | 2015-10-20 | Kabushiki Kaisha Toyota Chuo Kenkyusho | SiC single crystal, SiC wafer, and semiconductor device |
WO2014076893A1 (en) | 2012-11-19 | 2014-05-22 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Seed crystal for sic single-crystal growth, sic single crystal, and method of manufacturing the sic single crystal |
US9534317B2 (en) | 2012-11-19 | 2017-01-03 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Seed crystal for SiC single-crystal growth, SiC single crystal, and method of manufacturing the SiC single crystal |
WO2014129137A1 (en) | 2013-02-20 | 2014-08-28 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Sic single crystal, sic wafer, sic substrate, and sic device |
US10125435B2 (en) | 2013-02-20 | 2018-11-13 | Kabushiki Kaisha Toyota Chuo Kenkyusho | SiC single crystal, SiC wafer, SiC substrate, and SiC device |
JP2014031313A (en) * | 2013-09-26 | 2014-02-20 | Denso Corp | Single crystal substrate made of silicon carbide, and single crystal epitaxial wafer made of silicon carbide |
CN110088363A (en) * | 2016-12-26 | 2019-08-02 | 昭和电工株式会社 | The manufacturing method of SiC ingot |
US11008670B2 (en) | 2016-12-26 | 2021-05-18 | Showa Denko K.K. | Manufacturing method of SiC ingot |
CN110088363B (en) * | 2016-12-26 | 2021-06-22 | 昭和电工株式会社 | Method for producing SiC ingot |
WO2019088221A1 (en) * | 2017-11-01 | 2019-05-09 | セントラル硝子株式会社 | Method for producing silicon carbide single crystal |
JP2019085328A (en) * | 2017-11-01 | 2019-06-06 | セントラル硝子株式会社 | Production method for silicon carbide single crystal |
JP7352058B2 (en) | 2017-11-01 | 2023-09-28 | セントラル硝子株式会社 | Method for manufacturing silicon carbide single crystal |
WO2019176446A1 (en) * | 2018-03-15 | 2019-09-19 | 信越半導体株式会社 | Production method of silicon carbide single crystal |
JP2019156698A (en) * | 2018-03-15 | 2019-09-19 | 信越半導体株式会社 | Method for manufacturing silicon carbide single crystal |
Also Published As
Publication number | Publication date |
---|---|
JP4603386B2 (en) | 2010-12-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4603386B2 (en) | Method for producing silicon carbide single crystal | |
JP4469396B2 (en) | Silicon carbide single crystal ingot, substrate obtained therefrom and epitaxial wafer | |
CN106435733B (en) | Silicon carbide single crystal and silicon carbide single crystal wafer | |
JP4818754B2 (en) | Method for producing silicon carbide single crystal ingot | |
JP4964672B2 (en) | Low resistivity silicon carbide single crystal substrate | |
JP4926556B2 (en) | Method for manufacturing silicon carbide single crystal ingot and silicon carbide single crystal substrate | |
JP4585359B2 (en) | Method for producing silicon carbide single crystal | |
WO2013031856A1 (en) | Silicon carbide single crystal wafer and manufacturing method for same | |
JP2004099340A (en) | Seed crystal for silicon carbide single crystal growth, silicon carbide single crystal ingot and method of manufacturing the same | |
JP3750622B2 (en) | SiC wafer with epitaxial film, manufacturing method thereof, and SiC electronic device | |
JP4690906B2 (en) | Seed crystal for growing silicon carbide single crystal, method for producing the same, and method for producing silicon carbide single crystal | |
JP3776374B2 (en) | Method for producing SiC single crystal and method for producing SiC wafer with epitaxial film | |
JP6526811B2 (en) | Method of processing a group III nitride crystal | |
JP4408247B2 (en) | Seed crystal for growing silicon carbide single crystal and method for producing silicon carbide single crystal using the same | |
JP4664464B2 (en) | Silicon carbide single crystal wafer with small mosaic | |
JP5212343B2 (en) | Silicon carbide single crystal ingot, substrate obtained therefrom and epitaxial wafer | |
JP5614387B2 (en) | Silicon carbide single crystal manufacturing method and silicon carbide single crystal ingot | |
JP2005239496A (en) | Silicon carbide raw material for growing silicon carbide single crystal, silicon carbide single crystal, and method for producing the same | |
JP2008115036A (en) | SEED CRYSTAL FOR GROWING SiC SINGLE CRYSTAL AND METHOD FOR PRODUCING SiC SINGLE CRYSTAL USING THE SAME | |
JP4494856B2 (en) | Seed crystal for silicon carbide single crystal growth, method for producing the same, and crystal growth method using the same | |
JP4224195B2 (en) | Seed crystal for growing silicon carbide single crystal and method for producing silicon carbide single crystal | |
JP5370025B2 (en) | Silicon carbide single crystal ingot | |
JP4157326B2 (en) | 4H type silicon carbide single crystal ingot and wafer | |
JP4850807B2 (en) | Crucible for growing silicon carbide single crystal and method for producing silicon carbide single crystal using the same | |
JP2004262709A (en) | GROWTH METHOD FOR SiC SINGLE CRYSTAL |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070905 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090917 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090929 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091130 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100622 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100819 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100928 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20101001 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131008 Year of fee payment: 3 |
|
R151 | Written notification of patent or utility model registration |
Ref document number: 4603386 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131008 Year of fee payment: 3 |
|
S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131008 Year of fee payment: 3 |
|
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 |
|
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: R313111 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |