JP6178227B2 - Crystal growth method of silicon carbide - Google Patents
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本発明は、炭化珪素の結晶成長方法に関し、より詳細には、坩堝内のＳｉ−Ｃ溶液の組成変動を抑え、坩堝の内壁に析出する多結晶や添加金属元素Ｍと炭素Ｃが結合して形成される金属炭化物の発生も抑制して、低欠陥で高品質な単結晶炭化珪素を得ることを可能とする技術に関する。 The present invention relates to a method for crystal growth of silicon carbide. More specifically, the composition variation of the Si—C solution in the crucible is suppressed, and the polycrystals and additive metal elements M and carbon C deposited on the inner wall of the crucible are combined. The present invention relates to a technique capable of suppressing the generation of metal carbide to be formed and obtaining high-quality single crystal silicon carbide with low defects.
炭化珪素（ＳｉＣ）はワイドバンドギャップ半導体材料であり、熱伝導性および化学的安定性に優れ、絶縁破壊特性および飽和ドリフト速度等のトランジスタ特性の観点からも、パワーデバイスとしての優れた基本的物理特性を有している。このような理由により、ＳｉＣは、次世代のパワーデバイス用の材料としての期待が高まっており、ＳｉＣパワーデバイスの製品化も報告されている。 Silicon carbide (SiC) is a wide band gap semiconductor material that has excellent thermal conductivity and chemical stability, and excellent basic physics as a power device from the viewpoint of transistor characteristics such as dielectric breakdown characteristics and saturation drift velocity. It has characteristics. For these reasons, SiC is expected as a material for next-generation power devices, and the commercialization of SiC power devices has also been reported.
しかし、ＳｉＣ基板は、Ｓｉ基板に比較して高価であることに加え、単結晶基板の低欠陥化・高品質化が十分ではないという問題がある。 However, the SiC substrate has a problem that the single crystal substrate is not sufficiently low in defect and high in quality, in addition to being expensive compared to the Si substrate.
低欠陥で高品質なＳｉＣ単結晶基板の製造が難しい主な理由は、常圧下では融解しないことにある。半導体デバイス用基板として広く用いられるＳｉの場合、常圧下での融点は１４１４℃であり、このＳｉ融液から、ＣＺ法やＦＺ法により低欠陥・高品質で大口径の単結晶を得ることができる。 The main reason why it is difficult to produce a SiC single crystal substrate with low defects and high quality is that it does not melt under normal pressure. In the case of Si widely used as a substrate for semiconductor devices, the melting point under normal pressure is 1414 ° C. From this Si melt, it is possible to obtain a single crystal with a low defect, high quality and large diameter by the CZ method or the FZ method. it can.
これに対し、ＳｉＣの場合、常圧下で加熱すると２０００℃程度の温度で昇華してしまうため、ＣＺ法やＦＺ法による結晶成長方法は採用できない。そのため、現在では、ＳｉＣ単結晶は、主として、改良レーリ法をはじめとする昇華法により製造されている。 On the other hand, in the case of SiC, if it is heated under normal pressure, it sublimates at a temperature of about 2000 ° C., so that a crystal growth method by the CZ method or the FZ method cannot be adopted. Therefore, at present, SiC single crystals are mainly produced by a sublimation method including an improved Rayleigh method.
しかしながら、昇華法により得られたＳｉＣ単結晶を用いてパワーデバイスを作製しても、その特性は必ずしも十分とは言えない。その原因は、ＳｉＣ単結晶の低欠陥化が容易ではないことにある。昇華法による結晶成長は、気相からの析出現象であり、成長速度は遅く、反応空間内の温度管理も難しい。近年では、各種研究開発機関による精力的な改良・改善の結果、マイクロパイプの転移密度は低減してきているものの、貫通らせん転移や刃状転移、基底面転移などの、デバイスの電気特性に影響を与える格子欠陥に関しては、未だ、高い密度で内在しているという状況にある。 However, even if a power device is manufactured using a SiC single crystal obtained by the sublimation method, the characteristics are not necessarily sufficient. The cause is that it is not easy to reduce the defects of the SiC single crystal. Crystal growth by the sublimation method is a precipitation phenomenon from the gas phase, the growth rate is slow, and temperature control in the reaction space is difficult. In recent years, as a result of vigorous improvements and improvements by various research and development institutions, the transition density of micropipes has been reduced, but it has an effect on the electrical characteristics of devices such as threading spiral transition, edge transition, and basal plane transition. The lattice defects to be given are still present at a high density.
そこで、最近では、溶液法による炭化珪素の結晶成長方法が注目されるようになってきた（例えば、特許文献１〜３などを参照）。上述のように、ＳｉＣそのものは、常圧下では融解しない。そこで、溶液法によるＳｉＣ単結晶の製造方法では、黒鉛るつぼ内のＳｉ融液に、坩堝の下方の高温部からＣを溶解せしめ、このＳｉ−Ｃ融液に、ＳｉＣ種結晶を接触させ、ＳｉＣ種結晶上にエピタキシャル成長させてＳｉＣ単結晶を得ている。このような溶液法では、ＳｉＣの結晶成長が、熱平衡にきわめて近い状態で進行するため、昇華法で得られたＳｉＣ単結晶に比較して、低欠陥なものが得られる。 Therefore, recently, a silicon carbide crystal growth method using a solution method has been attracting attention (see, for example, Patent Documents 1 to 3). As described above, SiC itself does not melt under normal pressure. Therefore, in a method for producing an SiC single crystal by a solution method, C is dissolved in a Si melt in a graphite crucible from a high temperature portion below the crucible, and an SiC seed crystal is brought into contact with the Si-C melt, and SiC. An SiC single crystal is obtained by epitaxial growth on a seed crystal. In such a solution method, since crystal growth of SiC proceeds in a state very close to thermal equilibrium, a defect having a lower defect is obtained as compared with a SiC single crystal obtained by a sublimation method.
ＳｉＣ単結晶を得るための溶液法には、種々の手法があり、非特許文献１（ＳｉＣパワーデバイス最新技術）では、（ａ）溶媒移動結晶成長法（ＴＳＭ：Traveling Solvent Method）、（ｂ）徐冷法（ＳＣＴ：Slow Cooling Technique）、（ｃ）蒸気気相固相法（ＶＬＳ: Vapor Liquid Solid）、（ｄ）種付け溶液成長法（ＴＳＳＧ: Top Seeded Solution Growth）の４つに大別されている。本明細書で用いる「溶液法」なる用語は、種付け溶液成長法（ＴＳＳＧ: Top Seeded Solution Growth）を意味する。 There are various methods for the solution method for obtaining the SiC single crystal. In Non-Patent Document 1 (the latest technology of SiC power device), (a) Solvent Transfer Crystal Growth Method (TSM), (b) Slow cooling technique (SCT), (c) Vapor Liquid Solid (VLS), (d) Top Seeded Solution Growth (TSSG) . The term “solution method” as used herein refers to a seeded solution growth method (TSSG).
溶液法によるＳｉＣ単結晶の製造方法では、黒鉛るつぼ内にＳｉ融液を形成するが、Ｓｉ融液へのＣの溶解度は１ａｔ％程度と極めて小さいため、一般に、Ｃを溶解し易くするためにＳｉ融液中に遷移金属などを添加する（特許文献１〜３などを参照）。 In the method of producing a SiC single crystal by the solution method, a Si melt is formed in a graphite crucible. Since the solubility of C in the Si melt is as small as about 1 at%, generally, in order to make C easy to dissolve. A transition metal or the like is added to the Si melt (see Patent Documents 1 to 3).
このような添加元素の種類と量は、Ｃの溶解を助長させること、溶液からＳｉＣが初晶として析出し残部が液相として上手く平衡すること、添加元素が炭化物やその他の相を析出させないこと、ＳｉＣの結晶多型のうち目的とする多型が安定して析出すること、更には、なるべく単結晶の成長速度を高くする溶液組成とすること等を考慮して決定される。 The kind and amount of such an additive element promotes dissolution of C, SiC precipitates as a primary crystal from the solution, and the balance is well balanced as a liquid phase, and the additive element does not precipitate carbide and other phases. The crystal polymorphism of SiC is determined in consideration of stable precipitation of the target polymorphism, and a solution composition that increases the growth rate of the single crystal as much as possible.
しかし、黒鉛坩堝を用いる従来の溶液法には、下記のような問題点がある。 However, the conventional solution method using a graphite crucible has the following problems.
第１は、ＳｉＣの単結晶成長につれて、Ｓｉ−Ｃ溶液から徐々にＳｉ成分が失われ、溶液組成が次第に変化してしまう問題である。ＳｉＣの単結晶成長中に溶液組成が変化すれば、当然に、ＳｉＣの析出環境は変化する。その結果、ＳｉＣの単結晶成長を、長時間、安定して継続することは難しくなる。 First, as the SiC single crystal grows, the Si component is gradually lost from the Si—C solution, and the solution composition gradually changes. If the solution composition changes during the growth of the SiC single crystal, the SiC deposition environment naturally changes. As a result, it becomes difficult to continue the single crystal growth of SiC stably for a long time.
第２は、黒鉛坩堝からのＣの過剰な融け込みの問題である。ＳｉＣの単結晶成長につれてＳｉ−Ｃ溶液から徐々にＳｉ成分が失われる一方で、Ｃは継続的に黒鉛坩堝から供給される。そのため、Ｓｉ−Ｃ溶液には、相対的にＣが過剰に融け込むという結果となり、溶液中のＳｉ／Ｃ組成比が変化してしまう。 The second is a problem of excessive melting of C from the graphite crucible. While the Si component is gradually lost from the Si-C solution as the SiC single crystal grows, C is continuously supplied from the graphite crucible. Therefore, the result is that C is relatively excessively melted in the Si—C solution, and the Si / C composition ratio in the solution changes.
第３は、黒鉛坩堝内壁面での、Ｓｉ−Ｃ溶液と接触する黒鉛坩堝表面でのＳｉＣ多結晶の析出の問題である。上述のように、黒鉛坩堝からＳｉ−Ｃ溶液中にＣが過剰に融け込むと、黒鉛坩堝内壁面に微細なＳｉＣ多結晶が発生し易くなる。そして、このようなＳｉＣ多結晶は、ＳｉＣ溶液中を浮遊し、結晶成長中のＳｉＣ単結晶とＳｉ−Ｃ溶液の固液界面近傍に達して、単結晶成長を阻害する結果となる。 The third is a problem of SiC polycrystal precipitation on the surface of the graphite crucible in contact with the Si—C solution on the inner wall surface of the graphite crucible. As described above, when C is excessively melted from the graphite crucible into the Si-C solution, fine SiC polycrystals are easily generated on the inner wall surface of the graphite crucible. Such SiC polycrystals float in the SiC solution and reach the vicinity of the solid-liquid interface between the SiC single crystal and the Si-C solution during crystal growth, resulting in inhibition of single crystal growth.
本発明は、このような従来法が抱える問題に鑑みてなされたもので、その目的とするところは、従来の黒鉛坩堝を用いる方法に比べ、Ｓ−Ｃ溶液の組成変動を少なくし、坩堝の内壁に析出する多結晶の発生も抑制することで、低欠陥で高品質な単結晶炭化珪素を得るための技術を提供することにある。 The present invention has been made in view of the problems of the conventional method, and the object of the present invention is to reduce the composition fluctuation of the S—C solution compared to the conventional method using a graphite crucible, An object of the present invention is to provide a technique for obtaining single crystal silicon carbide with low defects and high quality by suppressing generation of polycrystals precipitated on the inner wall.
上述の課題を解決するために、本発明に係る炭化珪素の結晶成長方法は、溶液法による炭化珪素の結晶成長方法であって、Ｓｉ−Ｃ溶液の収容部としてＳｉＣを主成分とする坩堝を用い、前記Ｓｉ−Ｃ溶液に、金属元素Ｍ（Ｍは、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｌｕの群から選択される少なくとも１種の金属元素）を含有させ、前記坩堝を加熱して、前記Ｓｉ−Ｃ溶液と接触する坩堝表面の高温領域から前記坩堝の主成分であるＳｉＣを源とするＳｉおよびＣを前記Ｓｉ−Ｃ溶液内に溶出せしめて、前記Ｓｉ−Ｃ溶液と接触する坩堝表面でのＳｉＣ多結晶の析出を抑制し、前記坩堝の上部から、前記Ｓｉ−Ｃ溶液にＳｉＣ種結晶を接触させて、該ＳｉＣ種結晶上にＳｉＣ単結晶を成長させる、ことを特徴とする。 In order to solve the above-described problems, a silicon carbide crystal growth method according to the present invention is a silicon carbide crystal growth method by a solution method, wherein a crucible containing SiC as a main component is used as an Si-C solution container. Used, in the Si-C solution, metal element M (M is at least one metal element selected from the group of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Lu) And heating the crucible to elute Si and C from the high temperature region on the surface of the crucible in contact with the Si-C solution into the Si-C solution. Then, the precipitation of SiC polycrystal on the surface of the crucible in contact with the Si-C solution is suppressed, the SiC seed crystal is brought into contact with the Si-C solution from the upper part of the crucible, and the SiC seed crystal is placed on the SiC seed crystal. It is characterized by growing single crystals That.
好ましくは、前記加熱は、前記ＳｉＣを主成分とする坩堝内のＳｉ−Ｃ溶液の温度が上側から下側に向かって高くなる温度分布を形成するように実行される。 Preferably, the heating is performed so as to form a temperature distribution in which the temperature of the Si—C solution in the crucible containing SiC as a main component increases from the upper side to the lower side.
また、好ましくは、前記金属元素Ｍの前記Ｓｉ−Ｃ溶液中の総含有量を、１ａｔ％〜８０ａｔ％とする。 Preferably, the total content of the metal element M in the Si-C solution is 1 at% to 80 at%.
また、好ましくは、前記加熱により、前記Ｓｉ−Ｃ溶液を１３００℃〜２３００℃の温度範囲に制御する。 Moreover, Preferably, the said Si-C solution is controlled to the temperature range of 1300 degreeC-2300 degreeC by the said heating.
さらに、好ましくは、前記加熱が、前記ＳｉＣを主成分とする坩堝を耐熱性炭素材料から成る第２の坩堝内に収容した状態で行われる。 Further preferably, the heating is performed in a state where the crucible mainly composed of SiC is accommodated in a second crucible made of a heat-resistant carbon material.
本発明によれば、ＳｉＣを主成分とする坩堝を用いることにより、Ｓｉ−Ｃ溶液の組成変動が少なくなり、坩堝の内壁に析出する多結晶や添加金属元素Ｍと炭素Ｃが結合して形成される金属炭化物の発生も抑制される。その結果、黒鉛坩堝を用いる従来の方法に比較して、低欠陥で高品質な単結晶炭化珪素が得られる。 According to the present invention, by using a crucible containing SiC as a main component, the composition fluctuation of the Si-C solution is reduced, and a polycrystal or additive metal element M deposited on the inner wall of the crucible and carbon C are combined. The occurrence of metal carbides is also suppressed. As a result, single crystal silicon carbide with low defects and high quality can be obtained as compared with the conventional method using a graphite crucible.
以下に、図面を参照して、本発明に係る溶液法による炭化珪素の結晶成長方法について説明する。なお、以降の説明においては、本発明を、ＳｉＣ坩堝を高周波加熱する態様で説明するが、加熱方法は高周波によるものに限定される必要はなく、Ｓｉ−Ｃ溶液の制御温度等に応じて、抵抗加熱等の他の方法によってもよい。 A silicon carbide crystal growth method by a solution method according to the present invention will be described below with reference to the drawings. In the following description, the present invention will be described in terms of high-frequency heating of the SiC crucible, but the heating method need not be limited to high-frequency heating, depending on the control temperature of the Si-C solution, etc. Other methods such as resistance heating may be used.
図１は、本発明に係る方法により炭化珪素を結晶成長させる際の、結晶成長装置の主要部の構成例を説明するための図である。 FIG. 1 is a diagram for explaining a configuration example of a main part of a crystal growth apparatus when silicon carbide is crystal-grown by the method according to the present invention.
図中、符号１はＳｉ−Ｃ溶液の収容部であるＳｉＣを主成分とする坩堝、符号２はこのＳｉＣ坩堝１を収容する耐熱性炭素材料から成る第２の坩堝、符号３は種結晶としてのＳｉＣ単結晶、符号４はＳｉＣ坩堝１内に形成されるＳｉ−Ｃ溶液、符号５はＳｉＣの結晶成長中に坩堝１（および坩堝２）を回転させるための坩堝回転軸、符号６は種結晶３を保持し且つＳｉＣの結晶成長中に種結晶３を回転させるための種結晶回転軸、符号７は黒鉛材料等で形成されたサセプタ、符号８は同じく黒鉛材料等で形成された断熱材、符号９はＳｉ−Ｃ溶液の蒸発を抑えるための上蓋、そして、符号１０はＳｉＣ坩堝１を加熱するとともにＳｉＣ溶液４内を好ましい温度分布とするための高周波コイルである。 In the figure, reference numeral 1 is a crucible mainly composed of SiC, which is a storage part for the Si-C solution, reference numeral 2 is a second crucible made of a heat-resistant carbon material for storing the SiC crucible 1, and reference numeral 3 is a seed crystal. 1 is a Si-C solution formed in the SiC crucible 1, 5 is a crucible rotating shaft for rotating the crucible 1 (and the crucible 2) during SiC crystal growth, and 6 is a seed. A seed crystal rotation axis for holding the crystal 3 and rotating the seed crystal 3 during SiC crystal growth, reference numeral 7 is a susceptor formed of graphite material, and reference numeral 8 is a heat insulating material also formed of graphite material Reference numeral 9 denotes an upper lid for suppressing the evaporation of the Si—C solution, and reference numeral 10 denotes a high-frequency coil for heating the SiC crucible 1 and making the SiC solution 4 have a preferable temperature distribution.
なお、図示はしないが、炉内の雰囲気を真空にするための排気口及び排気バルブ、ガス導入のためのガス導入口及びガス導入バルブが設けられている。また、加熱前のＳｉＣ坩堝１にはＳｉが充填されるが、Ｃ源を一緒に充填しておいてもよい。 Although not shown, an exhaust port and an exhaust valve for evacuating the atmosphere in the furnace, and a gas introduction port and a gas introduction valve for introducing gas are provided. Moreover, although the SiC crucible 1 before heating is filled with Si, a C source may be filled together.
図２は、本発明に係る方法により炭化珪素を結晶成長させる際の、Ｓｉ−Ｃ溶液内の温度分布を概念的に説明するための図である。図中のＴ1〜Ｔ4で示した曲線はそれぞれ、Ｓｉ−Ｃ溶液内での等温度曲面の断面を意味する温度曲線であり、Ｔ1＞Ｔ2＞Ｔ3＞Ｔ4の関係にある。つまり、ＳｉＣ坩堝１内のＳｉ−Ｃ溶液４は、上側から下側に向かって高くなる温度分布を有するとともに、各温度曲線（等温線）は下側に凸となる温度分布となっている。 FIG. 2 is a diagram for conceptually explaining the temperature distribution in the Si—C solution when silicon carbide is crystal-grown by the method according to the present invention. The curves indicated by T 1 to T 4 in the figure are temperature curves that mean cross sections of isothermal curved surfaces in the Si—C solution, and have a relationship of T 1 > T 2 > T 3 > T 4. . That is, the Si—C solution 4 in the SiC crucible 1 has a temperature distribution that increases from the upper side to the lower side, and each temperature curve (isothermal line) has a temperature distribution that protrudes downward.
本発明では、高周波コイル１０からのＳｉＣ坩堝１の誘導加熱により、Ｓｉ−Ｃ溶液４に上記の温度分布を形成するとともに、このＳｉ−Ｃ溶液４と接触するＳｉＣ坩堝１の表面から、該坩堝の主成分であるＳｉＣを源とするＳｉおよびＣをＳｉ−Ｃ溶液４内に溶出せしめる。そして、ＳｉＣ坩堝１の上部から、Ｓｉ−Ｃ溶液４にＳｉＣ種結晶３を接触させて、該ＳｉＣ種結晶３上にＳｉＣ単結晶を成長させる。従って、図２に示したＴ1〜Ｔ4のうち、少なくとも、温度Ｔ1はＳｉＣ坩堝１からＳｉおよびＣをＳｉ−Ｃ溶液４内に溶出せしめるに充分な程度に高い温度とされ、温度Ｔ4はＳｉＣ種結晶３上にＳｉＣが単結晶として成長するために充分な程度の温度とされる。 In the present invention, the above-mentioned temperature distribution is formed in the Si—C solution 4 by induction heating of the SiC crucible 1 from the high-frequency coil 10, and the crucible is formed from the surface of the SiC crucible 1 in contact with the Si—C solution 4. Si and C derived from SiC, which is the main component, are eluted in the Si-C solution 4. Then, from the upper part of the SiC crucible 1, the SiC seed crystal 3 is brought into contact with the Si—C solution 4 to grow a SiC single crystal on the SiC seed crystal 3. Accordingly, at least the temperature T 1 among T 1 to T 4 shown in FIG. 2 is set to a temperature high enough to elute Si and C from the SiC crucible 1 into the Si—C solution 4. 4 is set to a temperature sufficient for SiC to grow as a single crystal on the SiC seed crystal 3.
図３は、本発明に係る方法により炭化珪素を結晶成長させる際の、ＳｉＣ坩堝の壁面からＳｉ−Ｃ溶液中にＳｉおよびＣが溶出する様子を概念的に説明するための図である。なお、図中にＭで示したものは、Ｓｉ−Ｃ溶液４中へのＣ溶解度を高める効果を有する金属元素であり、添加される金属元素は１種に限らず、複数種の金属元素を添加する場合もある。 FIG. 3 is a diagram for conceptually explaining how Si and C are eluted from the wall surface of the SiC crucible into the Si—C solution when silicon carbide is crystal-grown by the method according to the present invention. In addition, what was shown by M in the figure is a metal element having an effect of increasing the solubility of C in the Si-C solution 4, and the added metal element is not limited to one type, and a plurality of types of metal elements are included. Sometimes added.
上述した温度分布を形成すると、Ｓｉ−Ｃ溶液４と接触するＳｉＣ坩堝１の表面（の高温領域）から、該坩堝１の主成分であるＳｉＣを源とするＳｉおよびＣがＳｉ−Ｃ溶液４内に溶出する。当然のことながら、この溶出したＳｉおよびＣは、Ｓｉ−Ｃ溶液４の新たなＳｉ成分およびＣ成分となり、ＳｉＣ種結晶３上に成長する単結晶の源となる。 When the temperature distribution described above is formed, Si and C using SiC as the main component of the crucible 1 from the surface (high temperature region) of the SiC crucible 1 in contact with the Si—C solution 4 become Si—C solution 4. Elute in. As a matter of course, the eluted Si and C become new Si components and C components of the Si—C solution 4, and become a source of a single crystal growing on the SiC seed crystal 3.
このようなＳｉＣ坩堝１からのＳｉおよびＣのＳｉ−Ｃ溶液４への溶出が生じる環境下にあっては、Ｓｉ−Ｃ溶液と接触する坩堝表面でのＳｉＣ多結晶の析出の問題は生じない。なぜならば、坩堝１の主成分であるＳｉＣがＳｉおよびＣとしてＳｉ−Ｃ溶液４へ溶出する条件下では、ＳｉとＣがＳｉＣとして析出する余地はないからである。つまり、Ｓｉ−Ｃ溶液の収容部としてＳｉＣを主成分とする坩堝を用いることにより、Ｓｉ−Ｃ溶液と接触する坩堝表面でのＳｉＣ多結晶の析出が抑制される。 In an environment in which elution of Si and C from the SiC crucible 1 into the Si—C solution 4 occurs, the problem of precipitation of SiC polycrystals on the surface of the crucible in contact with the Si—C solution does not occur. . This is because there is no room for Si and C to precipitate as SiC under the condition that SiC, which is the main component of the crucible 1, elutes into the Si-C solution 4 as Si and C. In other words, by using a crucible mainly composed of SiC as the Si—C solution container, precipitation of SiC polycrystals on the surface of the crucible in contact with the Si—C solution is suppressed.
加えて、ＳｉＣ坩堝を用いることにより、添加金属元素Ｍと炭素Ｃが結合して形成される金属炭化物の形成が抑制されるという効果もある。黒鉛坩堝を用いた場合には、Ｓｉ−Ｃ溶液中のＳｉ組成比が低下したりＣが過剰に溶け込んだりしてＳｉ／Ｃ組成比が小さくなると、炭素Ｃの溶け込みを容易化するために添加されている金属元素Ｍが炭素Ｃと結合し易くなり金属炭化物が形成される傾向にある、このような金属炭化物の融点は高く、Ｓｉ−Ｃ溶液中を漂って種結晶表面近傍に達し、ＳｉＣの単結晶化を阻害する要因となる。これに対し、ＳｉＣ坩堝を用いた場合には、Ｓｉ−Ｃ溶液中に炭素Ｃが過剰に溶け込むことがなく、その結果、上記の金属炭化物の形成が抑制され、育成するＳｉＣ結晶の単結晶化が容易なものとなる。 In addition, the use of the SiC crucible also has an effect of suppressing the formation of metal carbide formed by combining the additive metal element M and carbon C. When a graphite crucible is used, if the Si composition ratio in the Si-C solution decreases or C dissolves excessively and the Si / C composition ratio decreases, it is added to facilitate carbon C penetration. The metal element M is easily bonded to carbon C and tends to form metal carbide. Such metal carbide has a high melting point, drifts in the Si-C solution and reaches the vicinity of the seed crystal surface. It becomes a factor which inhibits the single crystallization of. On the other hand, when the SiC crucible is used, carbon C is not excessively dissolved in the Si-C solution, and as a result, the formation of the above-mentioned metal carbide is suppressed and single crystallization of the SiC crystal to be grown is performed. Is easy.
このように、本発明に係る炭化珪素の結晶成長方法では、Ｓｉ−Ｃ溶液の収容部としてＳｉＣを主成分とする坩堝を用い、該坩堝を加熱して、前記坩堝内のＳｉ−Ｃ溶液の温度が上側から下側に向かって高くなる温度分布を形成するとともに、前記Ｓｉ−Ｃ溶液と接触する坩堝表面の高温領域から前記坩堝の主成分であるＳｉＣを源とするＳｉおよびＣを前記Ｓｉ−Ｃ溶液内に溶出せしめて、前記Ｓｉ−Ｃ溶液と接触する坩堝表面でのＳｉＣ多結晶の析出を抑制し、前記坩堝の上部から、前記Ｓｉ−Ｃ溶液にＳｉＣ種結晶を接触させて、該ＳｉＣ種結晶上にＳｉＣ単結晶を成長させる。通常、結晶成長時のＳｉ−Ｃ溶液温度は、１３００℃〜２３００℃の温度範囲で制御する。 As described above, in the silicon carbide crystal growth method according to the present invention, a crucible mainly composed of SiC is used as the Si-C solution container, the crucible is heated, and the Si-C solution in the crucible is heated. A temperature distribution is formed in which the temperature increases from the upper side to the lower side, and Si and C from the high temperature region of the crucible surface in contact with the Si-C solution as a source of SiC as a main component of the crucible are converted into Si. Elution in a -C solution to suppress precipitation of SiC polycrystals on the surface of the crucible in contact with the Si-C solution, and contact the SiC seed crystal with the Si-C solution from the top of the crucible; A SiC single crystal is grown on the SiC seed crystal. Usually, the temperature of the Si—C solution during crystal growth is controlled in a temperature range of 1300 ° C. to 2300 ° C.
なお、ＳｉＣ単結晶の成長プロセス中、高周波コイル１０からの誘導加熱条件を適切に制御して、上述の温度分布を好適なものとすることはもとより、坩堝１の位置を上下に移動させたり、坩堝１や種結晶３を回転させるなどして、ＳｉＣ単結晶の成長速度とＳｉＣ溶液４中へのＳｉおよびＣの溶出速度を適切に制御し、ＳｉＣ単結晶の成長に伴ってＳｉ−Ｃ溶液４から失われたＳｉおよびＣだけ坩堝１から供給するようにすると、Ｓｉ−Ｃ溶液４の組成変動を抑えることができる。 In addition, during the SiC single crystal growth process, the induction heating conditions from the high-frequency coil 10 are appropriately controlled to make the above temperature distribution suitable, and the position of the crucible 1 can be moved up and down, The growth rate of the SiC single crystal and the elution rate of Si and C into the SiC solution 4 are appropriately controlled by rotating the crucible 1 and the seed crystal 3, and the Si—C solution accompanying the growth of the SiC single crystal. If only Si and C lost from 4 are supplied from the crucible 1, the composition variation of the Si—C solution 4 can be suppressed.
図４は、ＳｉＣ坩堝を用いる本発明の炭化珪素の結晶成長方法で生じている、ＳｉＣ坩堝からのＳｉおよびＣの溶出反応と、ＳｉＣ種結晶上へのＳｉＣの析出反応のメカニズムを、概念的に説明するための図である。この図は、ＳｉＣとＳｉ−Ｃ溶液（Ｓｉ、Ｃ、およびＭを含む溶液）との固液界面を断面としたときの、擬二元系の状態図である。縦軸は温度であり、横軸は溶液中のＣ濃度を表している。横軸は、右に進むほどＣ濃度が高く、右端ではＳｉＣ結晶となる。 FIG. 4 conceptually shows the elution reaction of Si and C from the SiC crucible and the precipitation reaction of SiC on the SiC seed crystal, which are caused by the silicon carbide crystal growth method of the present invention using the SiC crucible. It is a figure for demonstrating. This figure is a quasi-binary phase diagram when the solid-liquid interface between SiC and Si—C solution (solution containing Si, C, and M) is taken as a cross section. The vertical axis represents temperature, and the horizontal axis represents C concentration in the solution. On the horizontal axis, the C concentration increases as it goes to the right, and becomes a SiC crystal at the right end.
また、図中にＳＴ1〜ＳＴ4で示した曲線はそれぞれ、図２に示した温度Ｔ1〜Ｔ4における液相（Liquid）と固液共存相（Liquid＋SiC)の境界を表しており、溶解度曲線とも言われる。これらの溶解度曲線は、Ｓｉ−Ｃ溶液が、各曲線の示すところまでＣをＳｉ−Ｃ溶液中に溶解することができることを表している。溶解度曲線より左上は、ＳｉとＣとＭからなる液相であって、ＳｉとＣが均一に溶けている。一方、溶解度曲線より右下は、ＳｉＣの固相と、ＳｉとＣとＭが溶けている溶液相の、２相共存状態となる。 In addition, the curves indicated by ST 1 to ST 4 in the figure represent the boundaries between the liquid phase (Liquid) and the solid-liquid coexisting phase (Liquid + SiC) at temperatures T 1 to T 4 shown in FIG. Also called a curve. These solubility curves indicate that the Si—C solution can dissolve C in the Si—C solution up to the point indicated by each curve. The upper left of the solubility curve is a liquid phase composed of Si, C, and M, and Si and C are uniformly dissolved. On the other hand, the lower right of the solubility curve is a two-phase coexistence state of a SiC solid phase and a solution phase in which Si, C and M are dissolved.
図４に示したように、Ｃの溶解度は、溶液温度が高くなるほど増大するので、相対的に高温であるＴ1の溶解度曲線ＳＴ1は、他の溶解度曲線よりも図中の右側にあることとなる。一方、相対的に低温になるほどＣの溶解量が少なくなるため、Ｔ4の溶解度曲線ＳＴ4は、他の溶解度曲線の左側に位置することになる。 As shown in FIG. 4, since the solubility of C increases as the solution temperature increases, the solubility curve ST 1 of T 1 , which is a relatively high temperature, is on the right side in the figure than the other solubility curves. It becomes. On the other hand, since the dissolution amount of C decreases as the temperature becomes lower, the solubility curve ST 4 of T 4 is positioned on the left side of the other solubility curves.
ここで、Ｃ濃度がＣ0の溶液Ｌ１を考える。この溶液Ｌ１中に、図２に示したような温度分布（Ｔ1＞Ｔ2＞Ｔ3＞Ｔ4）があるとすると、溶液Ｌ１中の各温度おける溶解度状態は、図４中に示したａ〜ｄの各点で示される。図４から分かるように、点ａは温度Ｔ1における溶解度曲線ＳＴ1からみて左側にあるので、溶液はさらにＳｉＣを溶解することができ、Ｌ１溶液の組成は図中のａ’方向に進むことになる。つまり、ａ点の状態にある溶液に、坩堝のＳｉＣがＳｉとＣとなって溶け込んでくる。 Here, a solution L1 having a C concentration of C 0 is considered. If there is a temperature distribution (T 1 > T 2 > T 3 > T 4 ) as shown in FIG. 2 in the solution L1, the solubility state at each temperature in the solution L1 is shown in FIG. It is shown by each point of ad. As can be seen from FIG. 4, the point a is on the left side as seen from the solubility curve ST 1 at the temperature T 1 , so that the solution can further dissolve SiC, and the composition of the L1 solution proceeds in the direction a ′ in the figure. become. That is, SiC in the crucible is dissolved as Si and C in the solution at the point a.
Ｔ1よりも低温のＴ2の点であるｂも、僅かではあるが、上記の点ａと同様に、ＳｉＣを溶解することができ、Ｌ１溶液の組成は図中のｂ’方向に進むことになる。 Although b, which is a point of T 2 lower than T 1 , is also slight, SiC can be dissolved similarly to the above point a, and the composition of the L1 solution advances in the b ′ direction in the figure. become.
更に低温であるＴ3となると、ｃ点は温度Ｔ3における溶解度曲線ＳＴ3の下側に位置することとなるため、溶液はＳｉＣを溶解することができず、逆に、ＳｉＣを析出する状態となる。しかし、析出現象が実際に生じるためには、ある程度の過冷却な状態が実現している必要である。このため、溶解度曲線ＳＴ3のすぐ下に位置しているｃ点が充分に過冷却な状態であるかどうかは、一概には判断できない。ここでは、ｃ点の過冷却が充分でなく、ＳｉＣの析出は起こらないと仮定する。 Further, when T 3 is lower, the point c is located below the solubility curve ST 3 at the temperature T 3, so that the solution cannot dissolve SiC, and conversely, SiC is precipitated. It becomes. However, in order for the precipitation phenomenon to actually occur, it is necessary to realize a certain degree of supercooling. Therefore, the solubility of the immediately whether the point c which is located below is sufficiently subcooled state curve ST 3, can not be determined unconditionally. Here, it is assumed that the supercooling at the point c is not sufficient and no SiC precipitation occurs.
Ｔ3よりもさらに低温のＴ4のｄ点では、充分に過冷却な状態にあり、このＴ4の近傍温度で、ＳｉＣの析出が生じる。種結晶はこのような温度にあるから、該ＳｉＣ種結晶上にＳｉＣ単結晶が成長する。この析出反応によって、Ｌ１からＳｉＣが析出し、それに従って液相Ｌ１の組成はｄ’方向へと移る。 At the point d of T 4 , which is lower than T 3, it is in a sufficiently supercooled state, and SiC is precipitated at a temperature near T 4 . Since the seed crystal is at such a temperature, a SiC single crystal grows on the SiC seed crystal. By this precipitation reaction, SiC is precipitated from L1, and the composition of the liquid phase L1 moves in the d ′ direction accordingly.
坩堝からは継続的にＳｉとＣが溶出してくるが、通常、坩堝と種結晶を回転させながら単結晶の育成を行うから、Ｓｉ−Ｃ溶液は撹拌効果により溶液内組成の均一化が図られる。その結果、図３に示したような、溶液内での状態が実現されることとなる。 Although Si and C are continuously eluted from the crucible, since the single crystal is usually grown while rotating the crucible and the seed crystal, the Si-C solution can be made uniform in solution by the stirring effect. It is done. As a result, the state in the solution as shown in FIG. 3 is realized.
本発明によれば、溶液法によるＳｉＣ単結晶の製造において、高品質のＳｉＣ単結晶を、長時間に渡って安定的に製造することができる。その理由は、下記のように整理することができる。 ADVANTAGE OF THE INVENTION According to this invention, in manufacture of the SiC single crystal by a solution method, a high quality SiC single crystal can be manufactured stably over a long time. The reason can be summarized as follows.
従来の溶液法では、黒鉛坩堝に代表されるような耐熱性炭素材料から成る坩堝を用い、この坩堝に溶液を収容するとともに、坩堝からＣを溶出させて溶液中にＣを補給する。しかし、ＳｉＣの結晶成長が進むにつれて、溶液中のＳｉ成分の組成比の低下は避けられない。 In the conventional solution method, a crucible made of a heat-resistant carbon material such as a graphite crucible is used, and the solution is stored in the crucible and C is eluted from the crucible to replenish C in the solution. However, as the SiC crystal growth proceeds, the composition ratio of the Si component in the solution is inevitably lowered.
これに対し、本発明では、ＳｉＣを主成分と坩堝を容器に用い、坩堝成分であるＳｉＣを源としてＳｉとＣを溶液中に供給する。この場合、種結晶上にＳｉＣが結晶成長しても、それにより失われた溶液中のＳｉとＣはＳｉＣ坩堝から供給され、その結果、溶液の組成変化が抑制され、ＳｉＣ単結晶を安定して長時間成長させることができる。 In contrast, in the present invention, SiC is used as a main component and a crucible is used as a container, and Si and C are supplied into the solution using SiC as a crucible component as a source. In this case, even if SiC grows on the seed crystal, Si and C in the solution lost thereby are supplied from the SiC crucible, and as a result, the change in the composition of the solution is suppressed and the SiC single crystal is stabilized. Can grow for a long time.
このような本発明の結晶成長方法は、ＦＺ法に類似の結晶成長方法、若しくは、一種のＦＺ法であるとも言える。ＦＺ法においては、多結晶部の溶融と単結晶部の成長が、Ｓｉ溶融部を介して進行する。本発明の結晶成長方法においても、上記の多結晶部に相当する坩堝が加熱により融解し、上記の溶融部に相当するＳｉとＣを含む溶液を介して、種結晶上にＳｉＣ単結晶が成長する。 It can be said that the crystal growth method of the present invention is a crystal growth method similar to the FZ method or a kind of FZ method. In the FZ method, the melting of the polycrystalline part and the growth of the single crystal part proceed through the Si melting part. Also in the crystal growth method of the present invention, the crucible corresponding to the polycrystal part is melted by heating, and a SiC single crystal grows on the seed crystal through the solution containing Si and C corresponding to the melt part. To do.
以下に、実施例により、本発明の結晶成長方法について具体的に説明する。 The crystal growth method of the present invention will be specifically described below with reference to examples.
図１に示した構造の装置を用いて、ＳｉＣ単結晶を育成した。原料としてのＳｉ多結晶（純度９９ｗｔ％）およびＳｉ−Ｃ溶液中へのＣ溶解度を高める効果を有する金属であるＣｒ（純度９９ｗｔ％）を充填したＳｉＣ坩堝１を、耐熱性炭素材料から成る第２の坩堝２内に収容し、真空乃至Ａｒ雰囲気下で、高周波コイル１０により誘導加熱し、３時間かけてＳｉＣ坩堝１内に充填した原料を溶解した。 A SiC single crystal was grown using the apparatus having the structure shown in FIG. SiC crucible 1 filled with Cr (purity 99 wt%), which is a metal having an effect of increasing the solubility of C in a Si-C solution, and Si polycrystal as a raw material, is made of a heat-resistant carbon material. 2 in a crucible 2 and induction heating by a high-frequency coil 10 in a vacuum or Ar atmosphere to dissolve the raw material filled in the SiC crucible 1 over 3 hours.
ここで用いたＳｉＣ坩堝１は、外径７０ｍｍ、内径５０ｍｍ、外壁高さ８０ｍｍ、内壁高さ７０ｍｍである。また、種結晶３には、２１ｍｍ径で厚みが０．４ｍｍの４Ｈ型のＳｉＣ単結晶を用いた。この種結晶３を、黒鉛製の種結晶回転軸６（１９ｍｍ径）の端面に、結晶育成面がＣ面となるよう接着した。 The SiC crucible 1 used here has an outer diameter of 70 mm, an inner diameter of 50 mm, an outer wall height of 80 mm, and an inner wall height of 70 mm. The seed crystal 3 was a 4H SiC single crystal having a diameter of 21 mm and a thickness of 0.4 mm. This seed crystal 3 was bonded to the end face of a graphite seed crystal rotating shaft 6 (19 mm diameter) so that the crystal growth surface was a C plane.
ＳｉＣ坩堝１に充填したＳｉ多結晶およびＣｒは、これらが溶解した状態での浴組成が、Ｃｒが３８ａｔ％でＳｉが６２ａｔ％となるように調合した。なお、これらの原料には、不純物としてのＦｅが１ｗｔ％以下で含まれている。 The Si polycrystal and Cr filled in the SiC crucible 1 were prepared such that the bath composition in the state in which they were dissolved was 38 at% for Cr and 62 at% for Si. These raw materials contain Fe as an impurity in an amount of 1 wt% or less.
ＳｉＣ坩堝１内の溶液の表面温度を、装置の上方から光温度計測定したところ、１８００℃であった。この状態で２時間保持し、ＳｉＣ坩堝１から、ＳｉとＣを溶液中に溶出させてＳｉ−Ｃ（−Ｃｒ）溶液とし、坩堝１の上部から、Ｓｉ−Ｃ溶液にＳｉＣ種結晶３を接触させて、該ＳｉＣ種結晶３上にＳｉＣ単結晶を成長させた。 When the surface temperature of the solution in the SiC crucible 1 was measured with an optical thermometer from above the apparatus, it was 1800 ° C. Holding in this state for 2 hours, Si and C are eluted from the SiC crucible 1 into a Si—C (—Cr) solution, and the SiC seed crystal 3 is brought into contact with the Si—C solution from the top of the crucible 1. Thus, a SiC single crystal was grown on the SiC seed crystal 3.
結晶成長中は、種結晶回転軸６の引き上げ速度を０．５ｍｍ/ｈ、回転速度を２０ｒｐｍとした。また、ＳｉＣ坩堝１は２０ｒｐｍで回転させた。１０時間の単結晶成長の後、炉内にＡｒガスを導入し、室温まで冷却した。 During crystal growth, the pulling speed of the seed crystal rotating shaft 6 was 0.5 mm / h, and the rotating speed was 20 rpm. The SiC crucible 1 was rotated at 20 rpm. After growing the single crystal for 10 hours, Ar gas was introduced into the furnace and cooled to room temperature.
図５は、結晶成長後に取り出したＳｉＣ坩堝１を切断して得た断面の光学写真である。ＳｉＣ坩堝１の底部の両側において、Ｓｉ−Ｃ溶液へのＳｉおよびＣの溶出に伴う浸食が、明瞭に認められる。 FIG. 5 is an optical photograph of a cross section obtained by cutting the SiC crucible 1 taken out after crystal growth. On both sides of the bottom of the SiC crucible 1, erosion associated with the elution of Si and C into the Si—C solution is clearly observed.
図６は、上記の単結晶成長条件をパラメータとして炉内の温度分布をシミュレーションした結果で、図中には、ＳｉＣ坩堝１の右側半分の輪郭を白線で示した。このシミュレーションから、図５で明瞭に認められるＳｉＣ坩堝１の底部の両側の浸食部分の温度は、最も高温となっていることが分かる。また、このシミュレーションは、後述する実施例６の条件下でのものであるが、この結果によれば、図２中に示した温度は、Ｔ1＝１９３４℃、Ｔ2＝１９２６℃、Ｔ3＝１９１８℃、Ｔ4＝１９１８℃となっている。 FIG. 6 shows the result of simulating the temperature distribution in the furnace using the above-mentioned single crystal growth conditions as parameters. In the figure, the outline of the right half of the SiC crucible 1 is shown by a white line. From this simulation, it can be seen that the temperature of the erosion part on both sides of the bottom of the SiC crucible 1 clearly seen in FIG. 5 is the highest. Further, this simulation is performed under the conditions of Example 6 to be described later. According to this result, the temperatures shown in FIG. 2 are T 1 = 1934 ° C., T 2 = 1926 ° C., T 3 = 1918 ° C. and T 4 = 1918 ° C.
図７は、上述の条件下で得られたＳｉＣ単結晶の上面の光学写真（Ａ）および側面の光学写真（Ｂ）で、図７（Ｂ）に矢印で示したものがＳｉＣ単結晶である。目視では欠陥は認められず、表面も平滑であることが確認できる。 FIG. 7 is an optical photograph (A) of the upper surface and an optical photograph (B) of the upper surface of the SiC single crystal obtained under the above-described conditions, and the SiC single crystal is indicated by an arrow in FIG. 7 (B). . It can be confirmed that no defects are visually recognized and the surface is smooth.
図８は、比較例１として、ＳｉＣ坩堝１に代えて黒鉛坩堝を用いた以外は上述の実施例１と同条件下で育成したＳｉＣ結晶の、上面の光学写真（Ａ）および側面の光学写真（Ｂ）である。結晶面には多数の結晶粒界が認められ、単結晶は得られていない。 FIG. 8 shows an upper surface optical photograph (A) and a side optical photograph of a SiC crystal grown under the same conditions as in Example 1 except that a graphite crucible was used instead of the SiC crucible 1 as a comparative example 1. (B). Many crystal grain boundaries are observed on the crystal plane, and no single crystal is obtained.
溶液の初期組成が、Ｔｉが２０ａｔ％でＳｉが８０ａｔ％となるように調合したこと以外、実施例１と同条件でＳｉＣ単結晶の育成を行った。なお、これらの原料には、不純物としてのＦｅが１ｗｔ％以下で含まれている。 An SiC single crystal was grown under the same conditions as in Example 1 except that the initial composition of the solution was adjusted so that Ti was 20 at% and Si was 80 at%. These raw materials contain Fe as an impurity in an amount of 1 wt% or less.
図９（Ａ）は、上述の条件下で得られたＳｉＣ単結晶の上面の光学写真である。目視では欠陥は認められず、表面も平滑であることが確認できる。 FIG. 9A is an optical photograph of the upper surface of the SiC single crystal obtained under the above conditions. It can be confirmed that no defects are visually recognized and the surface is smooth.
図９（Ｂ）は、比較例２として、ＳｉＣ坩堝１に代えて黒鉛坩堝を用いた以外は上述の実施例２と同条件下で育成したＳｉＣ結晶の、上面の光学写真である。結晶面には多数の結晶粒界が認められ、単結晶は得られていない。 FIG. 9B is an optical photograph of the upper surface of a SiC crystal grown under the same conditions as in Example 2 except that a graphite crucible was used instead of the SiC crucible 1 as Comparative Example 2. Many crystal grain boundaries are observed on the crystal plane, and no single crystal is obtained.
溶液の初期組成が、Ａｌが２０ａｔ％でＳｉが８０ａｔ％となるように調合したこと以外、実施例１と同条件でＳｉＣ単結晶の育成を行った。なお、これらの原料には、不純物としてのＦｅが１ｗｔ％以下で含まれている。 A SiC single crystal was grown under the same conditions as in Example 1 except that the initial composition of the solution was adjusted so that Al was 20 at% and Si was 80 at%. These raw materials contain Fe as an impurity in an amount of 1 wt% or less.
図１０（Ａ）は、上述の条件下で得られたＳｉＣ単結晶の上面の光学写真である。目視では欠陥は認められず、表面も平滑であることが確認できる。 FIG. 10A is an optical photograph of the upper surface of the SiC single crystal obtained under the above conditions. It can be confirmed that no defects are visually recognized and the surface is smooth.
図１０（Ｂ）は、比較例３として、ＳｉＣ坩堝１に代えて黒鉛坩堝を用いた以外は上述の実施例３と同条件下で育成したＳｉＣ結晶の、上面の光学写真である。結晶面には多数の結晶粒界が認められ、単結晶は得られていない。 FIG. 10 (B) is an optical photograph of the upper surface of a SiC crystal grown under the same conditions as in Example 3 except that a graphite crucible was used instead of the SiC crucible 1 as a comparative example 3. Many crystal grain boundaries are observed on the crystal plane, and no single crystal is obtained.
溶液の初期組成が、Ｐｒが２０ａｔ％でＳｉが８０ａｔ％となるように調合したこと以外、実施例１と同条件でＳｉＣ単結晶の育成を行った。なお、これらの原料には、不純物としてのＦｅが１ｗｔ％以下で含まれている。 A SiC single crystal was grown under the same conditions as Example 1 except that the initial composition of the solution was such that Pr was 20 at% and Si was 80 at%. These raw materials contain Fe as an impurity in an amount of 1 wt% or less.
図１１（Ａ）は、上述の条件下で得られたＳｉＣ単結晶の上面の光学写真である。目視では欠陥は認められず、表面も平滑であることが確認できる。 FIG. 11A is an optical photograph of the upper surface of the SiC single crystal obtained under the above-described conditions. It can be confirmed that no defects are visually recognized and the surface is smooth.
図１１（Ｂ）は、比較例４として、ＳｉＣ坩堝１に代えて黒鉛坩堝を用いた以外は上述の実施例４と同条件下で育成したＳｉＣ結晶の、上面の光学写真である。結晶面には多数の結晶粒界が認められ、単結晶は得られていない。 FIG. 11B is an optical photograph of the upper surface of a SiC crystal grown under the same conditions as in Example 4 except that a graphite crucible was used instead of the SiC crucible 1 as Comparative Example 4. Many crystal grain boundaries are observed on the crystal plane, and no single crystal is obtained.
溶液の初期組成が、Ｐｒが２０ａｔ％でＣｒが３０ａｔ％でＳｉが５０ａｔ％となるように調合したこと以外、実施例１と同条件でＳｉＣ単結晶の育成を行った。なお、これらの原料には、不純物としてのＦｅが１ｗｔ％以下で含まれている。 An SiC single crystal was grown under the same conditions as in Example 1 except that the initial composition of the solution was such that Pr was 20 at%, Cr was 30 at%, and Si was 50 at%. These raw materials contain Fe as an impurity in an amount of 1 wt% or less.
図１２（Ａ）は、上述の条件下で得られたＳｉＣ単結晶の上面の光学写真である。目視では欠陥は認められず、表面も平滑であることが確認できる。 FIG. 12A is an optical photograph of the upper surface of the SiC single crystal obtained under the above conditions. It can be confirmed that no defects are visually recognized and the surface is smooth.
図１２（Ｂ）は、比較例５として、ＳｉＣ坩堝１に代えて黒鉛坩堝を用いた以外は上述の実施例５と同条件下で育成したＳｉＣ結晶の、上面の光学写真である。結晶面には多数の結晶粒界が認められ、単結晶は得られていない。 FIG. 12B is an optical photograph of the upper surface of a SiC crystal grown under the same conditions as in Example 5 except that a graphite crucible was used instead of SiC crucible 1 as Comparative Example 5. Many crystal grain boundaries are observed on the crystal plane, and no single crystal is obtained.
溶液の初期組成が、Ｐｒが２０ａｔ％でＦｅが３０ａｔ％でＳｉが５０ａｔ％となるように調合したこと以外、実施例１と同条件でＳｉＣ単結晶の育成を行った。なお、これらの原料には、不純物としてのＣｒが１ｗｔ％以下で含まれている。 A SiC single crystal was grown under the same conditions as in Example 1 except that the initial composition of the solution was such that Pr was 20 at%, Fe was 30 at%, and Si was 50 at%. These raw materials contain 1 wt% or less of Cr as an impurity.
図１３は、上述の条件下で得られたＳｉＣ単結晶の上面の光学写真である。目視では欠陥は認められず、表面も平滑であることが確認できる。 FIG. 13 is an optical photograph of the upper surface of the SiC single crystal obtained under the above-described conditions. It can be confirmed that no defects are visually recognized and the surface is smooth.
上記実施例では、Ｓｉ−Ｃ溶液中に添加する金属元素として、Ｃｒ、Ｔｉ，Ａｌ、Ｐｒが選択されているが、これら以外にも、種々の金属元素を選択し得る。 In the above embodiment, Cr, Ti, Al, and Pr are selected as the metal elements to be added to the Si—C solution, but various metal elements can be selected in addition to these.
例えば、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｌｕの群から選択される少なくとも１種の金属元素であってよい。 For example, it may be at least one metal element selected from the group of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, and Lu.
また、例えば、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕの群から選択される少なくとも１種の金属元素であってよい。 For example, it may be at least one metal element selected from the group of Ti, V, Cr, Mn, Fe, Co, Ni, and Cu.
さらに、例えば、Ａｌ、Ｇａ、Ｇｅ、Ｓｎ、Ｐｂ、Ｚｎの群から選択される少なくとも１種の金属元素であってよい。 Furthermore, for example, it may be at least one metal element selected from the group of Al, Ga, Ge, Sn, Pb, and Zn.
なお、上記金属元素の組み合わせとしてもよく、例えば、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｌｕの群から選択される少なくとも１種の金属元素Ｍ１と、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕの群から選択される少なくとも１種の金属元素Ｍ２の組み合わせであってよい。 Note that a combination of the above metal elements may be used. For example, at least one metal element M1 selected from the group of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, and Lu, and Ti , V, Cr, Mn, Fe, Co, Ni, and a combination of at least one metal element M2 selected from the group of Cu.
通常は、このような金属元素の添加は、Ｓｉ−Ｃ溶液中の総含有量を１ａｔ％〜８０ａｔ％とする。 Usually, the addition of such metal elements makes the total content in the Si-C solution 1 at% to 80 at%.
上述したように、本発明に係る炭化珪素の結晶成長方法によれば、従来の黒鉛坩堝を用いる方法に比べ、Ｓ−Ｃ溶液の組成変動が少なく、坩堝の内壁に析出する多結晶の発生も抑制される。その結果、低欠陥で高品質な単結晶炭化珪素が得られる。 As described above, according to the crystal growth method of silicon carbide according to the present invention, the composition variation of the S—C solution is small compared to the conventional method using a graphite crucible, and polycrystals precipitated on the inner wall of the crucible are also generated. It is suppressed. As a result, high-quality single crystal silicon carbide with low defects can be obtained.
本発明に係る炭化珪素の結晶成長方法は、下記のような発明として整理することができる。 The silicon carbide crystal growth method according to the present invention can be organized as the following invention.
第１の態様のものは、溶液法による炭化珪素の結晶成長方法であって、Ｓｉ−Ｃ溶液の収容部としてＳｉＣを主成分とする坩堝を用い、該坩堝を加熱して、前記坩堝内のＳｉ−Ｃ溶液の温度が上側から下側に向かって高くなる温度分布を形成するとともに、前記Ｓｉ−Ｃ溶液と接触する坩堝表面の高温領域から該坩堝の主成分であるＳｉＣを源とするＳｉおよびＣを前記Ｓｉ−Ｃ溶液内に溶出せしめ、前記坩堝の上部から、前記Ｓｉ−Ｃ溶液にＳｉＣ種結晶を接触させて、該ＳｉＣ種結晶上にＳｉＣ単結晶を成長させる、ことを特徴とする炭化珪素の結晶成長方法。 The first aspect is a silicon carbide crystal growth method by a solution method, wherein a crucible containing SiC as a main component is used as an Si-C solution container, the crucible is heated, and the inside of the crucible is heated. A temperature distribution in which the temperature of the Si-C solution increases from the upper side to the lower side is formed, and Si from the high temperature region on the surface of the crucible in contact with the Si-C solution as a source of SiC as a main component of the crucible And SiC are eluted in the Si-C solution, and an SiC seed crystal is brought into contact with the Si-C solution from the upper part of the crucible to grow a SiC single crystal on the SiC seed crystal. A method for growing silicon carbide crystals.
好ましくは、前記加熱は、前記坩堝内における等温線が下側に凸となる温度分布となるように実行される。 Preferably, the heating is performed such that the isothermal line in the crucible has a temperature distribution that protrudes downward.
また、好ましくは、前記Ｓｉ−Ｃ溶液には、該Ｓｉ−Ｃ溶液中へのＣ溶解度を高める効果を有する金属Ｍが予め添加される。 Preferably, a metal M having an effect of increasing the solubility of C in the Si—C solution is added in advance to the Si—C solution.
第２の態様のものは、溶液法による炭化珪素の結晶成長方法であって、Ｓｉ−Ｃ溶液の収容部としてＳｉＣを主成分とする坩堝を用い、該坩堝を加熱して、前記Ｓｉ−Ｃ溶液と接触する坩堝表面の高温領域から前記坩堝の主成分であるＳｉＣを源とするＳｉおよびＣを前記Ｓｉ−Ｃ溶液内に溶出せしめて、前記Ｓｉ−Ｃ溶液と接触する坩堝表面でのＳｉＣ多結晶の析出を抑制し、前記坩堝の上部から、前記Ｓｉ−Ｃ溶液にＳｉＣ種結晶を接触させて、該ＳｉＣ種結晶上にＳｉＣ単結晶を成長させる、ことを特徴とする炭化珪素の結晶成長方法。 The second aspect is a silicon carbide crystal growth method by a solution method, wherein a crucible containing SiC as a main component is used as an Si-C solution containing portion, and the crucible is heated to obtain the Si-C. Si and C derived from SiC, which is the main component of the crucible, are eluted from the high temperature region on the crucible surface in contact with the solution into the Si-C solution, and SiC on the crucible surface in contact with the Si-C solution is obtained. A silicon carbide crystal characterized by suppressing precipitation of polycrystals, bringing a SiC seed crystal into contact with the Si-C solution from above the crucible, and growing a SiC single crystal on the SiC seed crystal. Growth method.
好ましくは、前記加熱は、前記ＳｉＣを主成分とする坩堝内のＳｉ−Ｃ溶液の温度が上側から下側に向かって高くなる温度分布を形成するように実行される。 Preferably, the heating is performed so as to form a temperature distribution in which the temperature of the Si—C solution in the crucible containing SiC as a main component increases from the upper side to the lower side.
また、好ましくは、前記Ｓｉ−Ｃ溶液には、該Ｓｉ−Ｃ溶液中へのＣ溶解度を高める効果を有する金属Ｍが予め添加される。 Preferably, a metal M having an effect of increasing the solubility of C in the Si—C solution is added in advance to the Si—C solution.
第３の態様のものは、溶液法による炭化珪素の結晶成長方法であって、Ｓｉ−Ｃ溶液の収容部としてＳｉＣを主成分とする坩堝を用い、前記Ｓｉ−Ｃ溶液に、第１の金属元素Ｍ１（Ｍ１は、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｌｕの群から選択される少なくとも１種の金属元素）と第２の金属元素Ｍ２（Ｍ２は、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕの群から選択される少なくとも１種の金属元素）を含有させ、前記坩堝を加熱して、前記Ｓｉ−Ｃ溶液と接触する坩堝表面の高温領域から前記坩堝の主成分であるＳｉＣを源とするＳｉおよびＣを前記Ｓｉ−Ｃ溶液内に溶出せしめて、前記Ｓｉ−Ｃ溶液と接触する坩堝表面でのＳｉＣ多結晶の析出を抑制し、前記坩堝の上部から、前記Ｓｉ−Ｃ溶液にＳｉＣ種結晶を接触させて、該ＳｉＣ種結晶上にＳｉＣ単結晶を成長させる、ことを特徴とする炭化珪素の結晶成長方法。 A third aspect is a silicon carbide crystal growth method by a solution method, wherein a crucible containing SiC as a main component is used as an Si-C solution container, and the first metal is used in the Si-C solution. An element M1 (M1 is at least one metal element selected from the group of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, and Lu) and a second metal element M2 (M2 is , Ti, V, Cr, Mn, Fe, Co, Ni, Cu), and the crucible surface in contact with the Si-C solution by heating the crucible Si and C originating from SiC, which is the main component of the crucible, are eluted from the high temperature region of the crucible into the Si-C solution to suppress the precipitation of SiC polycrystals on the surface of the crucible contacting the Si-C solution. And from the top of the crucible into the Si-C solution Contacting the iC seed crystal, growing a SiC single crystal on the SiC seed crystal, the crystal growth method of silicon carbide, characterized in that.
第４の態様のものは、溶液法による炭化珪素の結晶成長方法であって、Ｓｉ−Ｃ溶液の収容部としてＳｉＣを主成分とする坩堝を用い、前記Ｓｉ−Ｃ溶液に、金属元素Ｍ（Ｍは、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｌｕの群から選択される少なくとも１種の金属元素）を含有させ、前記坩堝を加熱して、前記Ｓｉ−Ｃ溶液と接触する坩堝表面の高温領域から前記坩堝の主成分であるＳｉＣを源とするＳｉおよびＣを前記Ｓｉ−Ｃ溶液内に溶出せしめて、前記Ｓｉ−Ｃ溶液と接触する坩堝表面でのＳｉＣ多結晶の析出を抑制し、前記坩堝の上部から、前記Ｓｉ−Ｃ溶液にＳｉＣ種結晶を接触させて、該ＳｉＣ種結晶上にＳｉＣ単結晶を成長させる、ことを特徴とする炭化珪素の結晶成長方法。 The fourth embodiment is a silicon carbide crystal growth method by a solution method, wherein a crucible containing SiC as a main component is used as a Si-C solution container, and the metal element M ( M contains at least one metal element selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, and Lu), and heats the crucible to -Si and C from the high temperature region on the surface of the crucible in contact with the -C solution are eluted into the Si-C solution from the main component of the crucible, and the surface of the crucible in contact with the Si-C solution The silicon carbide is characterized in that the precipitation of SiC polycrystal is suppressed, the SiC seed crystal is brought into contact with the Si-C solution from the upper part of the crucible, and the SiC single crystal is grown on the SiC seed crystal. Crystal growth method.
第５の態様のものは、溶液法による炭化珪素の結晶成長方法であって、Ｓｉ−Ｃ溶液の収容部としてＳｉＣを主成分とする坩堝を用い、前記Ｓｉ−Ｃ溶液に、金属元素Ｍ（Ｍは、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕの群から選択される少なくとも１種の金属元素）を含有させ、前記坩堝を加熱して、前記Ｓｉ−Ｃ溶液と接触する坩堝表面の高温領域から前記坩堝の主成分であるＳｉＣを源とするＳｉおよびＣを前記Ｓｉ−Ｃ溶液内に溶出せしめて、前記Ｓｉ−Ｃ溶液と接触する坩堝表面でのＳｉＣ多結晶の析出を抑制し、前記坩堝の上部から、前記Ｓｉ−Ｃ溶液にＳｉＣ種結晶を接触させて、該ＳｉＣ種結晶上にＳｉＣ単結晶を成長させる、ことを特徴とする炭化珪素の結晶成長方法。 A fifth aspect is a silicon carbide crystal growth method by a solution method, wherein a crucible containing SiC as a main component is used as a Si-C solution container, and the metal element M ( M is at least one metal element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, and Cu), and the crucible is heated to come into contact with the Si-C solution. Si and C derived from SiC, which is the main component of the crucible, are eluted from the high temperature region of the crucible surface into the Si-C solution, and SiC polycrystal is precipitated on the crucible surface in contact with the Si-C solution. And a SiC single crystal is grown on the SiC seed crystal by bringing the SiC seed crystal into contact with the Si—C solution from above the crucible.
第６の態様のものは、溶液法による炭化珪素の結晶成長方法であって、Ｓｉ−Ｃ溶液の収容部としてＳｉＣを主成分とする坩堝を用い、前記Ｓｉ−Ｃ溶液に、金属元素Ｍ（Ｍは、Ａｌ、Ｇａ、Ｇｅ、Ｓｎ、Ｐｂ、Ｚｎの群から選択される少なくとも１種の金属元素）を含有させ、前記坩堝を加熱して、前記Ｓｉ−Ｃ溶液と接触する坩堝表面の高温領域から前記坩堝の主成分であるＳｉＣを源とするＳｉおよびＣを前記Ｓｉ−Ｃ溶液内に溶出せしめて、前記Ｓｉ−Ｃ溶液と接触する坩堝表面でのＳｉＣ多結晶の析出を抑制し、前記坩堝の上部から、前記Ｓｉ−Ｃ溶液にＳｉＣ種結晶を接触させて、該ＳｉＣ種結晶上にＳｉＣ単結晶を成長させる、ことを特徴とする炭化珪素の結晶成長方法。 A sixth aspect is a silicon carbide crystal growth method by a solution method, wherein a crucible containing SiC as a main component is used as a Si-C solution container, and the metal element M ( M is at least one metal element selected from the group consisting of Al, Ga, Ge, Sn, Pb, and Zn), and heats the crucible so that the high temperature of the crucible surface in contact with the Si-C solution Si and C derived from SiC as a main component of the crucible from the region are eluted in the Si-C solution, and the precipitation of SiC polycrystals on the surface of the crucible in contact with the Si-C solution is suppressed, A silicon carbide crystal growth method, comprising bringing a SiC seed crystal into contact with the Si-C solution from above the crucible and growing a SiC single crystal on the SiC seed crystal.
上記の第３〜６の態様において、好ましくは、前記加熱は、前記ＳｉＣを主成分とする坩堝内のＳｉ−Ｃ溶液の温度が上側から下側に向かって高くなる温度分布を形成するように実行される。 In the above third to sixth aspects, preferably, the heating forms a temperature distribution in which the temperature of the Si—C solution in the crucible containing SiC as a main component increases from the upper side to the lower side. Executed.
本発明では、好ましくは、前記第１の金属元素Ｍ１と前記第２の金属元素Ｍ２の前記Ｓｉ−Ｃ溶液中の総含有量、若しくは、前記金属元素Ｍの前記Ｓｉ−Ｃ溶液中の総含有量を１ａｔ％〜８０ａｔ％とする。 In the present invention, preferably, the total content of the first metal element M1 and the second metal element M2 in the Si-C solution, or the total content of the metal element M in the Si-C solution. The amount is 1 at% to 80 at%.
また、本発明では、好ましくは、前記加熱により、前記Ｓｉ−Ｃ溶液を１３００℃〜２３００℃の温度範囲に制御する。 Moreover, in this invention, Preferably, the said Si-C solution is controlled to the temperature range of 1300 degreeC-2300 degreeC by the said heating.
さらに、本発明では、好ましくは、前記加熱が、前記ＳｉＣを主成分とする坩堝を耐熱性炭素材料から成る第２の坩堝内に収容した状態で行われる。 Furthermore, in the present invention, preferably, the heating is performed in a state where the crucible mainly composed of SiC is housed in a second crucible made of a heat-resistant carbon material.
本発明に係る炭化珪素の結晶成長方法によれば、従来の黒鉛坩堝を用いる方法に比べ、Ｓ−Ｃ溶液の組成変動が少なく、坩堝の内壁に析出する多結晶や添加金属元素Ｍと炭素Ｃが結合して形成される金属炭化物の発生も抑制される。その結果、低欠陥で高品質な単結晶炭化珪素が得られる。 According to the silicon carbide crystal growth method according to the present invention, the composition variation of the S—C solution is less than that in the conventional method using a graphite crucible, and the polycrystalline or additive metal element M and carbon C precipitated on the inner wall of the crucible. Generation of metal carbides formed by bonding is also suppressed. As a result, high-quality single crystal silicon carbide with low defects can be obtained.
１ ＳｉＣを主成分とする坩堝
２ 耐熱性炭素材料から成る第２の坩堝
３ 種結晶
４ Ｓｉ−Ｃ溶液
５ 坩堝回転軸
６ 種結晶回転軸
７ サセプタ
８ 断熱材
９ 上蓋
１０ 高周波コイル
DESCRIPTION OF SYMBOLS 1 Crucible which has SiC as a main component 2 2nd crucible which consists of heat resistant carbon materials 3 Seed crystal 4 Si-C solution 5 Crucible rotating shaft 6 Seed crystal rotating shaft 7 Susceptor 8 Heat insulating material 9 Top lid 10 High frequency coil
Claims (4)
Ｓｉ−Ｃ溶液の収容部としてＳｉＣを主成分とする坩堝を用い、
前記Ｓｉ−Ｃ溶液に、金属元素Ｍ（Ｍは、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｌｕの群から選択される少なくとも１種の金属元素）を含有させ、
前記坩堝内のＳｉ−Ｃ溶液の温度が上側から下側に向かって徐々に高くなり、かつ、断面で見たときに前記坩堝の底部の両側の温度が最も高くなる温度分布を形成するように加熱して、前記Ｓｉ−Ｃ溶液と接触する坩堝表面の高温領域から前記坩堝の主成分であるＳｉＣを源とするＳｉおよびＣを前記Ｓｉ−Ｃ溶液内に溶出せしめて、前記Ｓｉ−Ｃ溶液と接触する坩堝表面でのＳｉＣ多結晶の析出を抑制し、
前記坩堝の上部から、前記Ｓｉ−Ｃ溶液にＳｉＣ種結晶を接触させて、該ＳｉＣ種結晶上にＳｉＣ単結晶を成長させる、ことを特徴とする炭化珪素の結晶成長方法。 A crystal growth method of silicon carbide by a solution method,
Using a crucible containing SiC as a main component as a container for the Si-C solution,
The Si—C solution contains a metal element M (M is at least one metal element selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, and Lu). Let
A temperature distribution is formed so that the temperature of the Si-C solution in the crucible gradually increases from the upper side to the lower side, and the temperature on both sides of the bottom of the crucible becomes the highest when viewed in cross section. The Si-C solution is heated to elute Si and C from the high temperature region of the crucible surface in contact with the Si-C solution into the Si-C solution. The precipitation of SiC polycrystal on the crucible surface in contact with
A silicon carbide crystal growth method, comprising bringing a SiC seed crystal into contact with the Si-C solution from above the crucible and growing a SiC single crystal on the SiC seed crystal.
The silicon carbide crystal growth according to any one of claims 1 to 3, wherein the heating is performed in a state where the crucible mainly composed of SiC is accommodated in a second crucible made of a heat-resistant carbon material. Method.
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