JP2007223821A - Seed crystal for growing silicon carbide single crystal, silicon carbide single crystal ingot, and production methods therefor - Google Patents

Seed crystal for growing silicon carbide single crystal, silicon carbide single crystal ingot, and production methods therefor Download PDF

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JP2007223821A
JP2007223821A JP2006043739A JP2006043739A JP2007223821A JP 2007223821 A JP2007223821 A JP 2007223821A JP 2006043739 A JP2006043739 A JP 2006043739A JP 2006043739 A JP2006043739 A JP 2006043739A JP 2007223821 A JP2007223821 A JP 2007223821A
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crystal
silicon carbide
single crystal
carbide single
seed crystal
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JP4690906B2 (en
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Takashi Aigo
Tatsuo Fujimoto
Taizo Hoshino
Masakazu Katsuno
Masashi Nakabayashi
Noboru Otani
Mitsuru Sawamura
Hiroshi Tsuge
Hirokatsu Yashiro
正史 中林
正和 勝野
昇 大谷
泰三 星野
弘志 柘植
充 澤村
弘克 矢代
崇 藍郷
辰雄 藤本
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Nippon Steel Corp
新日本製鐵株式会社
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<P>PROBLEM TO BE SOLVED: To provide a seed crystal for growing a silicon carbide single crystal from which large diameter face wafers with good quality almost free from dislocation defects can be produced with good reproducibility, and to provide a silicon carbide single crystal ingot and a production method therefor. <P>SOLUTION: The seed crystal for growing the silicon carbide single crystal has grooves 12 on the crystal growth surface 15 and has characteristically a silicon carbide epitaxial thin film 13 on the surface 15 other than the grooves 12. The silicon carbide single crystal ingot is produced using the above seed crystal by a sublimation-recrystallization method. The silicon carbide epitaxial layer is grown on the silicon carbide substrate cut out of the above ingot to obtain a wafer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a silicon carbide single crystal and a method for manufacturing the same, and more particularly, to a high-quality and large-sized single crystal ingot that becomes a substrate wafer of an electronic device and a method for manufacturing the same.

  Silicon carbide (SiC) is excellent in heat resistance and mechanical strength, and has attracted attention as an environmentally resistant semiconductor material because of its physical and chemical properties such as 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 been increasing. 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 in spite of semiconductor materials having many advantages and possibilities as described above.

  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 manufacturing 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. Also, 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 chemical vapor deposition (CVD). 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 easily generated, and it is difficult to obtain a high-quality SiC single crystal.

  In order to solve these problems, an improved Rayleigh method has been proposed that performs sublimation recrystallization using a SiC single crystal {0001} plane wafer as a seed crystal (Non-patent Document 1), and has been implemented in many research institutions. Has been. In this method, since the seed crystal is used, the nucleation process of the crystal can be controlled, and the growth rate of the crystal can be controlled with good reproducibility by controlling the atmospheric pressure to about 100 Pa to 15 kPa with an inert gas.

  The principle of the improved Rayleigh method will be described with reference to FIG. The SiC single crystal as a seed crystal and the SiC crystal powder as a raw material are stored in a crucible (usually graphite) and heated to 2000 to 2400 ° C. in an inert gas atmosphere such as argon (133 to 13.3 kPa). 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 is diffused and transported in the direction of the seed crystal by a concentration gradient (formed by a temperature gradient). Single crystal growth is realized by recrystallization of the source gas that has arrived at the seed crystal on the seed crystal. At this time, the resistivity of the crystal can be controlled by adding an impurity gas in an atmosphere composed of an inert gas or mixing an impurity element or a compound thereof in the SiC raw material powder. Representative examples of substitutional impurities in SiC single crystals 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.) and the shape, carrier type and concentration of the SiC single crystal.

Currently, SiC single crystal wafers having a diameter of 2 inches (50.8 mm) to 3 inches (76.2 mm) are cut out from the SiC single crystals produced by the above-described improved Rayleigh method, and are used for epitaxial thin film growth and device fabrication. However, these SiC single crystal wafers contained about 10 4 cm −2 of micropipe defects and dislocation defects penetrating in the growth direction (crystal c-axis direction), which hindered the production of high-performance devices.

  As described above, the SiC single crystal produced by the conventional technique contained a large amount of micropipe defects and threading dislocation defects. According to Non-Patent Document 2, these defects extend substantially parallel to the c-axis, which is the crystal growth direction. These were newly introduced for some reason (mixed with different polytypes, generation of three-dimensional nuclei, thermal stress, etc.) in the initial stage of crystal growth, and those that were already present in the seed crystal. It is roughly divided into two types. Furthermore, these defects cause leakage current particularly when the device is manufactured, and the reduction thereof is regarded as one of the most important issues in SiC single crystal device application.

  These micropipe defects and threading dislocation defects that propagate almost parallel to the c-axis direction grow a SiC single crystal in a direction perpendicular to the <0001> c-axis direction, using a plane perpendicular to the {0001} plane as a seed crystal. Non-Patent Document 2 discloses that this can be completely prevented.

  On the other hand, Patent Document 1 has N growth steps (N is a natural number of N ≧ 3), and in the first growth step where n = 1, the off angle ± 20 from the {1-100} plane. A SiC single crystal in a direction perpendicular to the first growth plane, using a first seed crystal whose first growth plane is a plane of less than 0 ° or a plane with an off angle of ± 20 ° or less from the {11-20} plane In the intermediate growth step where n = 2, 3,..., (N-1) time (N ≧ 3 natural number), 45% from the (n-1) growth plane. An n-th seed crystal is formed from the (n-1) -th growth crystal with a plane inclined by ~ 90 ° and a plane inclined by 60-90 ° from the {0001} plane as the n-th growth plane. An n-th growth crystal is produced in a direction perpendicular to the n-growth plane, and in the final growth step where n = N, a plane having an off angle of ± 20 ° or less from the {0001} plane of the (N-1) -th growth crystal The final seed crystal as the final growth surface is prepared from the (N-1) th growth crystal and is orthogonal to the final growth surface of this final seed crystal. By producing bulk SiC single crystal in the direction, the manufacturing method of threading dislocations and stacking faults is very small high-quality SiC single crystals.

Patent Document 2 describes a method for producing a large-diameter SiC single crystal having a low micropipe defect density. In this publication, a rectangular groove having a width of 2 mm or more is formed on the growth surface of the seed crystal to induce crystal growth in the direction perpendicular to the c-axis in the groove. It is described that the growth and propagation of micropipe defects can be prevented by growing in the axial direction.
JP 2003-119097 Japanese Patent Laid-Open No. 2002-121099 Yu. M. Tairov and VF Tsvetkov, Journal of Crystal Growth, Vol.52 (1981) pp.146-150 J. Takahashi et al., Journal of Crystal Growth, Vol.167 (1996) pp.596-606

In the methods described in Non-Patent Document 2 and Patent Document 1 described above, the growth direction of the single crystal is greatly inclined from the c-axis direction (vertical direction of {0001} plane) (inclination angle: 60 ° or more). Therefore, when trying to obtain a {0001} plane wafer having a large diameter, it is necessary to grow a 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 methods described in Non-Patent Document 2 and Patent Document 1, the yield of crystal growth is reduced and the crystal manufacturing cost is remarkably increased as the crystal growth is prolonged.

  In addition, the method described in Patent Document 2 can suppress the propagation of micropipe defects and penetrating defects that existed in the seed crystal to the grown crystal, but the growth of basal plane dislocations that existed in the seed crystal. Propagation to crystals cannot be suppressed.

  The present invention has been made in view of the above circumstances, and is a SiC single crystal for producing a high-quality large-diameter {0001} plane wafer with few threading dislocations and basal plane dislocation defects at a low cost with good reproducibility. A manufacturing method and a SiC single crystal ingot are provided.

The present invention
(1) A seed crystal for growing a SiC single crystal having a groove on a crystal growth surface, and comprising an epitaxial thin film on a crystal growth surface other than the groove,
(2) The SiC single crystal growing seed crystal according to (1), wherein the side wall of the epitaxial thin film has a tilt angle of 60 ° or more and 120 ° or less from the {0001} plane,
(3) The epitaxial single crystal growth seed crystal according to (1) or (2), wherein the thickness of the epitaxial thin film is 0.1 μm or more and 1000 μm or less,
(4) The SiC single crystal growth seed crystal according to any one of (1) to (3), wherein the epitaxial thin film is a SiC thin film,
(5) The SiC single crystal growth seed crystal according to (1), wherein the off-direction of the crystal growth surface of the seed crystal is the [11-20] direction,
(6) The SiC single crystal growth seed crystal according to (1), wherein an off direction of a crystal growth surface of the seed crystal is a [1-100] direction,
(7) The seed crystal for growing a SiC single crystal according to (1), (5) or (6), wherein an inclination angle in the off direction of the crystal growth surface of the seed crystal is 1 ° or more and 12 ° or less,
(8) The angle formed between the formation direction of the groove and the off direction of the crystal growth surface of the seed crystal is -15 ° or more and 15 ° or less, according to any one of (1) and (5) to (7) Seed crystal for SiC single crystal growth,
(9) The single crystal growth seed crystal according to (1) or (8), wherein the width of the groove is 0.1 μm or more and less than 2 mm,
(10) The aspect ratio of the groove defined by a value obtained by dividing the depth of the groove by the width of the groove is 0.1 or more and 10 or less. (1) For growing an SiC single crystal according to (8) or (9) Seed crystals,
(11) The SiC single crystal growth seed crystal according to any one of (1) and (8) to (10), wherein an area ratio of the groove portion on the crystal growth surface of the seed crystal is 5% or more and 95% or less ,
(12) The seed crystal for growing a SiC single crystal according to any one of (1) to (11), wherein the diameter of the seed crystal is 40 mm or more and 300 mm or less,
(13) A method for producing a seed crystal for growing a silicon carbide single crystal having one surface as a crystal growth surface, wherein an epitaxial thin film is deposited on the crystal growth surface, and then a groove is formed in the crystal growth surface. A method for producing a seed crystal for SiC single crystal growth,
(14) A method for producing a SiC single crystal comprising a step of growing a SiC single crystal on a seed crystal by a sublimation recrystallization method, wherein the seed crystal according to any one of (1) to (12) A method for producing a SiC single crystal, characterized by using a crystal;
(15) A SiC single crystal ingot obtained by the production method according to (14), wherein the ingot has a diameter of 50 mm or more and 300 mm or less,
(16) The SiC single crystal ingot according to (15), wherein the threading dislocation density in the ingot is 1 × 10 4 cm −2 or less,
(17) A SiC single crystal substrate obtained by cutting and polishing the SiC single crystal ingot according to (15) or (16),
(18) A SiC epitaxial wafer formed by epitaxially growing a SiC thin film on the SiC single crystal substrate according to (17),
(19) A thin film epitaxial wafer formed 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 (17),
It is.

  By using the seed crystal of the present invention, a high-quality SiC single crystal with few dislocation defects can be grown with good reproducibility by the improved Rayleigh method. 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.

  In the method for producing a SiC single crystal according to the present invention, a dislocation defect is reduced by using a SiC single crystal in which a groove having a specific shape is formed after an epitaxial thin film is applied to the surface as a seed crystal, and a large-diameter {0001 } A surface wafer can be obtained.

  The effect of the present invention will be described with reference to FIG. The seed crystal for growing a SiC single crystal of the present invention has, for example, a rectangular groove 12 on the crystal growth surface 15 as schematically shown in a sectional view in FIG. The growth surface 15 has an epitaxial thin film (epitaxial growth layer) 13. Here, the crystal growth surface 15 refers to one surface of the seed crystal on which the crystal is grown, that is, the surface exposed on the surfaces of the epitaxial thin film 13 and the groove 12. According to the enlarged cross-sectional view in the vicinity of the groove 12 shown in FIG. 2B, the crystal growth surface 15 includes the inner wall surface 14 formed of the side wall (end surface) 13a of the epitaxial thin film 13 and the groove side wall 12a, and the bottom surface 12b of the groove 12 And the surface including the upper surface 13b of the epitaxial thin film. Note that the shape of the groove 12 of the growth surface 15 is not limited to the rectangle shown in FIG. 2 as long as it exhibits the effects described below. For example, the shape as shown in FIG. A similar effect can be expected even in the groove.

  In the case where an SiC single crystal having the rectangular groove 12 shown in FIG. 2 on the crystal growth surface 15 is used as a seed crystal, in the portion other than the groove on the seed crystal, the crystal growth is the same as in the conventional method. Proceeds parallel to the c-axis direction. At this time, the threading dislocation (A) existing in the seed crystal or the threading dislocation (B) newly introduced in the early stage of growth in the c-axis direction propagates in the grown crystal as it is in the c-axis direction. On the other hand, in the groove 12, in the first initial stage of crystal growth, the crystal growth proceeds in a direction substantially perpendicular to the c axis (that is, grows on the inner wall surface 14). This is because, compared to the {0001} plane, the plane perpendicular to the {0001} plane has a higher probability of attachment of atoms contributing to crystal growth. As a result, the inside of the trench is filled with the SiC single crystal grown perpendicular to the c-axis. At this time, as shown in Non-Patent Document 2, in this portion, the takeover and new generation of threading dislocation (B) propagating in the c-axis direction are completely suppressed.

  However, J. Takahashi et al., Journal of Crystal Growth, Vol. 181 (1997) pp. 229-240 describes the region where threading dislocations in the c-axis direction are suppressed (region grown in the groove). As shown, {0001} area layer defects exist, but in subsequent growth, the crystal grows again in the direction parallel to the c-axis, so that the crystal grown on the groove in the latter half of the growth. The stacking fault, which is a surface defect of the {0001} plane, is not inherited in the part. That is, in the SiC single crystal growth using the seed crystal having the rectangular groove portion 12 on the crystal growth surface 15, which is an embodiment of the present invention, the crystal portion grown on the groove portion 12 of the seed crystal has no seed crystal. Except for the very vicinity, there are no or very few threading dislocations and stacking faults propagating in the c-axis direction. Although there are threading dislocations extending in the c-axis direction as usual in the crystal part grown on the portion other than the groove portion of the seed crystal, if the method of the present invention is performed several times while changing the region of the groove portion 12, the crystal A SiC single crystal with a low dislocation density can be obtained over the entire region.

In addition, in the above-described crystal growth inside the groove, the present invention is characterized in that the propagation method of basal plane dislocations is greatly different between the epitaxial thin film of the seed crystal and the other part (lower part of the epitaxial thin film).
When the SiC thin film is epitaxially grown on the SiC single crystal, the basal plane dislocations existing in the SiC single crystal show a characteristic propagation manner in the epitaxial thin film. First, most of the basal plane dislocations (about 90%) are converted into edge dislocations penetrating in the c-axis direction. In addition, basal plane dislocations (the remaining 10% remaining) propagated in the epitaxial thin film as they are without being converted into threading edge dislocations, the extension direction of the basal plane dislocations is in the off direction of the underlying single crystal during epitaxial growth. It is known to change so as to be almost parallel. Here, the off direction refers to the direction in which the crystal growth surface ((0001) plane) of the base single crystal is inclined. Therefore, first, among the basal plane dislocations existing in the seed crystal, the basal plane dislocations converted into the threading edge dislocations during the epitaxial growth are completely transferred to the growth site in the crystal growth inside the groove as described above. Cannot be taken over. Further, the remaining basal plane dislocations aligned parallel to the off direction are also extended when the groove formation direction (perpendicular to the paper surface in FIG. 2) is parallel to the off direction. Since the directions are parallel, the crystal is hardly taken over by the growth site during crystal growth inside the groove.

  On the other hand, in the lower part of the epitaxial thin film (underlying single crystal region), the extension direction of the basal plane dislocations is distributed almost randomly in the basal plane, so that many basal plane dislocations intersect the inner wall of the groove. ing. As a result, when crystal growth is performed inside the groove, most of the basal plane dislocations existing in the seed crystal are taken over by the crystal growth site.

  The basal plane dislocation inherited to the crystal growth site in the groove is not succeeded to the crystal growth site in the subsequent crystal growth (growth on the groove portion of the seed crystal) like the threading dislocation, but the basal plane dislocation. It is known that when crystal growth is performed on a SiC single crystal containing a large amount of iron, threading dislocations are likely to occur in subsequent crystal growth, although indirectly. Therefore, when crystal growth is performed on a seed crystal having a groove portion that does not have an epitaxial thin film on the crystal growth surface, there are no threading dislocations in the crystal part grown inside the groove, but many basal plane dislocations exist. In addition, deterioration of crystallinity is induced at a site where crystal growth is subsequently performed thereon. On the other hand, in the case of a seed crystal having a groove with an epitaxial thin film as in the present invention, there is a crystal layer containing almost no basal plane dislocations on the outermost surface of the crystal part grown inside the groove. When crystal growth is performed on top, good quality crystal growth can be performed.

  As described above, when an SiC single crystal having a groove with a specific shape on the crystal growth surface on which an epitaxial thin film has been applied is used as a seed crystal, the groove formation direction should be parallel to the off direction of the seed crystal. As a result, not only threading dislocations but also basal plane dislocations can be reduced at the site grown inside the groove, and as a result, the crystallinity of the SiC single crystal grown thereon can be remarkably improved.

  As the arrangement of the grooves on the crystal growth surface of the seed crystal, a stripe shape is preferable in order to arrange it in parallel to the off direction, but other arrangements may be used as long as the above growth mode can be realized. Also, the regularity of the arrangement of the groove portions (for example, the grooves are arranged at equal intervals) is not necessarily required if the above growth mode can be realized.

  The angle formed between the groove forming direction on the seed crystal and the off-direction of the seed crystal is preferably -15 ° or more and 15 ° or less. When the angle formed between the groove formation direction and the seed crystal off-direction is less than -15 ° or more than 15 °, some of the basal plane dislocations aligned in the off direction cross the inner wall of the groove. As a result, in the crystal growth inside the groove, the basal plane dislocation is taken over at the crystal growth site, which is not preferable.

  The inclination angle from the {0001} plane of the epitaxial thin film side wall of the groove (for example, the portion denoted by 13a in FIG. 2) is preferably 60 ° or more and 120 ° or less. If the tilt angle is less than 60 ° or more than 120 °, the effect of suppressing threading dislocations at the crystal growth site in the groove is reduced, which is not preferable.

  The thickness of the epitaxial thin film on the seed crystal is preferably 0.1 μm or more and 1000 μm or less. If the thickness of the epitaxial thin film is less than 0.1 μm, epitaxial growth does not occur uniformly over the entire seed crystal, and the effects of the present invention cannot be obtained. Further, if the thickness of the epitaxial thin film exceeds 1000 μm, uniform step flow growth in the off direction does not occur over the entire surface of the seed crystal, which is also not preferable.

The width of the groove is 0.1 μm or more and less than 2 mm, the aspect ratio of the groove (groove depth ÷ groove width) is 0.1 or more and 10 or less, and the area ratio of the groove on the growth surface of the seed crystal (groove area ÷ seed The total area of the crystal growth surface is preferably 5% to 95%.
When the groove width is less than 0.1 μm, crystal growth in the direction perpendicular to the c-axis is not sufficiently performed, and the effect of suppressing threading dislocation as shown in Non-Patent Document 2 cannot be obtained sufficiently. . In addition, in the case of 2 mm or more, the propagation / generation of micropipes can be suppressed as described in Patent Document 2, but the crystal gathered from the both side walls of the groove (can be at the center of the groove). New dislocation defects are likely to occur, which is not preferable from the viewpoint of reducing dislocation defects. This is because, when the groove width is increased, lattice plane mismatch is likely to occur due to the influence of thermal strain when crystal parts (see FIG. 2) grown from both side walls of the groove meet.
When the aspect ratio of the groove is less than 0.1, crystal growth in the c-axis direction becomes dominant, and the effect described in Non-Patent Document 2 cannot be obtained. On the other hand, when the aspect ratio exceeds 10, crystal growth is likely to occur only at the upper part of the groove, and as a result, the groove is closed at the upper part and the lower part remains as a cavity, and defects are likely to enter from there.
Further, when the area ratio of the groove portion on the growth surface of the seed crystal is less than 5%, the area where the effect of the present invention can be obtained is small and the effect of reducing defects is not sufficient. If the area ratio of the groove portion exceeds 95%, the portion other than the groove portion becomes too thin, and it becomes difficult to perform good crystal growth due to thermal degradation of the portion.

  [11-20] or [1-100] direction is desirable as the off direction of the seed crystal having the groove. This is because the [11-20] direction or [1-100] is known as the off direction in which good quality epitaxial growth can be performed. Further, the tilt angle in the off direction is preferably 1 ° or more and 12 ° or less. When the tilt angle is less than 1 °, it is difficult to perform good quality epitaxial growth. On the other hand, when the tilt angle exceeds 12 °, it is difficult to grow a high-quality bulk single crystal, which is not preferable.

  There are several methods for forming an epitaxial thin film on the crystal growth surface of the seed crystal. First, the most common is epitaxial growth by the CVD method. In the CVD method, a thin film is formed by supplying a raw material with a gas and decomposing the raw material gas with heat, plasma, or the like. For growth from the same vapor phase, a sublimation epitaxy method is also applicable. In this method, a thin film is grown using a sublimation gas from a solid raw material (single crystal, polycrystal, sintered body, etc.) placed near the crystal growth surface of the seed crystal as a raw material. On the other hand, epitaxial growth from the liquid phase can also be used. Epitaxial growth is performed by immersing the seed crystal in a liquid containing the raw material and gradually solidifying the raw material. In addition, molecular beam epitaxy method, laser ablation method, ion plating method, plating method and the like can also be used, so long as they exhibit the dislocation conversion effect or orientation effect described in the present invention in principle. Any method is applicable to the present invention.

  There are several methods for providing the seed crystal groove. The simplest method is a method by machining (for example, cutting with a diamond blade). By selecting the tip shape, width, etc. of the blade, grooves of various shapes and arrangements can be formed. The groove can also be formed by a lithography process used in a semiconductor process or the like. A resin resist is patterned on the seed crystal surface, and then a groove is formed in the opening of the resist by etching (for example, dry etching using reactive plasma). Since the resist can be patterned in any shape, any groove arrangement is possible. The groove shape can be controlled by selecting the etching conditions. In addition, the groove can be formed by electrochemical etching, selective epitaxial growth of a SiC single crystal film on the seed crystal, or the like.

  The seed crystal of the present invention is preferably used as a seed crystal for the improved Rayleigh method and used for the production of a large-diameter SiC single crystal. In this case, as shown in FIG. 1, the seed crystal is stored in a crucible together with the SiC raw material powder, 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 is diffused and transported in the direction of the seed crystal by this temperature gradient. Single crystal growth is realized by recrystallization of the source gas that has arrived at the seed crystal on the seed crystal.

  The diameter of the seed crystal is preferably 40 to 300 mm. In the SiC single crystal growth by the modified Rayleigh method, a crystal having the same diameter as the seed crystal is produced. Therefore, if the diameter of the seed crystal is 40 to 300 mm, an SiC single crystal ingot having a diameter of 50 to 300 mm can be manufactured by a single growth.

Since the SiC single crystal substrate of the present invention has a diameter of 50 mm or more and 300 mm or less, conventional semiconductors (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. In addition, since the threading dislocation density of this substrate is as low as 1 × 10 4 cm −2 or less, 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 GaN, AlN, InN, and mixed crystal thin film epitaxial wafers of the SiC single crystal wafer are used. Since the dislocation density of the crystal wafer is small, the crystal wafer has good characteristics (withstand voltage, surface morphology of the epitaxial thin film, etc.).

  Below, the Example and comparative example of this invention are described.

FIG. 4 shows a SiC single crystal manufacturing apparatus used in the present invention, which is an example of an apparatus for growing a SiC single crystal by an improved Rayleigh method using a seed crystal.
First, this single crystal growth apparatus will be briefly described. Crystal growth is performed by sublimation-recrystallization of SiC powder 2 as a raw material on SiC single crystal 1 in which a groove is formed on the crystal growth surface subjected to the epitaxial thin film used as a seed crystal. 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 graphite support rod 6. 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 the evacuation device 11, and the internal atmosphere is pressure controlled by Ar gas by the Ar gas pipe 9 and the Ar gas mass flow controller 10. be able to. 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 (not shown) by providing an optical path with a diameter of 2 to 4 mm at the center of the felt covering the upper and lower parts of the crucible, and extracting 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.

[Example]
Next, an example of manufacturing a SiC single crystal using this crystal growth apparatus will be described. First, from a pre-grown SiC single crystal ingot, a {0001} plane 5 ° off wafer (off direction: [11-20] direction) with a diameter of 50 mm and a thickness of 1 mm is used as a seed crystal, and the diameter is 50 mm and thickness. A {0001} plane 8 ° off wafer (off direction: [11-20] direction) having a thickness of 0.5 mm was prepared as an etch pit density measurement wafer. Next, for the purpose of measuring the threading dislocation density and the basal plane dislocation density in the SiC single crystal ingot, the etch pit observation of the {0001} plane 8 ° off-wafer was performed. As a result, the values of 1.5 × 10 4 cm −2 and 2.3 × 10 3 cm −2 were obtained as etch pit densities due to threading dislocations and basal plane dislocations, respectively. Thereafter, an SiC thin film was epitaxially grown on the (000-1) C plane of the seed crystal cut from the same ingot as the evaluation wafer (the {0001} plane 5 ° off-wafer was polished). Conditions of epitaxial growth, the growth temperature of 1500 ° C., silane (SiH 4), propane (C 3 H 8), flow rate, respectively 5.0 × 10 -9 m 3 /sec,3.3×10 -9 m of hydrogen (H 2) 3 / sec, 5.0 × 10 −5 m 3 / sec. The growth pressure was atmospheric pressure. The growth time was 8 hours and the film thickness was about 20 μm.

  After the epitaxial growth, a rectangular groove having a width of 0.7 mm, an aspect ratio of 1, and an area ratio of 75% was formed by machining on the epitaxial growth surface ((000-1) C surface) of the seed crystal. The groove arrangement on the surface of the seed crystal was striped, and the groove formation direction was parallel to the off direction ([11-20] direction) of the seed crystal. Further, the processing damage layer formed on the growth surface of the seed crystal by this machining was removed by etching with a chemical solution. The SiC single crystal seed crystal 1 having the groove produced as described above 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. Next, the graphite crucible 3 filled with the raw material is closed with the lid 4 to which the seed crystal 1 is attached, covered with the graphite felt 7, and then placed on the graphite support rod 6, and inside the double quartz tube 5 installed.

  Then, after evacuating the inside of the quartz tube, a current was passed through the work coil to raise the raw material temperature to 2000 ° C. Thereafter, Ar gas containing 6% nitrogen was introduced as an 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 30 hours. At this time, the temperature gradient in the crucible was 15 ° C./cm, and the average growth rate was about 0.60 mm / hour. The diameter of the obtained crystal was 51.5 mm and the height was about 18 mm.

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 was grown. Further, for the purpose of evaluating threading dislocations and basal plane dislocation density existing in the grown crystal, the {0001} plane 8 ° off-wafer (off direction: [11] is obtained by cutting and polishing the latter half of the grown single crystal ingot. -20] direction). Thereafter, the surface of the wafer was etched with molten KOH at about 530 ° C., and the density of etch pits corresponding to threading dislocations and basal plane dislocations was examined with a microscope. The average of the entire wafer surface was 0.6 × 10 4 cm −2 , 1.9 A value of × 10 3 cm -2 was obtained. That is, it was confirmed that the threading dislocations decreased by 60% and the basal plane dislocations decreased by 17% at the site where the crystals grew as compared with the seed crystal.

Further, a {0001} plane SiC single crystal wafer with 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. Using this SiC single crystal wafer as a substrate, SiC was epitaxially grown. The SiC epitaxial film growth conditions, the growth temperature of 1500 ℃, SiH 4, C 3 H 8, the flow rate of H 2, respectively 5.0 × 10 -9 m 3 /sec,3.3×10 -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.

  After the epitaxial thin film was grown, the surface morphology of the obtained epitaxial thin film was observed with a Nomarski optical microscope. I found it growing up.

Similarly, a (0001) Si surface SiC single crystal wafer with an off angle of 0 ° was cut out from the SiC single crystal and mirror-polished, and then a GaN thin film was formed thereon by metal organic chemical vapor deposition (MOCVD). Epitaxially grown. Growth conditions are: growth temperature 1050 ° C., trimethylgallium (TMG), ammonia (NH 3 ), silane (SiH 4 ), 54 × 10 −6 mol / min, 4 liter / min, 22 × 10 −11 mol / min, respectively. Min shed. The growth pressure was atmospheric pressure. The growth time was 20 minutes, and n-type GaN was grown to a thickness of 1 μm.

  In order to investigate 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 surface of the wafer, and a high-quality GaN thin film was formed over the entire surface.

[Comparative example]
As a comparative example, a bulk SiC single crystal growth experiment using a flat seed crystal without an epitaxial thin film on the growth surface will be described.
First, from a pre-grown SiC single crystal ingot, a {0001} plane 4 ° off wafer with a diameter of 50 mm and a thickness of 1 mm is used as a seed crystal, and further a {0001} plane 8 ° off wafer with a diameter of 50 mm and a thickness of 0.5 mm Was prepared as an etch pit density measurement wafer. Next, for the purpose of measuring the threading dislocation density and the basal plane dislocation density in the SiC single crystal ingot, the etch pit observation of the {0001} plane 8 ° off-wafer was performed. As a result, the values of 1.7 × 10 4 cm −2 and 2.3 × 10 3 cm −2 were obtained as etch pit densities caused by threading dislocations and basal plane dislocations, respectively. Thereafter, crystal growth was performed for 50 hours in the same procedure as in the example, using the seed crystal 1 for the comparative example cut out from the same ingot as the evaluation wafer and having no groove. The diameter of the obtained crystal was 51.5 mm, the average crystal growth rate was about 0.64 mm / hour, and the height was about 32 mm.

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. Further, for the purpose of evaluating the threading dislocation and basal plane dislocation density existing in the grown crystal, a {0001} plane 8 ° off-wafer was cut out from the latter half of the grown single crystal ingot and polished. After that, the surface of the wafer was etched with molten KOH at about 530 ° C., and the density of etch pits corresponding to threading dislocations and basal plane dislocations was examined with a microscope. The average of the wafer entire surface was 1.8 × 10 4 cm −2 , 2.2 A value of × 10 3 cm -2 was obtained.

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 stage to obtain a mirror wafer. The plane orientation of the substrate was 8 ° off in the [11-20] direction on the (0001) Si plane. 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., the flow rates of silane (SiH 4 ), propane (C 3 H 8 ), and hydrogen (H 2 ) are 5.0 × 10 −9 m 3 / sec and 3.3 × 10 respectively. -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.
After the growth of the epitaxial thin film, the surface morphology of the obtained epitaxial thin film was observed with a Nomarski optical microscope. As a result, surface defects (pits) thought to be caused by dislocation defects were observed over almost the entire wafer surface.

Similarly, from the SiC single crystal, a (0001) Si surface SiC single crystal wafer having an off angle of 0 ° was cut out and mirror-polished, and then a GaN thin film was formed thereon by metal organic chemical vapor deposition (MOCVD) method. By epitaxial growth. Growth conditions are: growth temperature 1050 ° C., trimethylgallium (TMG), ammonia (NH 3 ), silane (SiH 4 ), 54 × 10 −6 mol / min, 4 liter / min, 22 × 10 −11 mol / min, respectively. Min shed. The growth pressure was atmospheric pressure. The growth time was 20 minutes, and n-type GaN was grown to a thickness of about 1 μm.
In order to investigate the surface state of the obtained GaN thin film, the growth surface was observed with a Nomarski optical microscope, and it was found that the surface morphology was somewhat rough.

FIG. 1 is a diagram for explaining the principle of the improved Rayleigh method. FIG. 2A is a diagram for explaining the effect of the present invention. FIG. 2B is an enlarged view of the vicinity of the groove. FIG. 3 is a diagram showing an example of the shape of a groove used in the present invention. FIG. 4 is a configuration diagram showing an example of a single crystal growth apparatus used in the manufacturing method of the present invention.

Explanation of symbols

1 seed crystal (SiC single crystal)
2 Raw material for SiC powder
3 Graphite crucible
4 Graphite crucible lid
5 Double quartz tube
6 Support rod
7 Graphite felt
8 Work coil
9 Ar gas piping
10 Ar gas mass flow controller
11 Vacuum exhaust system
12 Groove
12a Groove bottom
12b Groove side wall
13 Epitaxial thin film
13a Side wall of epitaxial thin film
13b Top surface of epitaxial thin film
14 Inner wall
15 Crystal growth surface

Claims (19)

  1.   A seed crystal for growing a silicon carbide single crystal having a groove on a crystal growth surface, wherein the seed crystal for growing a silicon carbide single crystal has an epitaxial thin film on a crystal growth surface other than the groove.
  2.   2. The seed crystal for growing a silicon carbide single crystal according to claim 1, wherein the side wall of the epitaxial thin film is a surface having an inclination angle of 60 ° or more and 120 ° or less from the {0001} plane.
  3.   3. The seed crystal for growing a silicon carbide single crystal according to claim 1, wherein the thickness of the epitaxial thin film is 0.1 μm or more and 1000 μm or less.
  4.   4. The seed crystal for growing a silicon carbide single crystal according to claim 1, wherein the epitaxial thin film is a silicon carbide thin film.
  5.   2. The seed crystal for growing a silicon carbide single crystal according to claim 1, wherein an off direction of a crystal growth surface of the seed crystal is a [11-20] direction.
  6.   2. The seed crystal for growing a silicon carbide single crystal according to claim 1, wherein an off direction of a crystal growth surface of the seed crystal is a [1-100] direction.
  7.   7. The seed crystal for growing a silicon carbide single crystal according to claim 1, wherein an inclination angle of the crystal growth surface of the seed crystal in an off direction is 1 ° or more and 12 ° or less.
  8.   The seed for growing a silicon carbide single crystal according to any one of claims 1 and 5 to 7, wherein an angle formed between the formation direction of the groove and the off direction of the crystal growth surface of the seed crystal is -15 ° or more and 15 ° or less. crystal.
  9.   9. The seed crystal for growing a silicon carbide single crystal according to claim 1, wherein a width of the groove is 0.1 μm or more and less than 2 mm.
  10.   10. The seed crystal for growing a silicon carbide single crystal according to claim 1, wherein an aspect ratio of the groove defined by a value obtained by dividing the depth of the groove by the width of the groove is 0.1 or more and 10 or less.
  11.   11. The seed crystal for growing a silicon carbide single crystal according to claim 1, wherein an area ratio of the groove portion on the crystal growth surface of the seed crystal is 5% or more and 95% or less.
  12.   12. The seed crystal for growing a silicon carbide single crystal according to claim 1, wherein the diameter of the seed crystal is 40 mm or more and 300 mm or less.
  13.   A method for producing a seed crystal for growing a silicon carbide single crystal having one surface as a crystal growth surface, characterized by depositing an epitaxial thin film on the crystal growth surface and then forming a groove in the crystal growth surface. A method for producing a seed crystal for growing a silicon single crystal.
  14.   A method for producing a silicon carbide single crystal comprising a step of growing a silicon carbide single crystal on a seed crystal by a sublimation recrystallization method, wherein the seed crystal according to any one of claims 1 to 12 is used as the seed crystal. A method for producing a silicon carbide single crystal.
  15.   15. A silicon carbide single crystal ingot obtained by the production method according to claim 14, wherein the ingot has a diameter of 50 mm or more and 300 mm or less.
  16. 16. The silicon carbide single crystal ingot according to claim 15, wherein the threading dislocation density in the ingot is 1 × 10 4 cm −2 or less.
  17.   17. A silicon carbide single crystal substrate obtained by cutting and polishing the silicon carbide single crystal ingot according to claim 15 or 16.
  18.   18. A silicon carbide epitaxial wafer obtained by epitaxially growing a silicon carbide thin film on the silicon carbide single crystal substrate according to claim 17.
  19.   18. A thin film epitaxial wafer obtained by epitaxially growing gallium nitride, aluminum nitride, indium nitride, or a mixed crystal thereof on the silicon carbide single crystal substrate according to claim 17.
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JP2012136391A (en) * 2010-12-27 2012-07-19 Mitsubishi Electric Corp Method for producing silicon carbide single crystal
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
WO2014034080A1 (en) * 2012-08-26 2014-03-06 国立大学法人名古屋大学 3c-sic single crystal and production method therefor
JP2014162649A (en) * 2013-02-21 2014-09-08 Mitsubishi Electric Corp SiC SUBSTRATE, PRODUCTION METHOD OF SiC SUBSTRATE, AND SiC EPITAXIAL SUBSTRATE
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JP2003176200A (en) * 2001-12-12 2003-06-24 Nippon Steel Corp Seed crystal for growing silicon carbide single crystal, silicon carbide single crystal ingot, and methods for manufacturing them
JP2005239496A (en) * 2004-02-27 2005-09-08 Nippon Steel Corp Silicon carbide raw material for growing silicon carbide single crystal, silicon carbide single crystal, and method for producing the same

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JPS63319294A (en) * 1987-06-19 1988-12-27 Sharp Corp Production of silicon carbide single crystal substrate
JPH10125905A (en) * 1996-10-17 1998-05-15 Denso Corp Semiconductor substrate, and method for correcting warping of semiconductor substrate
JP2001181095A (en) * 1999-12-22 2001-07-03 Kansai Electric Power Co Inc:The Silicon carbide single crystal and its growing method
JP2002121099A (en) * 2000-10-06 2002-04-23 Nippon Steel Corp Seed crystal for growing silicon carbide single crystal, silicon carbide single crystal ingot, silicon carbide single crystal wafer, and method for producing silicon carbide single crystal
JP2003176200A (en) * 2001-12-12 2003-06-24 Nippon Steel Corp Seed crystal for growing silicon carbide single crystal, silicon carbide single crystal ingot, and methods for manufacturing them
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JP2012136391A (en) * 2010-12-27 2012-07-19 Mitsubishi Electric Corp Method for producing silicon carbide single crystal
WO2014034080A1 (en) * 2012-08-26 2014-03-06 国立大学法人名古屋大学 3c-sic single crystal and production method therefor
JPWO2014034080A1 (en) * 2012-08-26 2016-08-08 国立大学法人名古屋大学 3C-SiC single crystal and method for producing the same
JP2014162649A (en) * 2013-02-21 2014-09-08 Mitsubishi Electric Corp SiC SUBSTRATE, PRODUCTION METHOD OF SiC SUBSTRATE, AND SiC EPITAXIAL SUBSTRATE
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
WO2019022053A1 (en) * 2017-07-28 2019-01-31 東洋炭素株式会社 Production method for mono-crystals

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