WO2023079880A1 - ヘテロエピタキシャルウェーハの製造方法 - Google Patents

ヘテロエピタキシャルウェーハの製造方法 Download PDF

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WO2023079880A1
WO2023079880A1 PCT/JP2022/036878 JP2022036878W WO2023079880A1 WO 2023079880 A1 WO2023079880 A1 WO 2023079880A1 JP 2022036878 W JP2022036878 W JP 2022036878W WO 2023079880 A1 WO2023079880 A1 WO 2023079880A1
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single crystal
sic
film
sic single
growth
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French (fr)
Japanese (ja)
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寿樹 松原
温 鈴木
剛 大槻
達夫 阿部
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Shin Etsu Handotai Co Ltd
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Shin Etsu Handotai Co Ltd
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Priority to KR1020247014975A priority patent/KR20240101577A/ko
Priority to JP2023557901A priority patent/JPWO2023079880A1/ja
Priority to EP22889704.7A priority patent/EP4431645A4/en
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/18—Epitaxial-layer growth characterised by the substrate
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/36—Carbides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/16—Controlling or regulating
    • C30B25/165—Controlling or regulating the flow of the reactive gases
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/18—Epitaxial-layer growth characterised by the substrate
    • C30B25/183—Epitaxial-layer growth characterised by the substrate being provided with a buffer layer, e.g. a lattice matching layer
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/18—Epitaxial-layer growth characterised by the substrate
    • C30B25/186—Epitaxial-layer growth characterised by the substrate being specially pre-treated by, e.g. chemical or physical means
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/403—AIII-nitrides
    • C30B29/406—Gallium nitride

Definitions

  • the present invention relates to a heteroepitaxial wafer manufacturing method for heteroepitaxially growing a 3C-SiC single crystal film on a single crystal silicon substrate.
  • 3C-SiC has excellent thermal conductivity, chemical stability in high-temperature environments, and a wider bandgap than silicon. It is valid. For this reason, heteroepitaxial growth on silicon substrates has been extensively studied (Non-Patent Document 1).
  • Two-step growth is adopted as a general heteroepitaxial growth method.
  • the method is carbonization of silicon followed by SiC growth.
  • CVD uses gases such as SiH4 and chlorosilane as silicon sources and gases such as C3H8 and CH4 as carbon sources. It is common to react these gases at temperatures higher than 1200°C.
  • gases such as SiH4 and chlorosilane as silicon sources and gases such as C3H8 and CH4 as carbon sources. It is common to react these gases at temperatures higher than 1200°C.
  • the growth is performed at a high temperature, there is a problem that tensile stress is generated due to the difference in lattice constant between Si and SiC.
  • Non-Patent Document 2 Low-temperature growth using a low-pressure CVD apparatus.
  • a low-pressure CVD apparatus is used for silicon carbonization and subsequent SiC growth, and growth is performed by diluting trimethylsilane or monomethylsilane gas with hydrogen at a low temperature of 1000° C. or less.
  • 3C—SiC epitaxial growth with good quality and less stress is possible by lowering the temperature of the CVD growth, which is exposed to high temperature for a long time.
  • Non-Patent Document 3 a method has been proposed in which carbonization of silicon, which requires a high temperature, is not performed.
  • a silicon substrate is heated to 900 to 1000° C. under high vacuum (less than 7 ⁇ 10 ⁇ 5 Pa (5 ⁇ 10 ⁇ 7 Torr)), and disilabutane is used as a source gas for growth. It does not contain , making it possible to form a film in a relatively low-temperature environment.
  • cracks in the GaN layer can be prevented by forming an SiC layer as an intermediate layer between silicon and GaN. It is said that cracks are generated not during epitaxial growth but during the cooling process after epitaxial growth. That is, the linear expansion coefficient of 3C—SiC is 4.6 ⁇ 10 ⁇ 6 K ⁇ 1 , whereas Si is 4.2 ⁇ 10 ⁇ 6 K ⁇ 1 and GaN is 5.59 ⁇ 10 ⁇ 6 K. ⁇ 1 , and 3C—SiC has an intermediate value between Si and GaN, which is considered to alleviate thermal contraction during substrate cooling after epitaxial growth.
  • Non-Patent Document 5 there are various reports on the growth of GaN on SiC, but in general, it is possible to grow high-quality GaN by performing surface modification (pretreatment) by flowing a gas such as trimethylaluminum before growing GaN.
  • pretreatment surface modification
  • the surface of SiC is said to be "the poor wetting", and this is because the surface is modified by performing a pretreatment with a gas such as trimethylaluminum before growing GaN.
  • a heteroepitaxial substrate obtained by growing SiC on a silicon substrate and then growing GaN is very attractive because it can be made as large as 300 mm in diameter, for example.
  • SiC epitaxial growth is performed at a high temperature, pretreatment is particularly necessary for GaN growth, and even if pretreatment is performed during GaN growth, GaN cannot always be grown on SiC. A great deal of effort was required to find the process conditions.
  • the present invention has been made to solve the above problems, and provides a wafer capable of heteroepitaxially growing high-quality GaN or the like on a 3C—SiC single crystal film formed on a single crystal silicon substrate. It is an object of the present invention to provide a method for producing a heteroepitaxial wafer that can be obtained.
  • the present invention provides a heteroepitaxial wafer manufacturing method for heteroepitaxially growing a 3C—SiC single crystal film on a single crystal silicon substrate, comprising: Using a reduced pressure CVD device, a first step of removing a native oxide film on the surface of the single crystal silicon substrate by hydrogen baking; a second step of supplying a source gas containing carbon and silicon into the low-pressure CVD apparatus to form the 3C—SiC single crystal film having wettability such that the contact angle with the liquid on the surface is 50° or less; ,
  • a method for producing a heteroepitaxial wafer comprising:
  • the 3C-SiC single crystal film can be formed in the second step (nucleation step, film formation step).
  • the wettability (contact angle) of the surface of the 3C-SiC single crystal film is newly used as an index, so that the subsequent heteroepitaxial growth on the 3C-SiC single crystal film can be performed. It is possible to obtain a heteroepitaxial wafer that can be carried out more easily and reliably. In particular, a heteroepitaxial wafer capable of heteroepitaxially growing high-quality GaN can be more reliably obtained without performing the pretreatment that is performed in the conventional method. Therefore, labor and costs can be reduced.
  • the contact angle as an index of the wettability of the 3C—SiC single crystal film can be the contact angle when H 2 O is used as the liquid.
  • the second step includes a nucleation step of forming nuclei of SiC on the single crystal silicon substrate, and a film forming step of growing a SiC single crystal to form the 3C-SiC single crystal film,
  • the nucleation step can be carried out under the condition that the pressure is 13332 Pa or less and the temperature is kept constant in the range of 300° C. or higher and 950° C. or lower.
  • the film forming step can be performed under the conditions of a pressure of 6666 Pa or less and a temperature of 800°C or more and 1200°C or less.
  • epitaxial growth can be rate-determined by supply gas transport, layer-by-layer epitaxial growth is possible, and surface free energy is in a state suitable for GaN growth in particular. can be controlled more reliably. Moreover, the occurrence of slip dislocations can be prevented. Further, while growing the 3C-SiC single crystal film, holes can be formed in the silicon layer (single crystal silicon substrate) immediately below the 3C-SiC single crystal film.
  • the first step can be performed under the condition that the temperature is 1000°C or higher and 1200°C or lower.
  • the native oxide film on the surface of the single crystal silicon substrate can be removed more efficiently, and the occurrence of slip dislocations can be prevented.
  • Monomethylsilane or trimethylsilane can be used as the source gas.
  • GaN can be further grown on the surface of the deposited 3C-SiC single crystal film to form a GaN layer.
  • the present invention is particularly effective when forming a GaN layer on a single crystal silicon substrate with a 3C-SiC single crystal film as an intermediate layer, and can obtain a GaN layer with better film quality more easily and reliably than before.
  • An epitaxial wafer can be provided. Furthermore, it is possible to provide a heteroepitaxial wafer in which a GaN layer is further formed on the 3C-SiC single crystal film.
  • FIG. 4 is a graph showing an example of a 3C-SiC growth sequence in the heteroepitaxial wafer manufacturing method of the present invention. It is also a graph showing the 3C-SiC growth sequence in Example 1. 4 is a graph showing the results of in-plane XRD analysis of 3C-SiC on Si(111) grown by the 3C-SiC growth sequence of Example 1.
  • FIG. 1 is a cross-sectional TEM image of GaN on 3C—SiC on Si (111) grown on the 3C—SiC single crystal film of Example 1.
  • FIG. 4 is a graph showing an XRD rocking curve of GaN grown on the 3C—SiC single crystal film of Example 1.
  • 4 is a graph showing a 3C-SiC growth sequence in a comparative example; 4 is a graph showing the results of in-plane XRD analysis of 3C-SiC on Si (111) grown by the 3C-SiC growth sequence of Comparative Example.
  • 1 is a cross-sectional TEM image of GaN on 3C--SiC on Si (111) grown on a 3C--SiC single crystal film of a comparative example.
  • 4 is a graph showing an XRD rocking curve of GaN grown on a 3C—SiC single crystal film of a comparative example; It is explanatory drawing of a contact angle. It is a schematic diagram of a vapor deposition (BCF) model.
  • BCF vapor deposition
  • the contact angle is the angle formed by the tangent line drawn to the liquid at the contact point of the three phases of solid, liquid, and gas when the liquid is on the surface of the solid in the air, and the solid surface. , points to the corner containing the liquid.
  • This contact angle as shown by Young's formula shown in the following (Formula 1 ), is the Determined by surface tension and interfacial tension between solids and liquids.
  • the surface tension between the solid and the liquid is generated by the appearance of the surface where the intermolecular force (van der Waals force) in the bulk is the interface (surface free energy). It can be seen that the (bulk) growth condition affects the contact angle.
  • ⁇ S ⁇ L ⁇ cos ⁇ + ⁇ SL (Equation 1) here,
  • the 3C—SiC single crystal film grown in this way is in a state where the contact angle, that is, the surface free energy is controlled, it is suitable as a substrate on which heteroepitaxial growth (especially GaN growth) is performed. It's becoming
  • the surface concentration of active species can be written as follows so that the surface tension affects the surface concentration.
  • k B Boltzmann constant
  • T temperature
  • F surface tension
  • FIG. 1 shows an example of a 3C-SiC growth sequence.
  • the first step of hydrogen baking hereinafter also referred to as H 2 annealing
  • the second step of the 3C-SiC single crystal film formation step is performed in order.
  • Each step will be described below.
  • a single crystal silicon substrate is placed in a low pressure CVD apparatus (hereinafter also referred to as an RP-CVD apparatus), hydrogen gas is introduced, and a natural oxide film on the surface is removed by H 2 annealing. If the oxide film remains, SiC nucleation cannot be formed on the single crystal silicon substrate.
  • the H 2 annealing at this time is preferably carried out under the condition that the temperature is, for example, 1000° C. or more and 1200° C. or less. By setting the temperature to 1000° C. or more, it is possible to prevent the processing time for preventing the remaining natural oxide film from becoming long, which is efficient. Further, if the temperature is 1200° C.
  • the H 2 annealing pressure and time are not particularly limited as long as the natural oxide film can be removed. In the example shown in FIG. 1, H 2 annealing is performed at 1080° C. for 1 minute.
  • hydrogen gas can be continuously introduced after the first step and also in the second step (carrier gas).
  • the single crystal silicon substrate is set to a predetermined pressure and temperature, and a source gas containing carbon and silicon is introduced into the RP-CVD apparatus as a source gas for SiC to form SiC nuclei.
  • a source gas containing carbon and silicon is introduced into the RP-CVD apparatus as a source gas for SiC to form SiC nuclei.
  • monomethylsilane or trimethylsilane (TMS) can be introduced as the source gas. It is simpler and easier to control than the case of using multiple kinds of gases, and it is possible to form a 3C—SiC single crystal film more reliably.
  • trimethylsilane is easier to set conditions in consideration of raw material efficiency.
  • the introduction of such a source gas is performed during the nucleation stage and the subsequent film formation stage of this second process.
  • this SiC nucleation can be efficiently carried out on the surface of the single-crystal silicon substrate under the conditions of constant temperature holding, for example, at a pressure of 13332 Pa (100 Torr) or less and a temperature of 300° C. or higher and 950° C. or lower.
  • the temperature is set to 950° C. or less, the reaction between the single crystal silicon substrate and the raw material gas progresses due to the excessive temperature, making it impossible to form SiC nuclei on the surface of the single crystal silicon substrate. You can more reliably prevent it from being put away.
  • the surface of the 3C—SiC single crystal film after film formation can more reliably obtain wettability such that the contact angle with liquid is 50° or less.
  • the temperature by setting the temperature to 900° C. or less, wettability with a contact angle of 40° or less can be easily obtained.
  • the liquid is not particularly limited, generally H 2 O can be used. If it is H 2 O, it can be easily prepared and measured when checking the contact angle after film formation.
  • the temperature by setting the temperature to 300° C. or more, it is possible to more reliably prevent SiC nucleation from being efficiently performed due to the temperature being too low.
  • the heteroepitaxial growth of SiC can be efficiently advanced by setting the temperature to 800° C. or higher during the film formation stage. Therefore, for example, the temperature for SiC nucleation can be set to preferably 800° C. or higher and 950° C. or lower, more preferably 850° C. or higher and 900° C. or lower, from the time of the nucleation stage.
  • the temperature in the nucleation stage can be set to 800° C. or more and 950° C. or less in this way, the preferred temperature ranges to be set in the SiC nucleation stage and the subsequent film formation stage for forming the 3C—SiC single crystal film overlap.
  • these nucleation and film formation steps can be carried out under the same temperature conditions.
  • the pressure is set to 13332 Pa (100 Torr) or less, it is possible to prevent secondary or higher-order reactions such as reaction of the reactive species with the raw material gas in the gas phase, which is efficient. . More preferably, it can be set to 133 Pa (1 Torr) or less, which is more efficient. Although the lower limit of the pressure is not particularly limited, it can be set to 13.3 Pa (0.1 Torr), for example.
  • the pressure can be the same in the nucleation stage and the film formation stage. In the example shown in FIG. 1, this nucleation step and the next film formation step are performed under the same conditions, the same pressure and the same holding temperature (900° C.).
  • the pressure is 13332 Pa (100 Torr), further 6666 Pa (50 Torr) or less
  • the temperature is 800 ° C. or more and less than 1200 ° C. It can be performed.
  • the SiC single crystal can be efficiently grown to form the 3C-SiC single crystal film.
  • the growth pressure is 13332 Pa (furthermore, 6666 Pa) or less, polycrystallization of the 3C-SiC to be formed can be prevented more reliably.
  • the pressure is 6666 Pa (50 Torr) or less, it is possible to suppress secondary or higher-order reactions in the gas phase as described above, prevent 3C-SiC from polycrystallizing, and A crystal film can be formed reliably and efficiently. And preferably, it can be 1333 Pa (10 Torr) or less, further 133 Pa (1 Torr) or less. can have the effect of alleviating Although the lower limit of the pressure is not particularly limited, it can be set to 13.3 Pa (0.1 Torr), for example.
  • the temperature setting the temperature to 800° C. or higher enables efficient growth of the SiC single crystal as described above, and setting the temperature to 1200° C. or lower effectively prevents slip dislocations from occurring. .
  • the nucleation step and the film formation step are performed under the same conditions as described above, and the nucleation of SiC and the formation of the 3C—SiC single crystal film are performed continuously.
  • the film formation time can be appropriately set based on the pressure and temperature conditions set so as to obtain the desired film thickness.
  • the film thickness of the 3C—SiC single crystal film can be, for example, from a thin film of about 2 nm to a thick film of several ⁇ m. layered growth is possible in a two-dimensional growth mode.
  • layered growth in the two-dimensional growth mode shown in FIG. 1 is layer-by-layer epitaxial growth.
  • the heteroepitaxial wafer grown in this manner and having a wettability with a liquid (H 2 O) contact angle of 50° or less (greater than 0°) on the 3C—SiC single crystal film is formed on the wafer.
  • growing GaN on the 3C—SiC single crystal film makes it possible to obtain a heteroepitaxial wafer having a high-quality GaN layer.
  • GaN is grown by MOCVD using organometallic materials such as trimethylgallium and trimethylammonium to grow GaN to a thickness of about 3 ⁇ m. It is also possible to heteroepitaxially grow Si, for example, instead of GaN.
  • the smaller the contact angle the more suitable the surface free energy is for GaN growth, and the more reliably a heteroepitaxial layer of excellent film quality can be formed on the 3C—SiC single crystal film.
  • the contact angle can be measured using, for example, a commercially available measuring device.
  • An example is PCA-11 from Kyowa Interface Science Co., Ltd.
  • the measurement can be performed by dropping 2.0 ⁇ L of pure water droplets on the surface of the 3C—SiC single crystal film at five locations, obtaining the contact angle from image analysis, and averaging the values.
  • it is not limited to this measuring method.
  • the conditions during film formation are not limited to the pressure range and temperature range described above. do not have.
  • the film formation conditions may be such that the contact angle on the surface of the 3C-SiC single crystal film after film formation is 50° or less, and various condition patterns are conceivable during the heteroepitaxial growth of the 3C-SiC single crystal film. , can be determined accordingly.
  • the correlation between the pressure and temperature conditions at the time of 3C-SiC single crystal film formation and the contact angle on the surface of the 3C-SiC single crystal film after film formation is performed by changing the pressure and temperature conditions.
  • Conditions of pressure and temperature during the formation of a 3C-SiC single crystal film that are obtained in advance by tests and have a contact angle of 50 ° or less after film formation based on the correlation when actually manufacturing the product. can be set and manufactured.
  • the present inventors have found that using the contact angle as a condition for the heteroepitaxial growth of a 3C—SiC single crystal film is extremely effective in further forming a heteroepitaxial layer such as GaN thereon. has great meaning. It may be manufactured by adjusting the conditions during the formation of the 3C-SiC single crystal film so as to satisfy the above contact angle conditions, and after the formation of the 3C-SiC single crystal film and before the formation of the heteroepitaxial layer such as GaN. Since there is no need to perform a pretreatment unlike the conventional method, the process is easy, and a high-quality heteroepitaxial film of GaN or the like can be reliably obtained.
  • Example 1 A 300 mm diameter, (111) plane orientation, boron-doped high resistivity single crystal silicon substrate was prepared, the wafer was placed on a susceptor in the reactor of an RP-CVD apparatus, and heated to 1080° C. like the growth sequence shown in FIG. A H 2 anneal was performed for 1 minute at (first step). Subsequently, trimethylsilane gas was introduced at a growth temperature of 900° C.
  • the film thickness was 13 nm.
  • this growth substrate (single crystal silicon substrate + 3C—SiC single crystal film) is placed in an MOCVD reactor, and a Group III nitride semiconductor thin film such as AlN, AlGaN and GaN is deposited on the growth substrate.
  • a Group III nitride semiconductor thin film such as AlN, AlGaN and GaN is deposited on the growth substrate.
  • Epitaxial growth was performed.
  • a growth substrate was placed in a wafer pocket called a satellite.
  • TMAl was used as an Al source
  • TMGa was used as a Ga source
  • NH3 was used as an N source.
  • Both N2 and H2 were used as the carrier gas.
  • the process temperature was about 900-1200°C.
  • AlN and AlGaN were deposited in order from the substrate side toward the growth direction, and then GaN was epitaxially grown.
  • FWHM Full Width Half Maximum
  • GaN growth on the 3C—SiC single crystal film was attempted under the same conditions as in Example 1.
  • a cross-sectional TEM image of the grown GaN is shown in FIG. 7, and an XRD rocking curve is shown in FIG.
  • GaN was grown in a three-dimensional island shape.
  • FWHM wide half width
  • Example 2 A single crystal silicon substrate similar to that of Example 1 was prepared, a wafer was placed on a susceptor in a reactor of an RP-CVD apparatus, and H 2 annealing was performed at 1080° C. for 1 minute (first step). Subsequently, trimethylsilane gas was introduced for 5 minutes at a growth temperature of 900° C. as a nucleation step of the second step. Next, as the film formation stage of the second process, the growth temperature was raised to 1190° C. and trimethylsilane gas was introduced to grow a 3C—SiC single crystal film. The growth pressure at this time was uniformly 133 Pa (1 Torr). As a result of growing for 1 minute, the film thickness was about 50 nm.
  • Example 2 when GaN was grown on the 3C-SiC single crystal film under the same conditions as in Example 1, a GaN film with good crystallinity was obtained. Although not as good as Example 1, the crystallinity was superior to that of Comparative Examples.
  • the present invention is not limited to the above embodiments.
  • the above embodiment is an example, and any device that has substantially the same configuration as the technical idea described in the claims of the present invention and produces similar effects is the present invention. It is included in the technical scope of the invention.

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PCT/JP2022/036878 2021-11-08 2022-10-01 ヘテロエピタキシャルウェーハの製造方法 Ceased WO2023079880A1 (ja)

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