JP2006321696A - Method for manufacturing silicon carbide single crystal - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a silicon carbide single crystal, by which an epitaxial layer of the silicon carbide single crystal can be grown on an inclined substrate having an inclination angle smaller than a conventional inclination angle without forming a 3C structure. <P>SOLUTION: In the method for manufacturing the silicon carbide single crystal by a CVD process comprising supplying a gaseous silicon hydride and a gaseous hydrocarbon together with a carrier gas onto a heated SiC substrate 5 to grow a single crystal by thermal decomposition reaction, an SiC single crystal substrate inclined from the (0001) plane at a small inclination angle is used as the SiC substrate 5, and the gaseous silicon hydride, the gaseous hydrocarbon, the carrier gas, and gaseous hydrochloric acid are simultaneously supplied onto the SiC single crystal substrate. The inclination angle is set to be within a range of 0.5-7.0° when the SiC single crystal substrate is 4H and within a range of 0.5-2.5° when the substrate is 6H. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a silicon carbide single crystal for a semiconductor device by a CVD method.

  Silicon carbide (SiC) is a semiconductor material that is excellent in chemical resistance against acids and alkalis, has high resistance to high energy rays, and is excellent in durability. In addition, since the dielectric breakdown voltage is high and the properties as a semiconductor are not lost even at high temperatures, it is also expected as a material for power devices and high-temperature devices.

  It is known that SiC has approximately 250 crystal forms. Typically, crystal forms such as 3C, 4H, 6H, and 15R (numbers indicate the repetition period of Si—C pairs in the <0001> axial direction, C is cubic, H is hexagonal, and R is rhombohedral system. Is present). Among these, SiC having a 3C structure (3C-SiC) is considered to be suitable for an active element that operates at a high temperature or in an environment irradiated with radiation. Further, SiC having 6H structure (6H-SiC) has a forbidden band width of about 2.9 eV and is used as a blue light emitting element. SiC with 4H structure (4H-SiC) has a wider band gap than about 3.2 eV and 6H-SiC, so it can be used in heterojunction devices with blue to purple light-emitting diodes and other crystalline SiC Is considered.

  As a method for forming an SiC crystal as a semiconductor material, a CVD method (chemical vapor deposition method) is used on a (0001) Si surface of a hexagonal (6H or 4H) SiC substrate obtained by an improved Rayleigh method (sublimation method). In general, the epitaxial growth is performed.

For example, it is known to form an n-type light emitting layer as follows using a metal organic chemical vapor deposition method (MOCVD method) (see Patent Document 1). That is, first, the 6H—SiC crystal substrate 11 cut out in the (11-20) plane is put in an MOCVD apparatus and subjected to surface treatment at a high temperature. Next, after the substrate temperature is lowered to the growth temperature (1500 ° C.), silane (SiH ₄ ) which is a raw material of silicon (Si) diluted with a carrier gas and propane (C ₃ H ₈ ) which is a raw material of carbon (C) Gas and gas are introduced alternately. In the middle of the switching, hydrogen chloride (HCl) gas is introduced to remove excess Si and C. By doing so, it is possible to grow one atom at a time. When this growth is performed, a layer to which impurities are added alternately and a layer to which no doping is performed are alternately grown for each SiC layer to form the n-type light emitting layer 12 having a superlattice structure. As impurities, nitrogen (N) is introduced for determining the conductivity type, and aluminum (Al) is introduced to the extent that the amount of nitrogen does not exceed the emission center.

  However, in the case of epitaxial growth by the CVD method, there is a problem that cubic (3C structure) SiC is partially formed. When this 3C structure occurs, a crystal defect occurs at the boundary with the 6H structure or 4H structure, which becomes a current leakage path when a voltage is applied and causes a significant decrease in the breakdown voltage of the device. Therefore, in order to suppress the generation of this cubic crystal (3C structure), it must be grown at a high temperature of 1800 ° C. or higher.

  The degree of occurrence of this 3C structure can be evaluated with a Nomarski microscope. This is because defects generated at the boundary can be easily observed. FIG. 7 shows a surface photograph of the 4H—SiC epitaxial substrate in which the 3C structure is generated in the epitaxial layer.

  Later, Matsunami et al. Of Kyoto University discovered a step-controlled epitaxy method that grows on a substrate tilted in the [11-20] direction from the (0001) plane, and found that it can be grown at a temperature of about 1500 ° C. It was issued. 6H-SiC has an optimum tilt angle of 3.5 °, but 4H-SiC requires a tilt angle larger than 8 °.

  With the discovery of this technology, it has become possible to carry out CVD growth of SiC at a more realistic temperature, the development of SiC electronic devices has been further promoted, and various devices have been proposed. The only Schottky barrier diode that has already been put into practical use as a SiC device and is on the market.

Device structure of the Schottky barrier diode, as shown in FIG. 8, n on the n ⁺ -type SiC substrate 31 ^- grown -type epitaxial layer 32, n ^- shot side key electrode 33, n ⁺ ohmic to the side electrode 34 is a relatively simple structure. Further, around the Schottky electrode 33, B is implanted to form a boron implanted region 35 in order to suppress current leakage, and the surface is protected by the SiO ₂ passivation film 36.

There are two types currently on the market: 600V breakdown voltage and 1.3kV breakdown voltage. Recently, however, a growth technique that eliminates micropipe defects (hollow penetration defects), which is a major cause of current leakage, has been reported, and it is expected that higher voltage specifications will be commercially available in the future. In addition, with the reduction of substrate defects, the development of JFET (junction field effect transistor) and the like is considered in the future, and the market of SiC electronic devices is expected to expand in the future.
Japanese Patent Laid-Open No. 5-7016 (paragraph numbers 0016 and 0017)

  However, an inclined substrate (off-axis substrate) inclined at an angle in the [11-20] direction from the (0001) plane has a lower yield than a substrate (on-axis substrate) parallel to the (0001) plane. Therefore, it is expensive. Furthermore, the greater the slope, the lower the yield and the higher the cost. In particular, a 4H—SiC substrate having high mobility in the c-axis direction is used for Schottky barrier diodes and other vertical devices. Therefore, the influence on the cost of the device due to the use of the inclined substrate cannot be ignored.

In addition, when SiC is grown on a tilted substrate by CVD, a phenomenon occurs in which the epitaxial layer is tilted and grown at the tilted substrate edge portion by the tilt angle. In FIG. 9, when the n ⁻ SiC epitaxial layer 32 is formed on the n ⁺ SiC substrate 31, which is an inclined substrate, the n ⁻ SiC epitaxial layer 32 grows at the substrate edge portion 37 with an inclination of the substrate inclination angle θ. Indicates. Depending on the growth conditions, the region 38 that grows at a different frequency or tilt differs, but as the tilt angle θ increases, the region that cannot be used for device fabrication (the region 38 that tilts and grows) becomes larger. Accordingly, the device acquisition yield that can be acquired from one epitaxial substrate is reduced.

  By the way, in the case of the conventional CVD method, the optimum inclination angle of the inclined substrate (off-axis substrate) to be used is 3.5 ° for 6H—SiC and 8 ° for 4H—SiC, which is relatively large. Here, if an epitaxial layer can be grown on a SiC substrate having a smaller inclination than the conventional one without generating a 3C structure, it is not necessary to use an inclined substrate having a large inclination angle as in the prior art. Such costs can be reduced, and further, the above-described problems occurring at the edge portion are reduced, and the device acquisition yield that can be acquired from one epitaxial substrate is improved.

  Accordingly, an object of the present invention is to provide a method for producing a silicon carbide single crystal capable of growing an epitaxial layer on a tilted substrate having a smaller tilt angle than before without producing a 3C structure.

  In order to achieve the above object, in the present invention, a SiC epitaxial layer is grown on a substrate having a smaller inclination than in the prior art by a CVD method in which HCl gas is supplied simultaneously with Si raw material, C raw material and carrier gas.

  The present invention is specifically configured as follows.

  A method for producing a silicon carbide single crystal according to the invention of claim 1 is based on a CVD method in which a silicon hydride gas and a hydrocarbon gas are supplied onto a SiC substrate heated together with a carrier gas, and a single crystal is grown by a thermal decomposition reaction. In the method for producing a silicon carbide single crystal, a SiC single crystal substrate inclined at a small inclination angle from the (0001) plane is used as the SiC substrate, and a silicon hydride gas, a hydrocarbon gas, and It is characterized in that HCl gas is supplied simultaneously with the carrier gas.

  According to this feature, by supplying HCl gas at the same time, the etching action of HCl is performed, a step appears on the surface, and the terrace is forcibly narrowed to form a kink, thereby suppressing the generation of 3C structure nuclei. Is done. Therefore, for example, an SiC epitaxial layer can be grown using an inclined substrate (off-axis substrate) inclined from the (0001) plane in the [11-20] direction at an inclination angle smaller than that of the prior art.

  A method for producing a silicon carbide single crystal according to the invention of claim 2 is based on a CVD method in which a silicon hydride gas and a hydrocarbon gas are supplied onto a SiC substrate heated together with a carrier gas, and a single crystal is grown by a thermal decomposition reaction. In the method for manufacturing a silicon carbide single crystal, an SiC single crystal substrate inclined at a small inclination angle from the (0001) plane is used as the SiC substrate, and a carrier gas and an HCl gas are first supplied onto the SiC single crystal substrate. Thereafter, silicon hydride gas and hydrocarbon gas are supplied.

  This is because a carrier gas and HCl gas are first supplied (introduced) before supplying a silicon hydride gas and a hydrocarbon gas onto a heated SiC substrate, and a SiC single crystal substrate having a small inclination is used as the SiC substrate. It is a manufacturing method of the silicon carbide single crystal of the form to be used. The operational effects are the same as in the case of claim 1.

  A third aspect of the present invention is the method for producing a silicon carbide single crystal according to the first or second aspect, wherein the SiC substrate is a 4H structure inclined from the (0001) plane within a range of 0.5 ° to 7.0 °. The SiC single crystal substrate or a SiC single crystal substrate having a 6H structure tilted in a range of 0.5 ° to 2.5 ° from the (0001) plane is used.

  Thus, the inclination angle of the SiC single crystal substrate is in the range of 0.5 ° to 7.0 ° for the SiC single crystal substrate having the 4H structure, and 0.5 ° to 2.5 ° for the SiC single crystal substrate having the 6H structure. This is because, if out of this range, deterioration in flatness and an increase in the number of defects are recognized, causing problems in practical use.

The invention of claim 4 is the method for producing a silicon carbide single crystal according to any one of claims 1 to 3, wherein the carrier gas is H ₂ gas, a mixed gas of He and H ₂ , or a mixture of Ar and H ₂ . One of the gases is used.

  The invention of claim 5 is the method for producing a silicon carbide single crystal according to any one of claims 1 to 4, wherein the flow rate of HCl gas is set to 0.1 to 5.0% of the carrier gas flow rate. And

  The HCl flow rate should be sufficient to cause a step on the growing epitaxial surface. However, if the flow rate of HCl is too large, the etching of the epitaxial layer proceeds excessively, and the film forming speed is reduced accordingly. Therefore, there is an optimum HCl flow rate, which varies depending on the apparatus used and the growth conditions, but the HCl gas flow rate is preferably 0.1 to 5.0% of the carrier gas flow rate.

A sixth aspect of the present invention is the method for producing a silicon carbide single crystal according to any one of the first to fifth aspects, wherein Si ₂ H ₆ , SiH _4−x Cl _x (X = 1, 2, 3, 4), Si ₂ H _6-x Cl _x (X = 1, ₂ , 3, 4, 5, 6) and CH ₄ , C ₂ H ₆ , C ( CH ₃ ) ₄ is used.

  A seventh aspect of the present invention is the method for producing a silicon carbide single crystal according to any one of the first to sixth aspects, wherein the growth rate is 20 μm / hour or less.

  According to this growth rate, the SiC single crystal can be reliably epitaxially grown.

  <Key points of the invention>

  The state of CVD growth of SiC using a conventional inclined substrate can be expressed as shown in FIG. Even on a flatly polished surface, there are an infinite number of steps on the substrate surface. Here, the upper surface of the step is referred to as a terrace 21, and the side surface is referred to as a kink 22. When SiC undergoes epitaxial growth, reactive species adhere to the surface of the terrace 21 and cause a random walk 23 on the surface. Finally, it is vaporized by re-evaporation 24 or reaches the kink 22 and is taken in as crystals (raw material adhesion 25).

  When this is viewed macroscopically, it can be observed that the steps grow so as to flow in the tilt direction. Such growth is called step flow growth, and when this is ideally performed, the underlying crystal form and polytype are completely taken over.

  At this time, the smaller the inclination angle, the wider the terrace 21 and the fewer kinks 22. An ideally polished on-axis substrate has an infinitely large terrace and no kink. If the terrace 21 is wide and the kink 22 is small, the reactive species form nuclei on the terrace 21 before reaching the kink 22. If this nucleus continues to grow, it is said to have a 3C structure.

  A feature of the present invention is that HCl is introduced simultaneously with SiC growth. The role of HCl is in the following two points.

  (1) Promotion of reevaporation from the substrate, thereby removing growth nuclei generated on the terrace.

  (2) Forced step formation by etching of the SiC substrate surface.

  If there is a certain temperature in the hydrogen atmosphere, SiC is etched by HCl. In particular, in a SiC substrate, it is recognized that a step having a width of several tens of nanometers appears on the surface by HCl etching (see FIG. 6). For this reason, the kinks are formed by forcibly narrowing the terrace even with an inclination angle smaller than that of the prior art, so that step flow growth is promoted and generation of 3C structure nuclei can be suppressed.

  According to the method for producing a silicon carbide single crystal according to the present invention, a high-quality SiC single crystal thin film is grown using a SiC single crystal substrate having a smaller inclination angle without using an inclined substrate having a larger inclination angle as in the prior art. Therefore, it becomes possible to manufacture a SiC epitaxial wafer with a lower price and a higher device yield. Thereby, it is possible to realize the development promotion of the SiC device and further the promotion to the end user.

  Hereinafter, the present invention will be described based on illustrated embodiments.

<CVD equipment>
FIG. 1 is a schematic view showing the structure of a reactor (CVD furnace) of a SiC manufacturing CVD apparatus used in the manufacturing method of the present invention.

  This CVD furnace is a hot wall type horizontal (substrate horizontal installation type) furnace using high frequency induction heating, in which a substrate having a diameter of 5.08 cm (2 inches) can be charged. A cylindrical susceptor 3 wrapped with a graphite heat insulating material 2 is installed in a cylindrical quartz outer tube 1. This susceptor 3 is also made of graphite, but the surface is coated with SiC. The appearance of the susceptor 3 is cylindrical, but the inside thereof is hollowed out to form a passage 4 along the axial direction, and the SiC substrate 5 is installed therein.

  Heating is performed by a high frequency induction method using a high frequency induction coil 6 wound around the quartz outer tube 1 so as to cover a hot wall portion composed of the heat insulating material 2 and the susceptor 3. The high frequency induction coil 6 heats a portion (substrate holder portion 3 a) of the susceptor 3 that holds the SiC substrate.

  The temperature measurement is a method in which the temperature in the quartz outer tube 1 is measured with a pyrometer from the radiation light during heating, and the temperature of the portion of the susceptor 3 holding the SiC substrate (substrate holder portion 3a) is set downstream. Is measured from. The measured temperature is fed back to the high frequency generator of the high frequency induction coil 6 to control the temperature in the quartz outer tube 1. The quartz outer tube 1 is air-cooled, and is always cooled by a fan during growth.

Exhaust is performed by a dry pump, and flows into the detoxification tower behind the pump. After the exhaust gas is detoxified, it is mixed with N ₂ for dilution and released into the atmosphere. There is a filter between the reactor and the pump to trap particles.

<Growth conditions>
SiH ₄ gas as silicon hydride gas (Si raw material gas), C ₃ H ₈ gas as hydrocarbon gas (C raw material gas), and carrier gas from the raw material introduction port of the quartz outer tube 1 into the passage 4 of the susceptor 3 Using H ₂ gas, these and HCl gas were simultaneously introduced into the quartz outer tube 1. That is, SiH ₄ was used as the Si raw material, C ₃ H ₈ was used as the C raw material, and H ₂ was used as the carrier gas. Growth was performed by mixing HCl with them.

  During the SiC epitaxial growth, the temperature of the substrate holder portion 3a was set to 1500 ° C. The pressure was about 13332 Pa (100 Torr). As the SiC substrate 5, a 4H—SiC substrate inclined by 2 ° in the [11-20] direction from the (0001) plane and a 4H—SiC substrate inclined by 3 ° in the [11-20] direction from the (0001) plane are used. Growing on the Si surface. Further, the SiC substrate 5 before growth was subjected to RCA cleaning, and the oxide film on the surface was removed.

The growth sequence is shown in FIG. Initially, the substrate holder portion 3a is heated to a growth temperature of 1550 ° C. (T1) while flowing only H ₂ gas (time a in FIG. 2).

  After raising the growth temperature to 1550 ° C. (T1) in a hydrogen atmosphere, the introduction of HCl gas is started, and the SiC surface is lightly etched to take steps (HCl treatment: times a to c in FIG. 2).

Before and after the end of the HCl treatment (time b and c in FIG. 2), C ₃ H ₈ gas and SiH ₄ gas are added into the furnace in this order to grow a SiC epitaxial layer (SiC growth treatment: FIG. 2 times cd). The amounts of SiH ₄ gas and C ₃ H ₈ gas during the growth of the SiC epitaxial layer were introduced so as to achieve 8 μm / hour when grown on a substrate inclined at 8 °, and the HCl flow rate was introduced at 50 sccm. The thickness of the grown epitaxial layer is 20 μm.

After the growth of the predetermined SiC epitaxial layer, the temperature lowering is started (time e in FIG. 2). The flow rate of the H ₂ gas to be flowed was constantly fixed at 20.0 slm from the temperature rise to the temperature rise (time a to e in FIG. 2), and the flow rate of the HCl gas during the surface treatment was 100 sccm.

<Epitaxial layer>
FIG. 3 is a photograph of the surface of the SiC epitaxial layer when grown on a 4H—SiC substrate inclined by 2 ° in the [11-20] direction from the (0001) plane, and FIG. 4 also shows the (0001) plane. The photograph of the surface of a SiC epitaxial layer when it grows on the 4H-SiC board | substrate inclined 3 degrees to [11-20] direction from FIG. Since the surface is flat and no linearly continuous defects are observed, it can be seen that no 3C structure is generated in the SiC epitaxial layer.

Note that the two SiC epitaxial layers whose surfaces are shown in FIGS. 3 and 4 are grown on the Si surface. Further, the amounts of SiH ₄ gas and C ₃ H ₈ gas at the time of SiC growth were introduced so as to achieve 8 μm / hour by growth on a substrate inclined at 8 °, and the HCl flow rate was introduced at 50 sccm. The thickness of the grown epitaxial layer is 20 μm.

<About optimum conditions>
The growth temperature, pressure, and C / Si ratio determined in the above examples are shown as the most proven conditions for the present inventors. If the quality of the epitaxial layer is not affected, there is no problem even if it is different from this condition.

  However, optimal growth conditions exist for the substrate tilt angle. The specifications of the inclined substrate to be used must be determined so that the inclination angle is as small as possible in consideration of the cost and the growth conditions that can be realized by the apparatus. This is because the SiC substrate is provided at a lower price as the tilt is smaller and the yield is improved.

  According to the experiments by the present inventors, when a 4H type SiC single crystal substrate is used, the inclination angle should be set as small as possible within the range of the inclination angle of 0.5 ° to 7.0 ° from the (0001) plane. For example, an SiC single crystal having a smaller tilt angle (0.5 ° to 7.0 °) than the conventional tilt angle (8 °), and having no problem in practical use without causing deterioration in flatness or increasing the number of defects. It turns out that can be obtained.

  Further, when a 6H-type SiC single crystal substrate is used, if the inclination angle is set as small as possible within the range of the inclination angle of 0.5 ° to 2.5 ° from the (0001) plane, the conventional inclination angle ( It is possible to obtain an SiC single crystal having no practical problem without deteriorating flatness and increasing the number of defects, while having an inclination angle smaller than (3.5 °) (0.5 ° to 2.5 °). I understood.

  Further, the HCl flow rate should be sufficient to cause a step on the growing epitaxial surface. However, if the flow rate of HCl is too large, the etching of the epitaxial layer proceeds excessively, and the film forming speed is reduced accordingly. There is therefore an optimal HCl flow rate. Although this differs depending on the apparatus used and the growth conditions, the flow rate of HCl gas is preferably 0.1 to 5.0% of the carrier gas flow rate.

  It was also found that the growth rate is preferably 20 μm / hour or less in order to reliably epitaxially grow the SiC single crystal.

<Other embodiments and modifications>
In the above embodiment, the carrier gas and the HCl gas are first supplied onto the SiC single crystal substrate, and then the hydrogenated hydrogen gas and the hydrocarbon gas are supplied. The hydrogen gas, the hydrocarbon gas, and the carrier gas can be supplied simultaneously with the HCl gas (for example, at the point a in FIG. 2), and this also achieves the intended effects of the present invention. be able to.

  Moreover, in the said Example, since the board | substrate used was a 4H-SiC board | substrate, the inclination angle was set to 2 degrees and 3 degrees, However, If a 6H-SiC board | substrate is used, an inclination angle may be made smaller. Is possible.

  Furthermore, in the above embodiment, the SiC substrate having the tilt direction of [11-20] is used. However, if the growth conditions are optimized, a substrate tilted in another direction can be used.

The structure of the CVD furnace for SiC manufacture of the board | substrate horizontal installation type used with the manufacturing method of this invention was shown, (a) is the schematic shown from the side, (b) is the cross-sectional schematic diagram. It is the figure which showed the growth sequence of SiC by CVD method which concerns on the manufacturing method of this invention. It is a drawing substitute photograph which shows the surface of the SiC epitaxial layer grown on the 2 degree inclination board | substrate by the manufacturing method of this invention. It is a drawing substitute photograph which shows the surface of the SiC epitaxial layer grown on the 3 degree inclination board | substrate by the manufacturing method of this invention. It is a figure which shows the progress state of the epitaxial growth on an inclination board | substrate. It is a drawing substitute photograph which shows the step which generate | occur | produces on SiC by high temperature HCl etching. It is a drawing substitute photograph which shows the surface of the SiC epitaxial layer which 3C structure generate | occur | produced. It is the figure which showed the structure of the SiC Schottky barrier diode obtained using the conventional CVD method. It is a schematic diagram of the epitaxial layer which inclines and grows in an edge part by use of an inclination board | substrate.

Explanation of symbols

1 Quartz outer tube 2 Heat insulation material (made of graphite)
3 Susceptor (made of graphite)
3a Substrate holder 4 Passage 5 SiC substrate 6 High frequency induction coil 21 Terrace 22 Kink 23 Random walk 24 Re-evaporation 25 Material deposition 31 n ⁺ type SiC substrate 32 n ⁻ type epitaxial layer 33 Schottky electrode 34 Ohmic electrode 35 Boron implantation region 36 SiO ₂ Passivate film 37 Substrate edge 38 Inclined region

Claims (7)

In a method for producing a silicon carbide single crystal by a CVD method in which a silicon hydride gas and a hydrocarbon gas are supplied onto a SiC substrate heated with a carrier gas, and a single crystal is grown by a thermal decomposition reaction,
As the SiC substrate, an SiC single crystal substrate inclined at a small inclination angle from the (0001) plane is used, and HCl gas is simultaneously supplied onto the SiC single crystal substrate together with a hydrogenated hydrogen gas, a hydrocarbon gas, and a carrier gas. A method for producing a silicon carbide single crystal, comprising: In a method for producing a silicon carbide single crystal by a CVD method in which a silicon hydride gas and a hydrocarbon gas are supplied onto a SiC substrate heated with a carrier gas, and a single crystal is grown by a thermal decomposition reaction,
As the SiC substrate, an SiC single crystal substrate tilted at a small tilt angle from the (0001) plane is used. A carrier gas and an HCl gas are first supplied onto the SiC single crystal substrate, and then a silicon hydride gas is used. A method for producing a silicon carbide single crystal, comprising supplying a hydrocarbon gas. In the manufacturing method of the silicon carbide single crystal of Claim 1 or 2,
As the SiC substrate, a SiC single crystal substrate having a 4H structure tilted in a range of 0.5 ° to 7.0 ° from the (0001) plane, or a range of 0.5 ° to 2.5 ° from the (0001) plane. A method for producing a silicon carbide single crystal, characterized by using a SiC single crystal substrate having a 6H structure tilted at 1. In the manufacturing method of the silicon carbide single crystal in any one of Claims 1-3,
H ₂ gas as a carrier gas, or He and the mixed gas of H ₂ or Ar and manufacturing method of silicon carbide single crystal, which comprises using one of a mixed gas of H _2,,. In the manufacturing method of the silicon carbide single crystal in any one of Claims 1-4,
A method for producing a silicon carbide single crystal, wherein a flow rate of HCl gas is set to 0.1 to 5.0% of a carrier gas flow rate. In the manufacturing method of the silicon carbide single crystal in any one of Claims 1-5,
Si ₂ H ₆ , SiH _4−x Cl _x (X = 1, ₂ , 3, 4), Si ₂ H _6−x Cl _x (X = 1, 2, 3, 4, 5) 6), and any one of CH ₄ , C ₂ H ₆ , and C (CH ₃ ) ₄ is used as the hydrocarbon gas. In the manufacturing method of the silicon carbide single crystal in any one of Claims 1-6,
A method for producing a silicon carbide single crystal, wherein the growth rate is 20 μm / hour or less.