JP2007186374A - Method for producing sic single crystal - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an SiC single crystal improved in crystal growth rate by a solution process. <P>SOLUTION: This production method comprises growing an SiC single crystal beginning at an SiC seed crystal 14 held just beneath a molten Si liquid level S while keeping a temperature gradient in a molten Si liquid M in a graphite crucible 10, where the temperature is lowered from inside toward the molten liquid level S, and applying an upward vertical magnetic field F heading for the molten liquid level S from the bottom of the crucible 10 to the molten liquid M in the crucible 10. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a SiC single crystal by a solution method.

  Since SiC has a larger energy band gap than Si, various techniques for producing high-quality SiC single crystals suitable as semiconductor materials have been proposed. As a method for producing an SiC single crystal, a sublimation method and a solution method are mainly known, and the solution method is attracting attention because it is effective for polytype controllability and reduction of micropipes.

  A method for producing an SiC single crystal by a solution method is disclosed, for example, in Patent Document 1 (Japanese Patent Laid-Open No. 4-193798). A temperature gradient is maintained in the Si melt in the graphite crucible that decreases in temperature from the inside toward the melt surface. C dissolved in the Si melt from the graphite crucible in the lower high temperature part rises mainly by the natural convection of the melt, reaches the low temperature part near the melt surface, and becomes supersaturated. An SiC seed crystal is held at the tip of the graphite rod immediately below the melt surface, and supersaturated C crystallizes as SiC by epitaxial growth on the SiC seed crystal.

  However, the solution method has a problem that the crystal growth rate is slower than the sublimation method.

  The manufacturing method of the SiC single crystal by the solution method has been improved from various viewpoints, and it has been proposed to apply a magnetic field to the Si melt. For example, Patent Document 2 (Japanese Patent Laid-Open No. 2004-323247) proposes that a downward vertical magnetic field from the Si melt surface toward the crucible bottom is applied to suppress natural convection and prevent polycrystallization. Has been. However, the growth rate does not improve.

  Patent Document 3 (Japanese Patent Application Laid-Open No. 2005-82435) describes that the growth surface is stabilized by adding any of Al, Ga, In, As, Sb, Au, Ag, and Pt to the Si melt. It has been proposed to keep it flat. Although a downward longitudinal magnetic field is applied in the embodiment, the growth rate is not improved.

  Further, although it is not a SiC single crystal, the same method for growing a Si single crystal as a semiconductor material can be applied by applying a lateral magnetic field transverse to the crystal growth direction in the pulling method from the Si melt. For controlling the oxygen concentration of silicon (Patent Document 4: JP-A-8-239292), improving the quality of Si single crystal by controlling the convection of the Si melt by applying a cusp magnetic field in particular in the transverse magnetic field A method (Patent Document 5: Japanese Patent Laid-Open No. 2000-119091) has been proposed. However, both are methods for growing a Si single crystal, not a SiC single crystal, and there is no suggestion regarding improvement of the growth rate.

  Further, Non-Patent Document 1 describes that the oxygen concentration in the Si single crystal is controlled by applying a downward longitudinal magnetic field by a current magnetic field application pulling method (EMCZ method). In this case as well, this is a method for growing an Si single crystal instead of an SiC single crystal, and there is no suggestion for improving the growth rate.

JP-A-4-193798 JP 2004-323247 A JP 2005-82435 A JP-A-8-239292 JP 2000-119091 A Watanabe Hayato “Journal of Japanese Society for Crystal Growth” 13-19, vol. 26, No. 5, 1999.

  An object of this invention is to provide the manufacturing method of the SiC single crystal by the solution method which improved the crystal growth rate.

In order to achieve the above object, according to the present invention, the Si melt in the graphite crucible is maintained immediately below the melt surface while maintaining a temperature gradient in which the temperature decreases from the inside toward the melt surface. In the method of growing a SiC single crystal starting from the SiC seed crystal,
There is provided a method for producing an SiC single crystal, wherein an upward vertical magnetic field from a crucible bottom to a melt surface is applied to a melt in a crucible.

  In the present invention, the growth rate of the SiC single crystal can be significantly improved by applying an upward vertical magnetic field from the bottom of the crucible toward the Si melt surface to the Si melt.

  The present inventor has newly found that when an upward vertical magnetic field directed from the bottom of the crucible toward the Si melt surface is applied to the Si melt, the growth rate of the SiC single crystal is greatly improved, and the present invention is based on this. Completed. The reason why the growth rate is improved by the application of the upward vertical magnetic field has not been clarified at present, but is considered as follows.

  That is, natural convection is generated in the Si melt when no magnetic field is applied due to a temperature gradient that decreases in temperature from the bottom of the crucible toward the melt surface. Since this natural convection is irregular and complicated, the transport efficiency of C from the bottom of the crucible to the vicinity of the seed crystal is low. For example, phenomena such as undesirable SiC nucleation at a place other than the seed crystal, such as the inner wall of the crucible, and the resulting polycrystalline formation are considered to contribute to the low C transport efficiency.

  On the other hand, when an upward longitudinal magnetic field is applied according to the present invention, complicated movement of natural convection is suppressed, undesirable SiC nucleation other than the seed crystal is avoided, and C from the crucible bottom to the vicinity of the seed crystal is avoided. It is thought that the growth rate is improved because the transportation efficiency is increased. At this time, if the strength of the upward vertical magnetic field is 0.03 to 0.15 T, the growth rate is particularly improved.

  When the melt is rotated in the crucible circumferential direction by applying a current to the melt in the crucible and generating a Lorentz force in addition to the longitudinal magnetic field, the growth rate can be further improved. At this time, if the current for generating the Lorentz force is 3 A to 10 A, the growth rate is particularly improved.

  When the crucible is rotated in the direction opposite to the rotation of the melt by the Lorentz force, the growth rate can be further improved. At this time, when the crucible is rotated at 3 to 20 rpm, the growth rate is particularly improved.

  FIG. 1 shows an example of the structure of an SiC single crystal manufacturing furnace suitable for carrying out the method of the present invention.

  The illustrated SiC single crystal manufacturing furnace 100 maintains a temperature gradient in the Si melt M in the graphite crucible 10 that decreases in temperature from the inside toward the melt surface S, while the graphite rod 12 is directly below the melt surface S. This is a furnace for growing a SiC single crystal starting from the SiC seed crystal 14 held by the above.

  A heat insulating material 18 surrounds the entire graphite crucible 10. An induction coil 22 for heating surrounds the heat insulating material. The upper coil 22A and the lower coil 22B constituting the induction coil 22 can be controlled independently, thereby forming a necessary temperature gradient in the Si melt M. The temperature of the bottom of the crucible 10 and the temperature of the melt surface S are each measured with a pyrometer (not shown), and the output of the induction coil 22 is adjusted based on the measured temperatures to determine the temperature and temperature gradient of the Si melt M. Control to value. A general SiC single crystal manufacturing process using the SiC single crystal manufacturing furnace 100 proceeds as follows.

  First, Si raw material is charged into the graphite crucible 10 and the induction coil 22 is operated to form the Si melt M.

  An SiC seed crystal 14 is attached to the lower end of the graphite rod 12 and inserted immediately below the Si melt surface S.

  The melt M is heated by increasing the output of the induction coil 22. At that time, the upper coil 22A output / lower coil 22B output is set to about 30 to 50%, and the temperature is raised as a whole while maintaining the temperature gradient in the Si melt from the lower part to the upper part. From the time when the temperature of the lower part of the melt exceeds the melting point of Si (1410 ° C.), C gradually begins to dissolve in the lower high-temperature Si melt from the graphite crucible 10.

  The dissolved C is transported upward in the Si melt by diffusion and convection, and arrives at the SiC seed crystal 14. The vicinity of the seed crystal 14 is maintained at a lower temperature than the lower part of the melt by the output control of the upper stage 22A / lower stage 22B of the induction coil 22 and the heat radiation from the melt surface S. When the C dissolved in the melt at a high temperature reaches the vicinity of the seed crystal 14 having a low solubility at a low temperature, a supersaturated state is reached, and a SiC single crystal grows on the seed crystal 14 using this supersaturation as a driving force. .

  A feature of the present invention is that an upward longitudinal magnetic field F directed from the bottom of the crucible 10 toward the Si melt surface S is applied to the Si melt M by the magnetic field coil 24, whereby natural convection in the Si melt is achieved. Is suppressed, the transport efficiency of C from the bottom of the crucible to the seed crystal 14 is increased, and the growth rate is improved.

  The strength of the upward longitudinal magnetic field applied to the melt M to suppress convection is preferably 0.03T to 0.15T. If the strength of the upward vertical magnetic field is too small, the effect of suppressing convection cannot be obtained, and if the strength is too large, convection due to the magnetic field occurs. When the magnetic field intensity is in the above range, the melt surface is stable, and fluctuations and swelling are not visually recognized.

  In the present invention, the reason why the applied magnetic field is limited to the upward vertical magnetic field is as follows. That is, when the apparatus of FIG. 1 is used, as shown in FIG. 2, four types of (1) upward vertical magnetic field, (2) downward vertical magnetic field, (3) vertical opposed cusp magnetic field, and (4) vertical discrete cusp magnetic field are used. The magnetic field of the form can be applied. In FIG. 2, the vertical direction in the figure corresponds to the actual vertical direction. Similarly to FIG. 1, 24 indicates a magnetic field coil, and F indicates a magnetic field.

  Actually, experiments were conducted by applying magnetic fields of these forms. In the case of a longitudinal magnetic field, the movement of the melt due to natural convection is suppressed regardless of the direction of the magnetic field (1) (2), and the melt surface S is It appears to be stationary. On the other hand, in the case of a cusp magnetic field, the movement of the melt surface S is the same as in natural convection and no change is observed even if the magnetic field strength is increased in any of the forms (3) and (4). Of these four forms, a clear improvement in the growth rate of the SiC single crystal was observed only in the case of (1) the upward vertical magnetic field. Therefore, the magnetic field applied to the Si melt M in the present invention is limited to the upward longitudinal magnetic field shown in FIG.

  Referring again to FIG. 1, the graphite rod 12 for mounting the seed crystal and the electrode rod 16 are used as a pair of current supply terminals, the lower ends of both are immersed in the Si melt, and the upper ends of both are connected to the DC power source via the power switch 19. 20 is connected. When the power switch 19 is turned on, a direct current is applied to the Si melt by the graphite rod 12 and the electrode rod 16, and a Lorentz force in the crucible circumferential direction is generated by Fleming's law. Rotate in the direction. When the Si melt rotates in the crucible circumferential direction in this way, the melt surface S is moderately disturbed, and the dissolved C is efficiently supplied to the seed crystal 14. The crystal growth rate is improved.

  Further, in FIG. 1, the crucible 10 can be rotated in the circumferential direction of the crucible as indicated by an arrow R. When the direction of the rotation R is opposite to the circumferential rotation of the Si melt M by the Lorentz force, the growth rate of the SiC single crystal is further improved. However, the mechanism has not been elucidated at this time.

  Using the SiC single crystal manufacturing furnace 100 of FIG. 1, an upward vertical magnetic field according to the present invention was applied to manufacture an SiC single crystal by a solution method. In the examples according to the preferred embodiments of the present invention, the melt was rotated by the Lorentz force in addition to the upward longitudinal magnetic field. In an example according to a further preferred embodiment of the present invention, the crucible was rotated in addition to the upward longitudinal magnetic field and the Lorentz force. Regarding the temperature gradient, the temperature gradient in the region up to 10 mm immediately below the seed crystal is particularly important, and in this example, the temperature gradient was controlled to 10 ° C./mm or less.

  The growth rate of the SiC single crystal was measured by changing various parameters of the longitudinal magnetic field strength, the applied current for generating the Lorentz force, and the number of revolutions of the crucible. The results are shown in Tables 1 and 2. In these tables, numerical ranges described in parentheses under the item names in the uppermost column are desirable ranges of the present invention.

  In Table 1, Sample Nos. 1 to 3 are the results when all of the above three parameters are within the desirable range of the present invention, and a high growth rate of 120 to 160 μm / h is obtained. Samples Nos. 4 to 8 are cases where only the upward longitudinal magnetic field among the three parameters (Nos. 4, 7, and 8), Lorentz force addition (No. 5), and crucible rotation taking Lorentz force are added. Although a high growth rate of h to 130 μm / h was obtained, pores and melt entrainment due to entrainment of gas occurred.

  Table 2 shows the results when at least one of the three parameters falls outside the desirable range of the present invention or is “none”, and the growth rate is 40 to 80 μm / h. Overall, the growth rate is faster under the conditions in Table 1 than in the conditions in Table 2.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the SiC single crystal by the solution method which improved the crystal growth rate is provided.

FIG. 1 is a longitudinal sectional view showing a structural example of a SiC single crystal manufacturing furnace suitable for carrying out the method for manufacturing a SiC single crystal of the present invention. FIG. 2 is a layout diagram showing four types of magnetic field forms that can be applied to the Si melt by the furnace of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 SiC single crystal manufacturing furnace 10 Graphite crucible 12 Graphite rod 14 SiC seed crystal 16 Electrode rod 18 Thermal insulation material 19 Power switch 20 DC power source 22 Induction coil 22A Upper coil 22B Lower coil 24 Magnetic field coil M Si melt S Si melt surface F magnetic field

Claims (6)

In a method of growing a SiC single crystal starting from a SiC seed crystal held immediately below the melt surface while maintaining a temperature gradient in the Si melt in the graphite crucible that decreases from the inside toward the melt surface ,
A method for producing an SiC single crystal, wherein an upward vertical magnetic field directed from a bottom of a crucible toward a melt surface is applied to a melt in a crucible.   2. The method according to claim 1, wherein the intensity of the longitudinal magnetic field is 0.03 to 0.15T.   3. The method according to claim 1, wherein the melt is rotated in the circumferential direction of the crucible by applying a current to the melt in the crucible to generate a Lorentz force.   4. The method according to claim 3, wherein the current is 3A to 10A.   5. The method according to claim 3, wherein the crucible is rotated in a direction opposite to the rotation of the melt by the Lorentz force.   6. The method of claim 5, wherein the crucible is rotated at 3-20 rpm.

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