(19)
(11)EP 0 916 750 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
05.03.2003 Bulletin 2003/10

(21)Application number: 98121099.0

(22)Date of filing:  06.11.1998
(51)Int. Cl.7C30B 29/36, C30B 25/02

(54)

Single crystal SiC and a method of producing the same

SiC-Einkristall und Verfahren zu seiner Herstellung

Monocristal de SiC et procédé pour sa préparation


(84)Designated Contracting States:
DE FR GB

(30)Priority: 17.11.1997 JP 31512697

(43)Date of publication of application:
19.05.1999 Bulletin 1999/20

(73)Proprietor: Nissin Electric Co., Ltd.
Kyoto-shi, Kyoto 615 (JP)

(72)Inventors:
  • Tanino, Kichiya c/oNippon Pillar Packing Co.,Ltd.
    Sanda-shi, Hyogo-ken (JP)
  • Hiramoto, Masanobu c/oNippon Pillar Pack. Co.,Ltd.
    Sanda-shi, Hyogo-ken (JP)

(74)Representative: Fleuchaus, Leo, Dipl.-Ing. et al
Fleuchaus & Gallo Melchiorstrasse 42
81479 München
81479 München (DE)


(56)References cited: : 
WO-A-98/53125
US-A- 4 912 064
  
  • PATENT ABSTRACTS OF JAPAN vol. 16, no. 249 (C-0948), 8 June 1992 & JP 04 055397 A (MITSUI ENG & SHIPBUILD CO LTD), 24 February 1992
  • PATENT ABSTRACTS OF JAPAN vol. 11, no. 396 (E-568), 24 December 1987 & JP 62 159444 A (FUJITSU LTD), 15 July 1987
  • PATENT ABSTRACTS OF JAPAN vol. 97, no. 4, 30 April 1997 & JP 08 323604 A (CANON INC)
  • CHIEN ET AL.: "Interface structures of beta SiC on alpha SiC substrates" JOURNAL OF CRYSTAL GROWTH., vol. 137, no. 1/2, 11 March 1994, pages 175-180, XP000480897 AMSTERDAM NL
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description

Background of the Invention


1. Field of the Invention



[0001] The present invention relates to single crystal SiC and a method of producing the same, and more particularly to single crystal SiC which is used as a semiconductor substrate wafer for a light-emitting diode, an X-ray optical element such as a monochromatic sorter, a high-temperature semiconductor electronic element, and a power device, and also to a method of producing the single crystal SiC.

2. Description of the Prior Art



[0002] SiC (silicon carbide) is superior in heat resistance and mechanical strength, and also has good resistance to radiation. In addition, it is easy to perform the valence control of electrons and holes by doping an impurity. Moreover, SiC has a wide band gap (for example, single crystal 6H-SiC has a band gap of about 3.0 eV, and single crystal 4H-SiC has a band gap of 3.26 eV). Therefore, it is possible to realize a large capacity, a high frequency, a high dielectric strength, and a high resistance to environments which cannot be realized by existing semiconductor materials such as Si (silicon) and GaAs (gallium arsenide). For these reasons, single crystal SiC receives attention and is expected as a semiconductor material for a next-generation power device.

[0003] As a method of growing (producing) single crystal SiC of this type, employed are the Achison method and the sublimation and recrystallization method which are generally known as an industrial method of producing an SiC abrasive material. In the Achison method, a seed crystal substrate is heated from the outer circumference by using a high frequency electrode, so as to generate many nuclei in a center portion of the seed crystal substrate, whereby a plurality of spiral crystal growths are developed with being centered at the center portion of the seed crystal substrate. In the sublimation and recrystallization method, powder SiC produced by the Achison method is used as a raw material, and a crystal is grown on a single crystal nucleus.

[0004] In the Achison method of the above-described conventional production methods, however, a single crystal is grown slowly over a long time period, so that the crystal growth rate is very low. In addition, a large number of crystal nuclei are generated in an initial growth stage, and they propagate to an upper portion of the crystal as the crystal growth advances. Thus, it is difficult to singly obtain a large-size single crystal.

[0005] In the sublimation and recrystallization method, a highspeed growth of about 1 mm/hr is adopted mainly for an economical reason (production cost), so that impurities and pin holes which have a diameter of several microns and which pass through the crystal in the growing direction are likely to remain in a growing crystal. Such pin holes are called micropipe defects and cause a leakage current when a semiconductor device is fabricated. Accordingly, there exists a problem in that single crystal SiC having sufficiently good quality cannot be obtained. This blocks a practical use of SiC which has superior characteristics as compared with other existing semiconductor materials such as Si and GaAs as described above.

Summary of the Invention



[0006] The invention has been conducted in view of the above-mentioned circumstances. It is an object of the invention to provide large-size single crystal SiC,which has high quality and in which no crystalline nucleus is generated by use of a method of producing single crystal SiC in which a single crystal having high quality can be stably efficiently produced at a higher growing rate.

[0007] In order to attain the mentioned object, the essential features of the method of producing single crystal SiC of the invention is defined in claim 1.

[0008] Further preferred embodiments of the invention are defined in the dependent claims 2 and 3.

[0009] According to the invention having the above-mentioned characteristics a single crystal SiC, a single crystal α-SiC substrate in which surface physical unevenness is small and in which the surface roughness is adjusted so as to be equal to or lower than 2 x 102nm (2,000 angstroms) RMS, and more preferably equal to or lower than 1 x 102nm (1,000 angstroms) RMS is produced. The surface roughness which is thus adjusted can easily eliminate a mismatch of a crystal lattice caused by a phenomenon in which phase transformation occurs simultaneously from a bottom face and a side face of a concave portion in the heat treatment.

[0010] The heat treatment at a high temperature which is equal to or higher than the film growing temperature, so that single crystal α-SiC can be integrally grown on the single crystal α-SiC substrate by recrystallization is performed in imitation of the growth of the single crystal α-SiC on the substrate side and in a substantially entire region other than end portions of the poly crystal on the polycrystalline α-SiC film side. Accordingly, it is possible to stably and efficiently obtain single crystal SiC of a large size and having high quality in which crystal nuclei are not generated by the mismatch of a crystal lattice and any micropipe defect or the like cannot occur. Thus, it is possible to attain the effect of expediting the practical use of single crystal SiC which is superior in a large capacity, a high frequency, a high dielectric strength, and a high resistance to environments to existing semiconductor materials such as Si (silicon) and GaAs (gallium arsenide) and which is expected as a semiconductor material for a power device.

[0011] Other objects and effects of the invention will be clarified in embodiments which will be described below.

Brief Description of the Drawings



[0012] 

Fig. 1 is a side view showing a single crystal α-SiC substrate in the method of producing single crystal SiC according to the invention;

Fig. 2 is a side view showing a state in which a polycrystalline α-SiC film is grown by thermal CVD on the surface of the single crystal α-SiC substrate;

Fig. 3 is a schematic side view showing a heat treatment state of a complex; and

Fig. 4 is a front view showing single crystal SiC obtained by the heat treatment.


Preferred Embodiments of the Invention



[0013] Hereinafter, an embodiment of the invention will be described with reference to the drawings.

[0014] Figs. 1 to 4 are views illustrating the method of producing single crystal SiC according to the invention, in the sequence of production steps. In Fig. 1, 1 denotes a single crystal hexagonal α-SiC substrate (6H type or 4H type) which is processed so as to have a disk-like shape of a diameter d of about 25 mm. The surface 1a of the single crystal α-SiC substrate 1 is ground or polished so as to remove physical unevenness. Specifically, the surface 1a is adjusted so as to have a surface roughness which is equal to or lower than 2x102nm (2,000 angstroms) RMS, preferably equal to or lower than 1x102nm (1,000 angstroms) RMS, and more preferably in the range of 1 x 101 to 5 x 101 nm (100 to 500 angstroms).

[0015] Thereafter, on the surface 1a of the single crystal α-SiC substrate 1, a polycrystalline α-SiC film 2 is grown as shown in Fig. 2 by thermal chemical vapor deposition (hereinafter referred to as thermal CVD) under conditions listed in Table 1 below. The polycrystalline α-SiC film 2 is grown so as to have a film thickness t of 200 to 500 µm, preferably about 300 µm.
Table 1
(Conditions of Thermal CVD)
Reaction gas carrier H2
carbon source CH4
silicon source SiCl4
Reaction temperature 1,850°C (equal to or higher than 1,650°C)
Total gas pressure 104 Pa (100 mbar) preferably 3x103 Pa (30 mbar) to 2 x 104 Pa (200 mbar)
Total gas flow rate 50 l/min (preferably equal to or higher than 50 l/min)
Specification of substrate single crystal α-SiC having a diameter of 25 mm
Film growing rate 10 µm/hr


[0016] Next, a complex M consisting of the single crystal α-SiC substrate 1 and the polycrystalline α-SiC film 2 is accommodated in a porous carbon container 3 as shown in Fig. 3. Under a state where the outer side of the porous carbon container 3 is surrounded and covered with α-SiC powder 4, a heat treatment is performed in an argon gas flow at a temperature of 1,900 to 2,400°C, preferably 2,200°C for about 2 hours. As a result, as shown in Fig. 4, in imitation of the growth of the single crystal of the single crystal α-SiC substrate 1, a polycrystal of the polycrystalline α-SiC film 2 is recrystallized to grow single crystal α-SiC 5 in an entire region other than end portions 2e and 2e of the polycrystalline α-SiC film 2 formed over the side face of the entire circumference of the single crystal α-SiC substrate 1. The single crystal α-SiC 5 is integrally grown in a range from the surface (crystal orientation face) 1a of the single crystal α-SiC substrate 1 to the polycrystalline α-SiC film 2. The single crystal α-SiC 5 has the same orientation as that of the crystal axis of the single crystal α-SiC substrate 1.

[0017] As described above, as the single crystal α-SiC substrate 1, used is a substrate with little physical unevenness in the surface, and having a surface roughness which is adjusted so as to be equal to or lower than 2x102nm (2,000 angstroms) RMS, preferably equal to or lower than 1x102nm (1,000 angstroms) RMS at which mismatch of the crystal lattice caused by simultaneous phase transformation from bottom and side faces of a concave portion in the heat treatment can be eliminated. The complex M which is formed by growing the polycrystalline α-SiC film 2 on the surface of the substrate 1 is subjected to the heat treatment at a high temperature (2,200°C, 2 hours) which is equal to or higher than the film growing temperature (1,850°C) in the thermal CVD. As a result, in imitation of the growth of the single crystal α-SiC on the side of the substrate 1, the polycrystal on the side of the polycrystalline α-SiC film 2 is recrystallized in a substantially entire region other than the end portions of the film growing portion. Thus, the single crystal α-SiC which is orientated in the same direction as the crystal axis of the single crystal α-SiC substrate 1 is integrally grown. In this way, it is possible to efficiently produce single crystal SiC of a large size and with high quality in which any crystal nucleus caused by the mismatch of the crystal lattice is not generated in an interface and any micropipe defect does not occur.

[0018] In this connection, results shown in Table 2 below were obtained when the surface roughness of the single crystal α-SiC substrate 1 was variously changed and the crystal qualities of respective single crystal α-SiC produced by the above-described producing process were evaluated by X-ray diffraction. As for the numerical values shown in Table 2, the values in the upper row denote values of the surface roughness RMS (unit: nm ), and those in the lower row denote half band widths (integrated intensity ratio) of an X-ray rocking curve of (0006) reflection of the respective single crystals. Each half band width was obtained by averaging measured values at arbitrary five points.
Table 2
Surface roughness RMS 3 x 102nm (3,000 Å) 2 x 102nm (2,000 Å) 1 x 102nm (1,000 Å) 0,5 x 102nm (500 Å)
Half band width 0.8° 0.9°


[0019] As apparent from Table 2 2 above, when the surface roughness of the single crystal α-SiC substrate 1 is 2 x 102nm (2,000 angstroms) RMS, the half band width is rapidly narrowed. Thus, it is understood that there is no variation in crystal quality and the crystals are good in unity.

[0020] In addition, in the heat treatment of the complex M, the complex M is placed in the porous carbon container 3, and the outer side of the carbon container 3 is covered with the α-SiC powder 4. The predetermined heat treatment is performed in the argon gas flow, so that the α-SiC powder 4 is decomposed in a high temperature atmosphere. At least part of the decomposed Si and C is moved into the porous carbon container 3 through the container 3, so that the predetermined heat treatment can be performed in a saturated SiC vapor atmosphere. Accordingly, the decomposition of the single crystal α-SiC substrate 1 and the polycrystalline α-SiC film 2 can be suppressed, and it is possible to produce single crystal SiC of higher quality. Moreover, it is possible to prevent the Si and C which are moved into the porous carbon container 3 through the container 3, from adhering to SiC before phase transformation. Accordingly, it is possible to produce good single crystal with higher quality.


Claims

1. A method of producing single crystal SiC, wherein a surface of a single crystal α-SiC substrate is adjusted to have a surface roughness equal to or lower than 2x102 nm (2000 angstroms) RMS,
   a polycrystalline α-SiC film is grown on the surface of said single crystal α-SiC substrate, and the complex is then heat-treated at a high temperature in a range of 1900 to 2400°C, said heat treatment of said complex is performed under a state where said complex is placed in a porous carbon container, and an outer side of said porous carbon container is covered with α-SiC powder, whereby single crystal α-SiC is integrally formed on said single crystal α-SiC substrate by crystal growth and recrystallization of said polycrystalline α-SiC film.
 
2. A method of producing single crystal SiC according to claim 1, wherein the surface roughness of said single crystal α-SiC substrate is adjusted to be equal to or lower than 1x102 nm (1000 angstroms) RMS.
 
3. A method of producing single crystal SiC according to claim 1 or 2, wherein said polycrystalline α-SiC film is grown by thermal chemical vapor deposition.
 


Ansprüche

1. Ein Verfahren zum Erzeugen eines SiC-Einkristalls, in dem eine Oberfläche eines α-SiC-Einkristall-Substrats so eingestellt wird, daß sie eine Rauhtiefe von höchstens 2x102 nm (2000 Å) RMS aufweist,
wobei eine polykristalline α-SiC-Dünnschicht auf der Oberfläche des α-SiC-Einkristall-Substrats gezogen wird, dann der Komplex bei hoher Temperatur im Bereich 1900 bis 2400°C wärmebehandelt wird, und die Wärmebehandlung des Komplexes in einem Zustand ausgeführt wird, in dem der Komplex in einen porösen Kohlenstoff-Behälter verbracht wird und eine Außenseite des porösen Kohlenstoffbehälters mit α-SiC-Pulver bedeckt wird, wobei ein α-SiC-Einkristall durch Kristall-Aufwachsen und Umkristallisieren der polykristallinen α-SiC-Dünnschicht auf dem α-SiC-Einkristall-Substrat ausgebildet wird.
 
2. Ein Verfahren zum Erzeugen eines SiC-Einkristalls gemäß Anspruch 1, in dem die Oberflächen-Rauhtiefe des α-SiC-Einkristall-Substrats so eingestellt wird, daß sie höchstens 1x102 nm (1000 Å) RMS beträgt.
 
3. Ein Verfahren zum Erzeugen SiC-Einkristalle gemäß Anspruch 1 oder 2, in dem die polykristalline α-SiC-Dünnschicht durch thermische chemische Dampfabscheidung aus der Gasphase gezogen wird.
 


Revendications

1. Procédé de production d'un monocristal de SiC, dans lequel une surface d'un substrat de α-SiC monocristallin est ajustée pour présenter une rugosité de surface inférieure ou égale à 2 x 102 nm (2 000 angströms) RMS,
   un film de α-SiC polycristallin est mis à croître à la surface dudit substrat de α-SiC monocristallin, et le complexe est ainsi traité thermiquement à une température élevée dans une plage de 1 900 à 2 400 °C, ledit traitement thermique dudit complexe est exécuté dans un état dans lequel ledit complexe est placé dans un récipient de carbone poreux, et un côté extérieur dudit récipient de carbone poreux est recouvert de poudre de α-SiC, grâce à quoi le monocristal de α-SiC est formé de façon intégrale sur ledit substrat de α-SiC monocristallin par la mise en croissance du cristal et la recristallisation dudit film de α-SiC polycristallin.
 
2. Procédé de production d'un monocristal de SiC selon la revendication 1, dans lequel la rugosité de surface dudit substrat de α-SiC monocristallin est ajustée de façon à être inférieure ou égale à 1 x 102 nm (1 000 angströms) RMS.
 
3. Procédé de production d'un monocristal de SiC selon la revendication 1 ou 2, dans lequel ledit film de α-SiC polycristallin est mis à croître par un dépôt chimique en phase vapeur thermique.
 




Drawing