SILICON CARBIDE DIFFUSION TUBE FOR SEMI-CONDUCTOR

Abstract: Disclosed is a silicon carbide type diffusion tube comprising a diffusion tube base made of reaction-sintered silicon carbide having an iron concentration of 20 ppm or below and a density of 3.0 g/cm³ or over, and a silicon carbide layer consisting of a high-purity silicon carbide film having an iron concentration of 5 ppm or below deposited on the inner surface of the tube base and a silicon carbide type diffusion tube comprising a diffusion tube base made of reaction-sintered silicon carbide, and a silicon carbide layer consisting of a Si-depleted layer formed in the inner wall of the reaction-sintered silicon carbide tube base and a high-purity silicon carbide film deposited on the Si-depleted layer, said silicon carbide film having a thickness of more than 0.5 mm.

Description: The present invention relates to a diffusion tube particularly used in a diffusion furnace in which a semiconductor is heat-treated, and more particularly relates to a silicon carbide type diffusion tube that will not allow silicon wafers to have defects due to the presence of impurities. Conventionally, as a diffusion tube for a semiconductor diffusion furnace, a quartz diffusion tube or a silicon carbide type diffusion tube is used. When these diffusion tubes are used to heat-treat a semiconductor, impurities present in the diffusion tube cause the silicon wafer to have defects, lowering considerably the yield of the semiconductor in the heat-treatment step. With respect to the purity, since quartz is superior to silicon carbide, a quartz diffusion tube is generally used. However, even quartz is not satisfactory enough with respect to the purity. Furthermore, quartz diffusion tubes are liable to deform at a high temperature and therefore have a defect that the life is short. Particularly, when the treating temperature is over 1,200 °C, the wear is severe due to deformation, devitrification, etc., so that quartz diffusion tubes have to be replaced frequently. On the other hand, if the treating temperature is lowered in order to avoid the problems of deformation and devitrification of quartz diffusion tubes, the treating time must be extended considerably, resulting in high cost of the production of the semiconductor. In contrast, a silicon carbide type diffusion tube deforms hardly even at a high temperature, and devitrification observed in a quartz diffusion tube will not take place in the case of a silicon carbide type diffusion tube. The usable period of a silicon carbide type diffusion tube can be extended considerably in comparison with a quartz diffusion tube. However, with respect to the purity, since a silicon carbide type diffusion tube in the prior art is inferior to a quartz diffusion tube, the application of a silicon carbide type diffusion tube is limited. US-A-4 619 798 discloses a method of manufacturing a silicon carbide type diffusion tube by molding a SiC powder, a sintering assistant and a binder to a predetermined form, purifying the molded body by subjecting it to an atmosphere of hydrogen halide gas at a temperature in the range of 800-1300 °C, sintering the molded body and coating a SiC film on at least part of the sintered body by CVD, preferably in a thickness of 100-300 µm. FR-A-2 535 312 describes a silicon carbide molded body for the manufacture of semiconductors having an iron content of less than 20 ppm. JP-A-60 246 264 discloses a method of producing a high density SiC diffusion tube for a heat treatment furnace to be used in the manufacture of a semiconductor device, wherein a SiC powder and carbon powder containing slip is formed into a desired shape and cured and, finally, the shaped body is immersed in a molten silicon to convert the carbon in the shaped body into silicon carbide. SUMMARY OF THE INVENTION The object of the present invention is to provide a silicon carbide type diffusion tube effective for a semiconductor diffusion furnace that does not have disadvantages such as deformation and devitrification even at a high temperature and does not allow a silicon wafer to have defects due to the presence of impurities. The above object is attained by a silicon carbide type diffusion tube comprising a diffusion tube base made of reaction-sintered silicon carbide having an iron concentration of 20 ppm or below and a density of 3.0 g/cm³ or more, and a silicon carbide layer consisting of a Si-depleted layer formed in the inner wall of the reaction-sintered silicon carbide tube base, the Si-depleted layer having a thickness of 0.4 to 0.7 mm, and a high-purity silicon carbide film deposited on the Si-depleted layer having an iron concentration of 5 ppm or below, said silicon carbide layer having a thickness of more than 500 µm and not more than 2000 µm. The inventors have found that since the silicon carbide type diffusion tube in the prior art is only made of a composite material of SiC and Si and the diffusion coefficient of impurities at a high temperature is far higher in Si than in SiC, the impurities contaminate the inside wall of the diffusion tube mainly through the Si phase. When a high-purity silicon carbide film having an iron concentration of 5 ppm or below is deposited on the inner surface of the diffusion tube base, for example, by CVD (chemical vapor deposition) process according to the present invention, the diffusion of impurities into the inside layer of the diffusion tube from the diffusion tube base and the outside of the diffusion tube can be intercepted by the film. The diffusion tube in which the tube base is made of reaction-sintered silicon carbide having a density of 3.0 g/cm³ or more and the silicon carbide film is deposited on the inner surface thereof according to the present invention would neither deform nor devitrify even at a high temperature, is excellent in strength, can be used for a long period of time under high-temperature conditions, and therefore can be used as a diffusion tube suitable for a semiconductor diffusion furnace. Specifically, the inventors have found that the diffusion of impurities from the diffusion tube base and the outside into the inside layer of the diffusion tube can be more positively intercepted and a diffusion tube for a semiconductor diffusion furnace that is positively prevented from deforming or devitrifying even at a high temperature can be provided, when a diffusion tube comprises a diffusion tube base made of reaction-sintered silicon carbide and a silicon carbide layer consisting of a Si-depleted layer formed in the inner wall of the reaction-sintered silicon carbide tube base and a high-purity silicon carbide film deposited on the Si-depleted layer, and the silicon carbide layer has a thickness of more than 500 µm. The technique of forming a silicon carbide film on the inner surface of a recrystallized silicon carbide type diffusion tube is known from Japanese Patent Publication No. 20128/1986, but the technique is intended to improve the corrosion resistance at the time when the diffusion tube is cleaned. In contrast, the inventors have found that by using reaction-sintered silicon carbide as a base material of a diffusion tube and by controlling the iron concentration of diffusion tube matrix to be 20 ppm or below and the density thereof to be 3.0 g/cm³ or more and depositing a high-purity silicon carbide film having an iron concentration of 5 ppm or below on the inner surface of the diffusion tube base, after the inner wall of the tube base has been subjected to a Si removing treatment, the diffusion of impurities from the diffusion tube matrix and the outside can be effectively intercepted by the film, and contamination of a silicon wafer due to the presence of impurities in the heat treatment step can be effectively prevented. Therefore the purpose of the present invention is quite different from that of the prior art. The technique described in Japanese Patent Publication No. 20128/1986 mentioned above uses recrystallized silicon carbide as the base material. Since the strength of the recrystallised silicon carbide is poor (the bend strength of reaction-sintered silicon carbide is 343 to 441 N/mm² (35 to 45 kg/mm²), whereas the bend strength of recrystallized silicon carbide is 147 to 245 N/mm² (15 to 25 kg/mm²), which is about half of that of reaction-sintered silicon carbide), the recrystallized silicon carbide having the film deposited thereon will break, when used under high-temperature conditions, due to the thermal stress generated by a difference in the thermal expansion coefficient between the film deposited on the inner surface and the base material. Particularly, when it is repeatedly used over and over again, it will break very easily due to the thermal cycles. In contrast, since the tube base formed from the reaction-sintered silicon carbide having a density of 3.0 g/cm³ or more is high in strength, even when the diffusion tube is used under high-temperature conditions or subjected to repeated thermal cycles, the diffusion tube according to the present invention will not break easily and can be used for a longer period of time. Thus, the present inventors have found that it can be used suitably for a semiconductor diffusion furnace. Further, in Japanese Patent Publication No. 20128/1986, the thickness of the silicon carbide film is 500 µm or below. In the process of forming a silicon carbide film on a recrystallized silicon carbide type diffusion tube surface in the prior art, the film is formed on the porous recrystallized silicon carbide type diffusion tube surface, and then the outer surface is impregnated with Si. Since the recrystallized silicon carbide is poor in strength, if the thickness of the silicon carbide film is made to be more than 0.5 mm, the film will break due to the thermal cycles when used. According to the present invention, since reaction-sintered silicon carbide having a density of 3.0 g/cm³ or more is used as the base material, the tube base is high in strength, and it has no problems if the thickness of the silicon carbide layer is made to be more than 0.5 mm or even to be 1 mm or over, thereby attaining a great effect on the interception of impurities. Thus, the reaction-sintered silicon carbide and the recrystallized silicon carbide are different in their methods of production and properties. Therefore, the present invention provides a silicon carbide type diffusion tube comprising a diffusion tube base made of reaction-sintered silicon carbide, and a silicon carbide layer consisting of a Si-depleted layer formed in the inner wall of the reaction-sintered silicon carbide tube base and a high-purity silicon carbide film deposited on the Si-depleted layer, said silicon carbide layer having a thickness of more than 0.5 mm, and not more than 2.0 mm. The above and other objects, features and advantages of the present invention will be more apparent from the following description. BRIEF DESCRIPTION OF THE DRAWING Fig. 1 is a sectional view showing an embodiment of a diffusion tube according to the present invention. PREFERRED EMBODIMENT OF THE INVENTION Since the reaction tube has a silicon carbide film formed on the inner surface of the diffusion tube base after the inner wall of the tube base has been subjected to a Si removing treatment, diffusion of impurities from the diffusion tube base and the outside of the diffusion tube is intercepted so that, when a semiconductor is heat-treated, the silicon wafer may be prevented from being contaminated with the impurities. In this case, if the purity of the silicon carbide film is poor, the silicon wafer will be contaminated with the impurities diffused from the silicon carbide film. Therefore, it is required to make the silicon carbide film highly pure, and particularly it is required to control the iron content of the film to be 5 ppm or below, preferably 1 ppm or below. Iron is a material that will most readily contaminate the diffusion tube in the production. By controlling the iron content to be 5 ppm or below, other detrimental impurities such as Ti, Cu, Mn, Mg, Ni, etc. can be controlled to be 5 ppm or below in total. The present diffusion tube comprises a reaction-sintered silicon carbide diffusion tube base and the above-mentioned silicon carbide film with an iron concentration of 5 ppm or below. In this case, the purity of the tube base is very important in order to keep the iron concentration of the silicon carbide film at 5 ppm or below. It is necessary to control the iron concentration of the tube base to 20 ppm or below, preferably 10 ppm or below, and most preferably 5 ppm or below. If the iron content in the tube base exceeds 20 ppm, it is impossible to keep the iron concentration in the silicon carbide film at 5 ppm or below, although the pure silicon carbide film having an iron concentration of 5 ppm or below is firstly formed. The reaction-sintered silicon carbide is one obtained, as shown in Japanese Patent Publication No. 38061/1970, by adding a large amount (about 15 to about 40 % by weight) of a carbonaceous material initially to a siliceous material, and carrying out the reaction at about 1,500°C to about 1,900°C, while in the recrystallization process a carbonaceous material is added in a small amount (generally 10% by weight or below), and the heat treatment temperature is required to be about 2,000°C or over. The silicon carbide produced by the reaction of the large amount of the added carbon consequently strengthens the bond between the particles, so that the strength of the reaction-sintered silicon carbide is increased. Since the present diffusion tube uses reaction-sintered silicon carbide as the base material, it will not disadvantageousely deform or devitrify even at a high temperature. Further, it is excellent in strength and would not break due to the thermal stress caused by a difference in thermal expansion coefficient between the silicon carbide layer and the tube base. In this case, if the Si content in the reaction-sintered silicon carbide is too high, the difference in thermal expansion coefficient between the reaction-sintered silicon carbide base and the silicon carbide layer may become high, and the diffusion tube may become apt to break easily. From this viewpoint, Si content in the base material is preferably 25 vol. % or below, more preferably 20 vol %. or below. The lower limit of Si content may preferably be 8 vol %. In other words, it is required that the density of the base material is 3.0 g/cm³ or more, preferably 3.0 to 3.10 g/cm³, most preferably 3.03 to 3.10 g/cm³. The size of the diffusion tube base is not limited, although it is general that the inner diameter is in the range of about 80 mm to about 250 mm, the thickness is in the range of about 4 mm to about 8 mm, and the length is in the range of about 1200 mm to about 3500 mm. Although any process which can form a high-purity silicon carbide film having an iron concentration of 5 ppm or below can be used, a vapor phase synthesis process, which is commonly called CVD (chemical vapor deposition) process, for depositing a silicon carbide film on the Si-depleted layer on the inner surface of the tube base is preferably employed. In the chemical vapor deposition process, a raw material gas comprising CH₃SiCl₃, CH₃SiHCl₂, (CH₃)₂SiCl₂, SiCl₄ + CH₄, SiCl₄ + C₃H₈, or the like is passed over the Si-depleted layer on inner surface of the reaction-sintered silicon carbide diffusion tube base loaded in a CVD furnace thereby depositing SiC on the Si-depleted layer of the tube base. The raw material gas is not limited to the above gases, and any gases for forming a SiC film that are generally used in the CVD process can be used The pressure may be normal pressure or reduced pressure, and generally a pressure of 1.33 to 26.6 kPa (10 to 200 mm Hg) can be employed. The temperature is preferably 1,000 to 1,400°C. If the temperature is below 1,000°C, the deposited film may be apt to become amorphous and unstable. On the other hand, if the temperature is over 1,400°C, the Si of the base material may be melted and come outside. Fig. 1 shows one embodiment of a diffusion tube 20 according to the present invention. The diffusion tube 20 comprises a diffusion tube base 22 made of reaction-sintered silicon carbide, and a silicon carbide layer 24 consisting of a Si-depleted layer 26 formed in the inner wall of the tube base 22 and a high-purity silicon carbide film 28 deposited on the Si-depleted layer 26. By forming the Si-depleted layer, the thickness of the silicon carbide film to be deposited can be decreased, thereby reducing the production cost. In this diffusion tube 20, the silicon carbide layer 24 consisting of the Si-depleted layer 26 and the deposited silicon carbide film 28 has a thickness of more than 500 µm. The upper limit of the thickness of the silicon carbide layer is 2000 µm. In this case, the thickness of the Si-depleted layer 26 is 0.4 to 0.7 mm. If the thickness of the Si-depleted layer is below 0.4 mm, it is required that deposition of a silicon carbide film is made excessively to obtain a prescribed thickness of the silicon carbide layer, and therefore the merit that decreases the production cost may not be obtained. On the other hand, if the thickness of the Si-depleted layer is over 0.7 mm, pores are liable to remain in the inner surface of the tube base, and these pores render the strength low, causing the breakage, and the pores themselves may act as a gas generating source, that is, an impurity generating source. The thickness of the silicon carbide film may preferably be more than 500 µm. The Si-depleted layer can be formed by a Si removing treatment to the inner wall of the reaction-sintered silicon carbide diffusion tube base to allow the inner wall thereof to be free of Si or to reveal only SiC. As a process of removing Si from the inner wall of the tube base, a solution treatment or hydrochloric acid gas treatment is preferably employed. The solution treatment is carried out by immersing the tube base in conc. hydrofluoric acid, conc. nitric acid or a mixture thereof, if necessary with dilution of water, preferably at 10 to 30°C, typically room temperature. The preferred acid is a mixture of conc. hydrofluoric acid and conc. nitric acid. The concentration of the acid may preferably be more than 40% by weight, more preferably more than 50% by weight in the acid solution. The gas treatment is carried out by passing hydrochloric acid gas into the tube base heated at about 1000°C to about 1200°C for 2 to 8 hours. After the treatment, it is desirable to wash well the inner wall of the tube base with water not to allow the acid to remain. Thereafter, the film deposition by CVD process is carried out. In this case, pores in the Si-depleted or Si-free layer which are formed in the Si removing treatment can be filled with the silicon carbide deposit at the time when the silicon carbide film is formed on the Si-depleted or Si-free layer by CVD process. As described above, the present silicon carbide type diffusion tube does not have disadvantages such as deformation and devitrification even at a high temperature, is excellent in strength, can be used for a long period of time under high-temperature conditions, and would not cause a silicon wafer to have defects due to the presence of impurities. Therefore, when a semiconductor is heat-treated by using the present diffusion tube, the yield of the semiconductor in its production can be improved. In this case, as described above, the prior art production of a silicon carbide diffusion tube uses a recrystallization process and the recrystallized silicon carbide obtained in this method is low in strength. If this silicon carbide is used to produce a diffusion tube and a thick silicon carbide layer of more than 500 µm is formed on the inner surface thereof, the layer is liable to break when it is used. In contrast, the present diffusion tube is high in strength because reaction-sintered silicon carbide is used as the base material, and even if a thick silicon carbide layer is formed on the inner surface of the reaction tube, it hardly breaks, allowing the formation of a thick silicon carbide layer of more than 500 µm. The present invention will now be specifically described with reference to an Example and Comparative Examples, but the present invention is not limited to this Example. Example 1 Three constricted diffusion tubes of reaction-sintered silicon carbide type material having an outer diameter of 184 mm, an inner diameter of 170 mm, and a length of 2,300 mm were prepared, and the inner surfaces thereof were treated with an aqueous solution of HF : HNO₃ : water = 1 : 1 : 1 (weight ratio) for 1, 6 and 15 hours, respectively, thereby removing Si on the inner surface. Dummy samples were treated simultaneously therewith and were examined, and the results were such that the eroded layers (Si-depleted layers) had thicknesses of 0.15 mm, 0.5 mm and 0.8 mm respectively. Then, the diffusion tubes were washed well with water and dried to load in a CVD furnace. The pressure in the furnace was reduced to 4 kPa (30 Torr), and trichloromethylsilane and hydrogen gas were passed at rates of 1 ℓ/min and 10 ℓ/min respectively over the inner surface of each of the diffusion tubes and the dummy samples whose temperature was kept at 1,300°C by resistance heating to deposit a silicon carbide film on the inner surface of the Si-depleted layer. At that time, the depositing time was varied to vary the thickness of the silicon carbide layer on the inner surfaces of the three diffusion tubes. The thicknesses of the silicon carbide layers (Si-depleted layer + SiC film deposited thereon) of the dummy samples treated simultaneously therewith were measured and found to be 0.35 mm, 1.2 mm, and 2.1 mm, respectively. These results were in conformity with the results that were obtained by the measurement of a diffusion tube destruction test after the below-mentioned lifetime test of wafers. The purity of the silicon carbide film of the dummy sample was determined and it contained Fe in an amount of 4 ppm. Then, the three diffusion tubes were loaded in a diffusion furnace, and a silicon wafer (CZ-P type 〈111〉) was inserted into each diffusion tube. The wafers were heat-treated in dry oxygen at 1,100°C for 4 min. To examine the degree of the contamination of each silicon wafer, the lifetime of the wafers was measured. The results are shown in Table 1. For comparison, a quartz diffusion tube and a silicon carbide type diffusion tube having no silicon carbide layer on the inner surface thereof were subjected to the same test, and the results are also shown in Table 1. It should be noted that the lower the contamination is, the longer the lifetime of the wafer is. To examine the influence of a long-period operation, No. 1 to No. 3 diffusion tubes were loaded in a diffusion furnace, and a heat cycle consisting of 800°C (kept for 2 hours) and 1,200°C (kept for 4 hours) was repeated, and the lifetime was measured in the same manner as before. The results are shown in table 2. No. 3 test tube broke at 27 cycles. Thickness of SiC layer (mm) Lifetime of wafer (µ sec) No. 1 1.1 114 No. 2 0.35 87 No. 3 2.1 -

Claims: A silicon carbide type diffusion tube comprising a diffusion tube base made of reaction-sintered silicon carbide having an iron concentration of 20 ppm or below and a density of 3.0 g/cm³ or more, and a silicon carbide layer consisting of a Si-depleted layer formed in the inner wall of the reaction-sintered silicon carbide tube base, the Si-depleted layer having a thickness of 0.4 to 0.7 mm, and a high-purity silicon carbide film deposited on the Si-depleted layer having an iron concentration of 5 ppm or below, said silicon carbide layer having a thickness of more than 500 µm and not more than 2000 µm. The diffusion tube of claim 1, wherein the silicon carbide film has a thickness of more than 500 µm. A process for manufacturing a silicon carbide type diffusion tube, which comprises: forming a diffusion tube base with reaction-sintered silicon carbide having an iron concentration of 20 ppm or below and a density of 3.0 g/cm³ or more, subjecting the inner wall of the tube base to a Si removing treatment by immersing the tube base in an acid solution containing concentrated hydrofluoric acid and/or concentrated nitric acid or by passing hydrochloric acid gas through the tube base at a high temperature of from 1000 to 1200°C. such that a Si-depleted layer having a thickness of 0.4 to 0.7 mm is formed, and forming a high-purity silicon carbide film having an iron concentration of 5 ppm or below by chemical vapor deposition on said Si-depleted layer so that a silicon carbide layer comprising said Si-depleted layer and said silicon carbide film having a thickness of more than 500 µm and not more than 2000 µm is obtained.

Inventors: HAYASHI, MICHIO, MATSUMOTO, FUKUJI, TAWARA, YOSHIO
Applicants: SHIN-ETSU CHEMICAL CO., LTD.
Application year: 1989
Main classification: C04B35
IPC codes: C04B35, C30B31