JP7484516B2 - Exhaust gas treatment method and silicon carbide polycrystalline wafer manufacturing method - Google Patents

Description

The present invention relates to an exhaust gas treatment method and a method for manufacturing silicon carbide polycrystalline wafers. For example, the present invention relates to an exhaust gas treatment method and a method for manufacturing silicon carbide wafers using a substrate processing apparatus with a vertical arrangement structure in which multiple silicon carbide single crystal substrates are arranged in a stacking direction with gaps between them.

Silicon carbide (SiC) is a wide bandgap semiconductor with a wide bandgap of 2.2 to 3.3 eV. Due to its excellent physical and chemical properties, there has been active research and development into the fabrication of devices (semiconductor elements) using silicon carbide, including high-frequency electronic devices, high-voltage and high-power electronic devices, and short-wavelength optical devices from blue to ultraviolet. In order to advance the practical application of SiC devices, there is a demand for the production of large-diameter silicon carbide substrates for high-quality SiC epitaxial growth. Currently, most of these are manufactured by the sublimation recrystallization method using seed crystals (also known as the improved Rayleigh process or modified Rayleigh process) or the CVD method.

The manufacturing method for silicon carbide substrates using the CVD method (chemical vapor deposition method) involves causing a gas-phase reaction of raw material gases to cause the silicon carbide product to precipitate on the substrate surface to form a coating, after which the substrate is removed, resulting in a dense, high-purity silicon carbide substrate. The substrate is removed by cutting or polishing, but if a carbon material is used for the substrate, it can be removed by heat treatment in air.

Patent Document 1 proposes a method for manufacturing a silicon carbide substrate by a CVD method, which is characterized in that a silicon carbide film is formed on the surface of a base material by a chemical vapor deposition method, and then the base material is removed to obtain a silicon carbide substrate, and a silicon carbide film is further formed on both sides of the resulting silicon carbide substrate.

In addition, Non-Patent Documents 1 and 2 propose using chlorosilane gases (SiCl4, SiHCl3, etc.) as silicon source gases to suppress the generation of Si particles and form SiC films at high speed. Of the chlorosilane gas source gas, only a portion precipitates on the substrate, while the majority is exhausted, and as the gas temperature drops, it becomes a higher-order chlorosilane polymer and precipitates in the exhaust piping, etc. This can cause the piping to become clogged.

Higher order chlorosilane polymers not only clog pipes, but are also known to hydrolyze when exposed to moisture in the air, and incomplete hydrolysis products form explosive compounds, as shown in Non-Patent Document 3. Therefore, care must be taken when handling and cleaning pipes and parts that have chlorosilane polymers (oily silanes) attached.

As shown in the non-patent literature, oily silanes are also a problem in Si epitaxial growth using chlorosilane gases, and since _SiCl2 is generated at high temperatures of 1000°C or higher in Si epitaxial growth, the generation of _SiCl2 can be suppressed by setting the epitaxial growth temperature below 1000°C, and the amount of oily silane generated can be suppressed. However, a high temperature of 1400K or higher is required to form a SiC film at a practical growth rate, and the method of suppressing the generation of SiCl2 during low-temperature growth cannot be adopted.

On the other hand, Patent Document 2 proposes a method in which, in a film formation apparatus that produces SiC using methyltrichlorosilane gas as a raw material, exhaust gas from the film formation apparatus is introduced into an exhaust gas treatment device (reformer) whose temperature is maintained at 750° _C to 850°C without lowering it, and chloromethane gas is added to the exhaust gas containing chlorosilanes and reacted to reform the _SiCl2 -based gas in the exhaust gas into _SiCl4 , _{SiHCl3 , CH3SiCl3} , _{C2H3SiCl3 , etc.} , thereby preventing the production of higher-order chlorosilane polymers even when the exhaust gas temperature is lowered.

Patent Document 2 (for example, paragraph 0090 and Figure 35) describes that exhaust gas precipitates as solid SiC in the exhaust gas treatment device, and that forming solid SiC is effective in reducing higher chlorosilane polymers.

Japanese Patent Application Laid-Open No. 8-188408 WO2018/008642

ECS J. Solid State Sci. Technol. 2015 volume 4, issue 2, P16-P19 Toshio Hirai, Takashi Goto, Toshihiko Kaji, Journal of the Ceramic Association, Vol. 91, No. 11, (1983) 503 Yuuki Ishida J. Vac. Soc. Jpn. Vol. 54, No. 6, (2011) 346 Mitsubishi Materials Corporation Yokkaichi Plant High Purity Polycrystalline Silicon Manufacturing Facility Explosion and Fire Accident Investigation Report http://www.mmc.co.jp/corporate/ja/01/01/14-0612a.pdf

However, in the method of manufacturing silicon carbide wafers, in which silicon chloride gas is used as the raw material gas to grow a silicon carbide thin film on the surface of a carbon substrate, there is a problem in that the efficiency of raw material usage decreases when chlorosilane in the exhaust gas is converted into solid SiC. In addition, if chloromethane gas is used and not all of it is consumed in the deposition of solid SiC, harmful and flammable chloromethane gas is present in the exhaust gas, which requires treatment.

In view of the above problems, the present invention aims to provide an exhaust gas treatment method and a method for manufacturing silicon carbide polycrystalline wafers that can prevent high-order chlorosilane polymers from precipitating in exhaust pipes, etc., and suppress blockage of exhaust pipes, etc.

In order to solve the above problems, the present inventors have conducted a chemical kinetics study on the relationship between the chemical reaction conditions and the products. As a result, they have found that the problem of the deposition of the higher chlorosilane polymer on the exhaust piping, etc., can be solved by providing an exhaust gas treatment chamber adjacent to the SiC film formation chamber in the CVD apparatus, adding hydrogen chloride gas to the exhaust gas after film formation containing _SiCl2 to prepare a mixed gas, and heat treating the mixed gas at a heat treatment temperature of, for example, 1000K or higher and 1500K or lower for 10 seconds or higher and 3600 seconds or lower. This makes it possible to efficiently convert _SiCl2 into the raw material _SiCl4 .

In order to solve the above problems, the exhaust gas treatment method of the present invention includes a mixing step of obtaining a mixed gas by mixing exhaust gas containing _SiCl2 discharged from a film formation chamber in which silicon carbide polycrystalline is formed on the surface of a carbon substrate by chemical vapor deposition using silicon chloride gas and a carbon-based gas as raw material gases with hydrogen chloride gas, and a heat treatment step of heat-treating the mixed gas for 10 seconds or more and 3600 seconds or less.

The heat treatment temperature of the mixed gas may be 1100K or more and 1300K or less.

The mixing ratio of SiCl ₂ in the exhaust gas to the hydrogen chloride gas in the mixing step may be SiCl ₂ :HCl=1:3-8 in molar ratio.

In addition, in order to solve the above problems, the method for producing a silicon carbide polycrystalline wafer of the present invention includes the exhaust gas treatment method of the present invention.

The present invention provides an exhaust gas treatment method and a method for manufacturing silicon carbide polycrystalline wafers that can prevent high-order chlorosilane polymers from precipitating in exhaust pipes, etc., and suppress blockage of exhaust pipes, etc.

FIG. 1 is a diagram showing the relationship between reaction coordinates and energy. This is the result of a chemical kinetic calculation of the change in molar concentration of a gas phase gas with temperature. This is the result of a chemical kinetic calculation of the change in the molar concentration of the gas phase gas with temperature under conditions different from those in FIG. The graph shows the results of chemical kinetic calculations of the change in the molar concentration of the gas phase gas with temperature under conditions different from those shown in FIGS. FIG. 5 is a graph showing the change in concentration of _SiCl2 . FIG. 6 is a graph showing the change in concentration of _SiCl4 . 1 is a contour line showing the _SiCl2 conversion rate when the heat treatment time is 1 sec. 1 is a contour plot showing the _SiCl2 conversion rate for a heat treatment time of 10 seconds. 1 is a contour plot showing the _SiCl2 conversion rate for a heat treatment time of 100 seconds. 1 is a contour plot showing the _SiCl2 conversion rate for a heat treatment time of 1000 sec. Schematic diagram of the homogeneous reactor (C1_PSR). 3 is a schematic diagram showing a cross section of a manufacturing apparatus 3000 for producing a silicon carbide polycrystalline wafer as viewed from above. FIG. FIG. 1 is a schematic diagram showing a cross section seen from above of a manufacturing apparatus 1000 as one embodiment of a silicon carbide polycrystalline wafer manufacturing apparatus that can be used in the exhaust gas treatment method and the silicon carbide polycrystalline wafer manufacturing method of the present invention. 1 is a schematic front view of the first surface 110 as viewed from inside the film formation chamber 110. FIG. 1 is a schematic front view of the second surface 120 as seen from inside the film formation chamber 100. FIG. FIG. 5 is a schematic diagram of a substrate holder 500. 5A and 5B are schematic diagrams illustrating the ejection of mixed gas.

Below, an embodiment of the exhaust gas treatment method and the method for producing silicon carbide polycrystalline wafers of the present invention will be described with reference to the drawings. However, the present invention is not limited to these embodiments.

[Production of silicon carbide by reaction of silicon chloride gas and carbon-based gas]
The chemical reaction for producing SiC using _SiCl4 as the silicon chloride gas and _CH4 as the carbonaceous source gas is stoichiometrically described by the following formula (1). However, in reality, the molecules do not react according to this formula, and multiple reactions are thought to proceed in parallel or sequentially.

[Equation 1]
_SiCl4 + _CH4 → SiC + 4HCl (1)

Unlike formula (1), the elementary reaction equations used in reaction kinetics refer to reactions that cannot be decomposed any further, and show the collision phenomenon between molecules and the resulting change in molecular state. For example, when considering formula (1) kinetically, _SiCl4 and _CH4 decompose to produce _{SiCl2 and C2H2} , etc., which are adsorbed on the surface of the supporting substrate and react to form SiC. For example, the following reactions can be mentioned.

[Equation 2]
_SiCl4 ⇔ _SiCl3 + 1/ _2Cl2
SiCl3 ⇔ _SiCl2 + 1/ _2Cl2
Cl2 + _H2 ⇔ 2HCl
_CH4 ⇔ _CH3 +1/ _{2H2
2CH3 ⇔C2H5 +} H
_{C2H5 ⇔ C2H4} + _{H
C2H4 ⇔ C2H2 + H2
SiCl2} ⇒Si_substrate + _Cl2
C2H2 ⇒C_substrate _{+ CH2}
Si_substrate + C_substrate ⇒ SiC_substrate

Here, "⇒" indicates a one-way reaction, "⇔" indicates a reversible reaction, the chemical species are gas phase molecules, and "_substrate" indicates that they are adsorbed onto the substrate. The stoichiometric reaction equation corresponding to equation (1) is a summary of this series of reactions, taking into account the conservation of the number of atoms.

The elementary reaction rate constant k(T) of elementary reaction i can be written as the following equation (2).

[Equation 3]
k(T) = A × ^Tn × exp(-Ea/RT) (2)

The unit of ki (T) is cm ³ /molecule/s, T is temperature (unit: K), Ea (unit: kcal/mol) is activation energy, R is the gas constant 1.987 (unit: cal/K/mol), and n is the reaction order.

Additionally, A is a frequency constant, and for example, when molecule X decomposes into Y and Z (X → Y + Z), the change is -d[X]/dt = A1[X], where A1 is a frequency factor with a dimension of 1/s. When X is synthesized from molecules Y and Z (Y + Z → X), -d[Y]/dt = -d[Z]/dt = A2[Y][Z], and the dimension of the frequency factor A2 is ^cm3 /(mol*s). In this way, the dimension of the constant changes depending on the order of the reaction.

The elementary reaction rate ri(T) is calculated by multiplying the elementary reaction rate constant ki(T) by the concentration Ci (molecule/cm ³ ) of molecule i, as shown in the following formula (3).

[Equation 4]
ri(T)＝ki(T)・Cj (3)

The reaction rate r(T) in the forward direction (A+B→C+D) of the chemical equation A+B⇔C+D can be calculated using the following formula (4).

[Equation 5]
r(T) = k(T) x [A] x [B] (4)

The reaction rate r*(T) in the reverse direction of the chemical equation A+B⇔C+D (A+B←C+D) can be calculated using the following equation (5).

[Equation 6]
r*(T) = k*(T) x [C] x [D] (5)

Figure 1 shows the relationship between reaction coordinates and energy. In the reversible reaction A+B⇔C+D shown in Figure 1, if there is a free energy change ΔG between the state of A+B and the state of C+D, the activation energy E _CD can be calculated as shown in the following formula (6).

[Number 7]
E _CD = E _AB -ΔG (6)

The elementary reaction equations and reaction parameters thought to occur in the gas phase are shown in Tables 1 and 2. Table 1 is for silicon-based gases, and Table 2 is for carbon-based gases. Thermodynamic parameters such as ΔG were obtained from a thermodynamic database (e.g. HSC: Autotech).

Using elementary reactions, the change in the molar concentration of the gas phase gas due to temperature was calculated chemically. Chemkin-pro was used for the calculation, and a homogeneous reactor ( _{C1_PSR} ) was used as the calculation model, assuming that a homogeneous reaction occurs in the reactor, as shown in Figure 11. In the calculation model, the composition ratio (molar ratio) of the inflowing gas was _SiCl4 : _CH4 : _H2 :Ar = 1:1:10:5, and HCl gas was not used. The residence time (heat treatment time) in the reactor was 10 seconds. The calculation was performed at reaction temperatures from 900K to 1700K in increments of 100K.

The results are shown in Figure 2. Figure 2 shows the results of a chemical kinetic calculation of the change in the molar concentration of the gas phase gas with temperature. The main components of the gas are Ar gas and _H2 gas, but Ar gas is independent of the reaction and has a molar concentration of about 0.3, while the molar concentration of _H2 gas is 0.5 to 0.6, with little temperature dependency. The concentration scale in Figure 2 was selected with a focus on the temperature change of the _SiCl4 gas concentration, and Ar gas and _H2 gas were removed from Figure 2.

As can be seen from Figure 2, at a deposition temperature of 1100K, _SiCl4 begins to decompose into _SiCl2 and _SiCl3 , and as the temperature rises the decomposition progresses, with almost the entire amount being converted to _SiCl2 at 1600K. _SiCl3 is present in the same amount as _SiCl2 at 1100-1200K, but decomposes at higher temperatures. It can also be seen that the concentration of the by-product HCl increases with temperature. _CH4 also begins to decompose at 1400K _, which is higher than _SiCl4 , and _C2H2 is produced, but some of it remains even at 1700K. Note that _C2H2 contains two carbon atoms, so even if all of the _CH4 decomposes _, its concentration will be half.

Next, as shown in Table 3, the calculation was performed with the composition where _SiCl4 in the input gas was _SiCl2 and HCl was added twice as much as _SiCl2 (Ar: _H2 : _CH4 : _SiCl2 :HCl=0.407:0.390:0.065:0.046:0.092). In this case, the molar ratio is _SiCl2 :HCl=1:2. The reason why HCl was added twice as much as _SiCl2 is because in the stoichiometric equation of the reaction in which _SiCl4 changes to _SiCl2 in the exhaust gas of an actual CVD furnace, it is assumed that HCl is at least twice as much as _SiCl2 ( _SiCl4 + _H2 → _SiCl2 +2HCl). Furthermore, the concentration of _SiCl2 decreases as it becomes SiC, so it is more than twice as much. The residence time in the furnace was set to 10 seconds.

Figure 3 shows the calculation results under conditions of a molar ratio of _SiCl2 :HCl = 1:2 and a heat treatment time of 10 seconds. Figure 3 shows the results of a chemical kinetic calculation of the change in molar concentration of the gas phase gas with temperature under conditions different from those in Figure 2. _SiCl2 reaches a minimum at 1300K, with 78% of the _SiCl2 in the exhaust gas being converted to _SiCl4 and _SiCl3 . ( _SiCl2 + 2HCl → _SiCl4 + _H2 )

In the results of Figure 3, as expected from the stoichiometric formula of the reaction, the _H2 concentration increases and HCl decreases with the reaction of _SiCl2 . In the silicon carbide deposition apparatus owned by the applicant, the conversion rate from _SiCl2 to SiC is 50% or less, so the HCl concentration in the exhaust gas is estimated to be about four times that of _SiCl2 . Next, a calculation was performed for the case of _SiCl2 :HCl = 1:4.

Figure 4 shows the results of calculations performed under the same conditions as in Figure 3, except that the molar ratio was _SiCl2 :HCl = 1:4. The heat treatment time was also set to 10 seconds. Figure 4 shows the results of a chemical kinetic calculation of the change in the molar concentration of the vapor phase gas with temperature under conditions different from those in Figures 2 and 3. When the molar ratio is _SiCl2 :HCl = 1:4, the _SiCl2 concentration is lower at 1200-1400K than when _SiCl2 :HCl = 1:2, and it can be seen that at 1300K almost the entire amount is converted to _SiCl4 .

Although _SiCl4 is more stable than _SiCl2 at 1100K or less in a thermal equilibrium state, the results in Figure 4 show that _SiCl2 remains at temperatures below 1300K with a heat treatment time of 10 seconds. This is because the reaction rate slows down as the heat treatment temperature decreases. Therefore, in order to examine whether _SiCl2 can be efficiently converted to _SiCl4 by extending the heat treatment time even at a heat treatment temperature below 1300K, calculations were performed by changing the heat treatment time from 1 second to 1000 seconds.

It is possible to calculate when the heat treatment time is 1000 seconds or more, but it is assumed that _SiCl2 polymerizes at low temperatures (below 900K) to form oily silane, and when held at high temperatures of 900K or more for a long time, SiC, the final form of the reaction, is generated on the inner side of the deposition device. The reaction mechanism of oily silane is not clear, so calculations have not been performed. It is possible to deposit SiC at 1000K to 1800K, and it is said that the reaction speed slows down at low temperatures.

The ratios of gases such as source gas and carrier gas are the same as those in Fig. 4, and the heat treatment temperature is 1000 to 1400 K. The changes in the concentrations of _SiCl2 and _SiCl4 with respect to the heat treatment time are shown in Figs. 5 and 6. Fig. 5 is a graph showing the changes in the concentration of _SiCl2 . Fig. 6 is a graph showing the changes in the concentration of _SiCl4 .

From the results of FIG. 5, it can be seen that when the heat treatment temperature is 1000K, the _SiCl2 starts decreasing at 10 seconds, and after 1000 seconds, the concentration is about 20% of the concentration before heat treatment, and the concentration of _SiCl2 tends to decrease further as the heat treatment time is extended. When the heat treatment temperature is 1100K, the _SiCl2 decreases to a molar concentration of 0.005 or less (1/100 of the inflow amount) at a heat treatment time of 1000 seconds, and at a heat treatment temperature of 1200K, the molar concentration decreases to 0.01 at a heat treatment time of 10 seconds, but the molar concentration does not change even if the heat treatment time is extended and an equilibrium state is reached. When the heat treatment temperature is 1400K, the molar concentration decreases to 0.02 (50% of the inflow amount) at a heat treatment time of 1 second, and the molar concentration does not change even if the heat treatment time is extended and an equilibrium state is reached.

From these results, it can be seen that under the condition of a gas ratio of SiCl ₂ :HCl=1:4, if the heat treatment temperature is low, below 1200, and the heat treatment time is extended to 100 seconds or more, SiCl ₂ can be reduced to nearly zero.

On the other hand, from the results of Fig. 6, the change in the molar concentration of _SiCl4 increases from 10 seconds onwards when the heat treatment temperature is 1000K, and most of the _SiCl2 is converted to _SiCl4 when the heat treatment temperature is 1100K and when the heat treatment time is 1000 seconds, and when the heat treatment temperature is 1200K and when the heat treatment time is 100 seconds, the molar concentration of _SiCl4 is equilibrated when the heat treatment temperature is 1300K and when the heat treatment time is 10 seconds, and when the heat treatment temperature is 1400K and when the heat treatment time is 1 second.

Looking at the results in Figures 5 and 6, as the heat treatment time increases, the molar concentration of _SiCl2 decreases and the molar concentration of _SiCl4 increases, so the behavior of the molar concentrations of these gases is opposite. When the sum of the gas concentrations of both is taken, it becomes almost constant for all heat treatment time conditions when the heat treatment temperature is 1200K and _1100K . It was also found that when the heat treatment temperature is 1000K, _SiH2Cl2 is generated, and when the heat treatment temperature is 1300K and 1400K, _SiCl3 is generated.

Next, the gas ratio of HCl to _SiCl2 (HCl/ _SiCl2 ) was changed from 1 to 8 in increments of 0.5, the ratios of other gases such as raw material gas and carrier gas were the same as in Fig. 4, and the heat treatment time was changed to 1, 10, 100, and 1000 sec, and the chemical reaction was calculated. From the calculation results, the _SiCl2 concentration after the chemical reaction calculation (SiCl2c) was divided by the input amount before the reaction (SiCl2i) using formula (7) to calculate the _SiCl2 residual rate.

[Number 8]
_SiCl2 residual rate = SiCl2c / SiCl2i (7)

Table 4 and Figures 7 to 10 show the calculation results for heat treatment times of 1, 10, 100, and 1000 seconds. In Figures 7 to 10, the temperature is on the x-axis, the HCl/ _SiCl2 ratio at the time of input is on the y-axis, and the _SiCl2 residual rate is shown as a contour line. Table 4 provides the data on which the contour lines in Figures 7 to 10 are based.

From the results of Table 4 and Figures 7 to 10, the range in which the _SiCl2 residual ratio is 0.1 or less is the condition where the heat treatment time is 1 sec, the heat treatment temperature is 1300K, and the Hcl/ _SiCl2 ratio is 8, and further, the heat treatment time is 10 sec, the heat treatment temperature is 1300K, and the Hcl/ _SiCl2 ratio is 5 or more, the heat treatment time is 100 sec, the heat treatment temperature is 1200K, and the Hcl/ _SiCl2 ratio is 3 or more, and the heat treatment time is 1000 sec, the heat treatment temperature is 1100K, and the Hcl/ _SiCl2 ratio is 4 or more. When the heat treatment time is 10 times, the range in which the _SiCl2 residual ratio is 0.1 or less spreads to the low temperature side. This phenomenon corresponds to the change in the time to reach the equilibrium state depending on the temperature.

From the above, it can be seen that by setting the HCl/ _SiCl2 molar ratio to 3 or more, more preferably 4 or more, and setting the heat treatment temperature to 1100 K to 1400 K, more preferably 1100 K or more and 1300 K or less, _SiCl2 in the exhaust gas can be efficiently converted to the raw material _SiCl4 .

<Silicon carbide polycrystalline wafer manufacturing apparatus 1000>
13 is a schematic diagram showing a cross section seen from above of a manufacturing apparatus 1000 as one embodiment of a silicon carbide polycrystalline wafer manufacturing apparatus that can be used in the exhaust gas treatment method and the silicon carbide polycrystalline wafer manufacturing method of the present invention. The manufacturing apparatus 1000 includes a film formation chamber 100, a mixed gas outlet 200, a mixed gas outlet 300, a heater 400, a substrate holder 500, an exhaust gas treatment device 900, a quadrupole mass spectrometer 1600, and a cold trap 1700.

<Film formation chamber 100>
The film formation chamber 100 has a rectangular parallelepiped inner shape consisting of a first surface 110, a second surface 120 facing the first surface 110, and four side surfaces 130 connecting the first surface 110 and the second surface 120. By making the inner shape rectangular parallelepiped, when a plurality of substrates 600 are placed in the film formation chamber 100, the shape of the gap between the substrates and the gap between the substrates and the side surface 130 can be made the same or similar. Therefore, like the mixed gas flowing between the substrates, the mixed gas flowing between the side surface 130 and the substrate can also flow uniformly from the mixed gas outlet 200 toward the mixed gas outlet 300. As a result, a uniform film with little variation can be formed on the substrate.

For example, if the internal shape of the film formation chamber 100 is cylindrical rather than rectangular, the shape of the gap between the substrates and the gap between the substrate and the side surface 130 will be significantly different, and the mixed gas flowing between the substrates and the mixed gas flowing between the side surface 130 and the substrate will not flow uniformly. As a result, the film formed between the substrates and the film formed between the substrate and the side surface 130 will be non-uniform, and there is a risk that a film with large variation between the substrates will be formed.

The internal dimensions of the film formation chamber 100 need only be large enough to accommodate the substrate holder 500 and the substrate 600 held by the substrate holder 500, and it is preferable to avoid excess space as much as possible that would allow mixed gas not involved in film formation to flow from the mixed gas outlet 200 toward the mixed gas outlet 300 and be discharged from the film formation chamber 100.

The deposition chamber 100 is preferably made of graphite. Graphite can be easily processed into a rectangular shape, and by using an inert atmosphere during deposition, the chamber can be sufficiently durable to withstand high-temperature deposition conditions.

<Mixed gas outlet 200>
The mixed gas outlet 200 is located on or near the first surface 110 of the film formation chamber 100, and ejects a mixed gas containing a raw material gas and a carrier gas into the film formation chamber 100. Although it is preferable that there are a plurality of mixed gas outlets 200, there may be only one. By having a plurality of mixed gas outlets 200, the mixed gas can be ejected more uniformly into the film formation chamber 100 compared to the case where there is only one. As an example of the mixed gas outlet 200, it corresponds to an opening end from which the mixed gas is ejected in a mixed gas introduction pipe 210 through which the mixed gas flows. The mixed gas outlet 200 may be located on the first surface 110, or may be located near the first surface 110 as shown in FIG. 13, on the inside side of the film formation chamber 100, or outside the film formation chamber 100 on the premise that there is no gas leakage of the mixed gas. The vicinity is, for example, approximately 20 mm from the first surface 110. In order to control the temperature of the mixed gas outlet 200, a temperature control means such as a heater capable of appropriately heating the mixed gas introduction pipe 210 or a cooler capable of cooling the mixed gas introduction pipe 210 may be provided.

Figure 14 is a front schematic view of the first surface 110 as viewed from inside the film formation chamber 110. In Figure 14, four mixed gas outlets 200 are arranged in a row on the first surface 110. The direction in which the four mixed gas outlets 200 are arranged can be aligned with the direction in which the substrates 600 are arranged and stacked in the substrate holder 500. It is possible to discharge the mixed gas evenly from each of the mixed gas outlets 200. The inner diameter of the mixed gas outlet 200 can be set to an optimal value depending on the number of mixed gas outlets 200 and the ejection conditions, and is not particularly limited as long as there is no problem with the ejection of the mixed gas, but can be set to a range of, for example, 10 mm to 25 mm. In addition, the distance between adjacent mixed gas outlets 200 can be set to an optimal value depending on the number of mixed gas outlets 200 and the ejection conditions, and is not particularly limited as long as there is no problem with the ejection of the mixed gas, but can be set to a range of, for example, 2 mm to 16 mm. Additionally, the mixed gas outlets 200 may be arranged in multiple rows and multiple columns on the first surface 110.

<Mixed gas outlet 300>
The mixed gas outlet 300 is located on or near the second surface 120 of the film formation chamber 100, and discharges the mixed gas from the film formation chamber 100. An example of the mixed gas outlet 300 corresponds to an open end of the mixed gas outlet pipe 310 through which the mixed gas flows to be discharged to the outside of the film formation chamber 100, through which the mixed gas is discharged. The mixed gas outlet 300 may be located on the second surface 120, or may be located near the second surface 120 as shown in FIG. 13, on the inside of the film formation chamber 100, or outside the film formation chamber 100 on the premise that there is no gas leakage of the mixed gas. The vicinity is, for example, approximately 20 mm from the second surface 120. In addition, in order to prevent silicon carbide or the like from precipitating in the mixed gas outlet 300 or the mixed gas outlet pipe 310, a temperature control means such as a heater that can heat appropriately or a cooler that can cool may be provided to control the temperature of the mixed gas outlet 300 or the mixed gas outlet pipe 310.

Figure 15 is a schematic front view of the second surface 120 as viewed from inside the film formation chamber 100. In Figure 15, one mixed gas exhaust port 300 is disposed in the center of the second surface 120. There may be one or more mixed gas exhaust ports 300 as long as the mixed gas can be discharged without problems even if some silicon carbide or the like is formed, but it is preferable for the opening diameter to be about 1/5 to 1/2 of one side of the second surface so that the mixed gas can be discharged without problems even if some silicon carbide or the like is formed.

<Heater 400>
The heater 400 surrounds the four side surfaces 130 of the film formation chamber 100 and heats the film formation chamber 100. By controlling the heater 400, the temperature of the film formation chamber 100 can be controlled to a temperature suitable for forming a film on a substrate. As the heater 400, a heater useful for a thermal CVD method can be used, such as a cylindrical carbon heater or a Kanthal heater.

<Substrate holder 500>
Fig. 16 is a schematic diagram of the substrate holder 500. Fig. 16(a) is a side view of the substrate holder 500 holding a substrate 600, and Fig. 16(b) is a front view of the substrate holder 500 seen from the first surface 110 side inside the film formation chamber 100. The substrate holder 500 can hold a plurality of substrates 600 by stacking the substrates 600 at equal intervals without contacting each other, and can install a film formation target surface 610 of the substrate 600 parallel to a side surface 130 of the film formation chamber 100 between the first surface 110 and the second surface 120 of the film formation chamber 100.

In FIG. 16, the substrate holder 500 can hold the substrate 600 by clamping it at two points, top and bottom, with the upper holding bar 510 and the lower holding bar 520, both of which have grooves 511, 521 for holding the substrate 600. However, the substrate holder is not limited to this, and can have holding bars at the front and back in addition to the top and bottom, and can hold the substrate at three or four points.

The substrate holder 500, for example, has an upper holding rod 510 and a lower holding rod 520 that are in close contact with the upper side 130a and the lower side 130b of the side surface 130 of the film formation chamber 100, respectively, thereby preventing a large amount of mixed gas not involved in film formation from flowing from the mixed gas outlet 200 toward the mixed gas outlet 300 and being discharged in large amounts from the film formation chamber 100.

In FIG. 16(b), the film-forming surface 610 of the substrate 600 is set parallel to the left side surface 130c and the right side surface 130d of the side surface 130 of the film-forming chamber 100, and is set perpendicular to the upper side surface 130a and the lower side surface 130b. However, by changing the shape of the substrate holder 500, the film-forming surface 610 of the substrate 600 can be set perpendicular to the left side surface 130c and the right side surface 130d, and can be set parallel to the upper side surface 130a and the lower side surface 130b. That is, the substrates 600 may be stacked vertically or horizontally. However, if the substrate 600 is set so that the film-forming surface 610 faces the mixed gas nozzle 200 and is parallel to the first surface 110 and the second surface 120, the mixed gas will not flow uniformly between the substrates, which is not preferable.

In addition, if the width 700 of the gap between the film-forming surface 610 of the substrate 600 and the left side surface 130c, and the width 710 of the gap between the left side surface 130d and the right side surface 130d are the same as the width 720 of the gap between the substrates 600 stacked at equal intervals, the mixed gas flows uniformly through these gaps, making it possible to form a film with little variation in thickness between substrates or on the same film-forming surface.

<Ejection speed of mixed gas>
17 is a schematic diagram for explaining the ejection of mixed gas. It shows the spread of mixed gas when collisions between molecules in the mixed gas are ignored, and the diffusion speed when the mixed gas naturally diffuses from the mixed gas ejection port 200 on the first surface without pressurizing the mixed gas is Vd, and the ejection speed when the mixed gas is ejected from the mixed gas ejection port 200 after pressurizing the mixed gas is Vg.

When the diffusion speed Vd is faster than the jet speed Vg, the diffusion of the mixed gas 800 proceeds slowly (Figure 17 (a)), which may reduce the amount of raw material gas supplied to the film formation chamber 100 and slow the film formation speed. If an attempt is made to control the temperature of the mixed gas outlet 200 to a low temperature (e.g., 1200K or less) by providing a certain distance between the substrate 600 and the mixed gas outlet 200 in the film formation chamber 100 so that the mixed gas does not form a film at the mixed gas outlet 200, the mixed gas 800 has to travel a distance to reach the substrate 600, which means that it takes longer to form the film.

In consideration of this point, in the manufacturing apparatus 1000, the ejection speed of the mixed gas ejected from the mixed gas ejection port 200 can be made faster than the diffusion speed of the mixed gas. That is, by making the ejection speed Vg faster than the diffusion speed Vd (FIG. 17(b)), the mixed gas 810 is forcibly discharged from the mixed gas ejection port 200. This makes it possible to suppress a decrease in the film formation speed even when a certain distance is provided between the substrate 600 and the mixed gas ejection port 200 in the film formation chamber 100. That is, while maintaining the same film formation speed as the conventional method, it is possible to prevent the mixed gas ejection port 200 from forming a film with the mixed gas and becoming smaller in diameter, or to prevent the mixed gas ejection port 200 from becoming clogged.

In order to make the ejection velocity Vg faster than the diffusion velocity Vd, the mixed gas 810 can be forcibly discharged from the mixed gas nozzle 200 by adjusting the amount of gas using an ejection velocity control means such as a regulator, compressor, or suction device. For example, by setting the ejection velocity Vg to 0.4 m/sec or more, it is possible to easily prevent the mixed gas nozzle 200 from becoming smaller in diameter due to the deposition of the mixed gas and from being blocked while maintaining the same film formation speed as in the conventional method. Furthermore, if the ejection velocity Vg is 1 m/sec or more, it is possible to clearly increase the film formation speed compared to the conventional method, and the film formation processing time can be more effectively shortened. In addition, in the manufacturing apparatus 1000 of the present invention, when multiple mixed gas nozzles 200 are provided, the ratio of the number of substrates 600 that the substrate holder 500 can hold to the number of ports of the mixed gas nozzle 200 is preferably 1:0.4 to 1.5. If the ratio of the number of substrates 600 that the substrate holder 500 can hold to the number of mixed gas nozzles 200 is 1:0.4 to 1.5, it is possible to prevent a decrease in the film formation rate while satisfying the uniformity of the gas velocity and gas flow rate described above.

In the manufacturing apparatus 1000, the shortest distance between the mixed gas nozzle 200 and the substrate holder 500 is preferably 150 mm or more. Although the optimal shortest distance varies depending on the ejection speed and gas flow rate of the mixed gas 810, and the number of ports of the mixed gas nozzle 200, if the shortest distance is 150 mm or more, the temperature around the mixed gas nozzle 200 can be sufficiently lowered below the film formation temperature around the substrate 600 in the film formation chamber 100. This makes it easy to prevent the diameter of the mixed gas nozzle 200 from becoming smaller due to film formation of the mixed gas, and to prevent the mixed gas nozzle 200 from becoming clogged.

<Exhaust Gas Treatment Device 900>
The exhaust gas treatment device 900 is a device for treating the exhaust gas discharged from the film formation chamber 100, specifically, it is a device arranged downstream of the film formation chamber 100, and converts SiCl ₂ to SiCl ₄ by reacting SiCl ₂ in the exhaust gas with hydrogen chloride gas mixed with the exhaust gas in the exhaust gas treatment device 900. By converting SiCl ₂ in the exhaust gas to SiCl ₄ in the exhaust gas treatment device 900, it is possible to dilute SiCl ₂ in the exhaust gas. Therefore, it is possible to prevent high-order chlorosilane polymers from precipitating in equipment, such as the exhaust piping 350, which is downstream of the exhaust gas treatment device 900 and discharges the exhaust gas discharged from the exhaust gas treatment device 900 to the outside of the manufacturing device 1000, and to suppress clogging of the inside of the equipment.

The exhaust gas treatment device 900 is preferably surrounded by a heater 410 so that the inside of the device can be adjusted to a temperature suitable for converting _SiCl2 to _SiCl4 . As the heater 410, a heater useful for a thermal CVD method can be used, such as a cylindrical carbon heater or a Kanthal heater. The inside of the exhaust gas treatment device 900 is heated by the heater 410, and the temperature can be set to a range from 1000K to 1500K.

The exhaust gas treatment device 900 is connected to the film formation chamber 100 via a cylindrical exhaust gas introduction pipe 910 made of graphite. The exhaust gas introduction pipe 910 is provided with a hydrogen chloride gas introduction pipe 320 for introducing hydrogen chloride gas into the exhaust gas so that the exhaust gas discharged from the film formation chamber 100 is mixed with hydrogen chloride gas to obtain a mixed gas. The mixed gas is then sent to a reaction chamber 920 where _SiCl2 in the mixed gas is reacted and converted to _SiCl4 .

The exhaust gas treatment device 900 has a box-shaped housing 930, and inside, a plurality of cylindrical graphite tubes 940 each having an inner diameter of 200 mm and a length of 500 mm can be connected to form a meandering or spiral exhaust gas flow path so that the mixed gas can remain in the exhaust gas treatment device 900 for a long time. By forming the exhaust gas into such a shape, the mixed gas can be kept in an environment suitable for converting _SiCl2 to _SiCl4 for a long time.

The residence time t of the mixed gas in the exhaust gas treatment device 900 can be calculated from the flow rate of the raw gas (amount of substance n moles/sec), the temperature of the deposition chamber (T), the internal volume of the treatment chamber (Va), and the pressure inside the tube (P). For example, the gas state equation PV=nRT can be used to calculate the temperature T and the inflow volume VL in 1 sec, and t=Va/VL.

Each component of the exhaust gas treatment device 900 is preferably made of graphite so that it can withstand the operating environment. Graphite makes it easy to process the exhaust gas treatment device 900 into any shape, and by using an inert atmosphere during exhaust gas treatment, the device can have sufficient durability to withstand high-temperature film formation conditions.

<Quadrupole Mass Spectrometer 1600>
The quadrupole mass spectrometer 1600 is a mass spectrometer that can form an electric field through which only ions of a specific mass (m/z value) can pass without being repelled by applying a DC voltage and an AC voltage to four electrode rods (quadrupoles). A sampling pipe 1610 for sampling exhaust gas is connected to the exhaust pipe 350, and the exhaust gas is sampled by performing differential pumping, so that the components of the exhaust gas can be detected by the quadrupole mass spectrometer 1600.

<Cold Trap 1700>
The cold trap 1700 is a device that condenses gas into liquid during a decompression operation. In the manufacturing apparatus 1000, the cold trap 1700 is disposed downstream of the sampling pipe 1610, and exhaust gas is introduced from the exhaust pipe 350 into the cold trap 1700, whereby gaseous SiCl ₄ can be liquefied and concentrated.

(Other configurations)
The manufacturing apparatus 1000 according to an embodiment of the present invention may have a further configuration in addition to the above configuration. For example, as shown in FIG. 13, a cylindrical outer cylinder 1100, for example made of carbon, into which the film formation chamber 100 is inserted, a holding jig 1200 that fixes the film formation chamber 100 from the outside of the first surface 110 inside the outer cylinder 1100, a ceramic furnace core tube 1300 into which the outer cylinder 1100 is inserted and through which an inert gas such as Ar gas flows between the outer cylinder 1100 and the ceramic furnace core tube 1300, a fixing flange 1400 that fixes the outer cylinder 1100 and the ceramic furnace core tube 1300 at both ends, and a housing 1500 that houses the film formation chamber 100 together with the outer cylinder 1100 and the ceramic furnace core tube 1300. Although not shown, the apparatus may be provided with a temperature measuring means such as a thermometer that can measure the temperature inside the film formation chamber 100, the temperature of the first surface 100, and the temperature of the mixed gas outlet 200, a control means such as a switch that controls the heat generation of the heater 400, a power source for generating heat, and the like.

[Exhaust gas treatment method]
Next, as one example of the exhaust gas treatment method of the present invention, a description will be given of an exhaust gas treatment method using the production apparatus 1000. The exhaust gas treatment method of the present invention includes a mixing step and a heat treatment step, which will be described below.

<Mixing process>
This process is a process in which a mixed gas is obtained by mixing hydrogen chloride gas with exhaust gas containing _SiCl2 discharged from a deposition chamber 100 in which polycrystalline silicon carbide is deposited on the surface of a carbon substrate by chemical vapor deposition using silicon chloride gas and a carbon-based gas as raw material gases.

The exhaust gas contains silicon chlorine gas and carbon-based gas, which are the raw material gases for silicon carbide, as described below, as well as carrier gases such as rare gases such as argon gas and helium gas, and hydrogen gas, which serve to transport these raw material gases, and may also contain dopant gases such as nitrogen gas and argon gas as appropriate.

(silicon chloride gas)
The silicon chloride gas is not particularly limited as long as it _is used for CVD growth of silicon carbide by thermal CVD. For example, the chlorosilane gas may be _SiH3Cl , _SiH2Cl2 , _SiHCl3 , _SiCl3 , _SiCl4 , etc., and one or a mixture of two or more of these may be suitably used. In addition, not only the monomers of these chlorosilanes but also the dimer gases may be used. For example, the silicon chloride gas may be _SiCl4 or _SiCl3 .

(Carbon-based gas)
As the carbon-based gas, a known gas can be used like silicon chloride gas, and generally, a hydrocarbon gas can be used. For example, since it is in a gaseous state near room temperature and is convenient for handling, a carbon-based gas consisting of a saturated hydrocarbon having a carbon number of 5 or less, or an unsaturated hydrocarbon having a carbon number of 5 or less is preferable, and a mixture of one or more of these can be suitably used. In particular, one or more of the hydrocarbon gases selected from the hydrocarbons having a carbon number of 5 or less, such as methane, ethane, propane, butane, or similar hydrocarbon gases, can be appropriately used as the carbon-based gas. In addition, gases such as aromatic hydrocarbons can also be used, but they generally have a slow decomposition rate and tend to form carbon aggregates, so care must be taken. In addition, hydrogen is preferably used as a carrier gas for the carbon-based gas, since it can suppress the reaction between the gases.

<Heat treatment process>
This step is a step of heat-treating the mixed gas for 10 seconds or more and 3600 seconds or less, and the mixed gas can be heat-treated, for example, by an exhaust gas treatment device 900. This step can convert _SiCl2 to _SiCl4 .

(Heat treatment time)
If the heat treatment time is less than 10 seconds, the conversion from _SiCl2 to _SiCl4 may be insufficient, and the amount of _SiCl2 remaining in the exhaust gas may be large. If the heat treatment time is 3600 seconds, the conversion from _SiCl2 to _SiCl4 is sufficient.

(Heat treatment temperature)
In the heat treatment step, the heat treatment temperature of the mixed gas is 1100 K or more and 1300 K or less, so that high-order chlorosilane polymers such as _SiCl2 can be efficiently converted to _SiCl4 . If the heat treatment temperature of the mixed gas is outside the condition of 1100 K or more and 1300 K or less, the conversion of _SiCl2 to _SiCl4 may not be efficient. The indoor temperature of the exhaust gas treatment device 900 can be controlled using the heater 410.

(Mixing ratio of _SiCl2 and HCl)
In the mixing step, the mixing ratio of _SiCl2 and hydrogen chloride gas in the exhaust gas is _SiCl2 :HCl=1:3-8 in molar ratio, so that high-order chlorosilane polymers such as _SiCl2 can be efficiently converted to _SiCl4 . If the mixing ratio of _SiCl2 and hydrogen chloride gas in the exhaust gas does not meet the above conditions, the conversion of _SiCl2 to _SiCl4 may not be efficient. The exhaust gas and hydrogen chloride gas can be mixed by introducing hydrogen chloride gas from the outside into the exhaust gas through the hydrogen chloride gas inlet pipe 320.

The mixture ratio of SiCl ₂ and hydrogen chloride gas in the exhaust gas can be measured and controlled using a detection means capable of detecting the contents of SiCl ₂ and hydrogen chloride gas.

(Other processes)
The exhaust gas treatment method of the present invention may include other steps in addition to the steps described above, such as a step of discharging the exhaust gas from the exhaust gas treatment device 900 to the exhaust pipe 350 and a step of warming the hydrogen chloride gas before it is introduced into the exhaust gas treatment device 900.

In addition, the process may include a step of detecting the components of the exhaust gas using a quadrupole mass spectrometer 1600, and a recovery step of introducing the exhaust gas from the exhaust pipe 350 into a cold trap 1700, liquefying and concentrating the gaseous _SiCl4 , and recovering the _SiCl4 .

[Method for manufacturing silicon carbide polycrystalline wafer]
Next, the method for producing a silicon carbide polycrystalline wafer of the present invention will be described. The method for producing a silicon carbide polycrystalline wafer of the present invention includes the exhaust gas treatment method of the present invention. The exhaust gas treatment method is as described above, and therefore a description thereof will be omitted.

The method for producing a silicon carbide polycrystalline wafer of the present invention can include a process for producing a silicon carbide polycrystalline wafer, such as a film formation process, in addition to the exhaust gas treatment method of the present invention. Below, a method for producing a silicon carbide polycrystalline wafer using the production apparatus 1000 will be described as an example of the method for producing a silicon carbide polycrystalline wafer of the present invention.

(Film forming process)
The film formation process is a process in which the substrates 600 are stacked on the substrate holder 500 in a non-contact manner at equal intervals in the film formation chamber 100, and the substrates 600 are arranged with their film formation target surfaces 610 parallel to the side surfaces 130. The mixed gas 810 is ejected from the mixed gas ejection ports 200 into the film formation chamber 100, and the mixed gas 810 is exhausted from the mixed gas exhaust port 300 from the film formation chamber 100, and the mixed gas 810 is caused to flow in a direction parallel to the film formation target surfaces 610, thereby forming a film on the substrates 600. By forming a film in this manner, a film with little variation in thickness can be formed between the substrates or on the same film formation target surface.

In addition, if the width 700 of the gap between the film-forming surface 610 of the substrate 600 and the left side surface 130c, and the width 710 of the gap between the right side surface 130d are the same as the width 720 of each gap between the equally spaced stacked substrates 600, the mixed gas flows uniformly through these gaps, making it possible to form a film with less variation in thickness between substrates or on the same film-forming surface.

For example, as described with reference to FIG. 17, it is preferable to set the ejection velocity Vg of the mixed gas 810 ejected from the mixed gas ejection port 200 faster than the diffusion velocity Vd of the mixed gas 810.

In the method for manufacturing silicon carbide polycrystalline wafers, silicon chloride gas and carbon-based gas, which are the raw materials for silicon carbide, are the raw material gases, and the raw material gases are mixed with a carrier gas, such as a rare gas such as argon gas or helium gas, or hydrogen gas, which serves to transport these raw material gases, to form a mixed gas 810. The mixed gas 810 may further contain a dopant gas such as nitrogen gas or argon gas as appropriate. The silicon chloride gas, carbon-based gas, carrier gas, etc. are the same as those described in the exhaust gas treatment method, so their description will be omitted here.

Furthermore, when forming a silicon carbide polycrystalline film, the ratio of the number of carbon atoms in the carbon-based gas to the number of silicon atoms in the silicon chloride gas (C/Si) is important. By controlling C/Si to 0.7 to 1.3, it becomes easy to epitaxially grow a thin film of silicon carbide polycrystalline on the substrate 600, and the growth rate can be increased, leading to improved productivity. If C/Si is out of the range of 0.7 to 1.3, the balance between the abundance ratio of silicon atoms and carbon atoms becomes poor, which may make it difficult to form a silicon carbide polycrystalline film, slow down the film formation rate, or increase the amount of raw material gas that is not involved in the film formation and be wasted. For example, if C/Si is less than 0.7, there is a risk that unreacted Si will adhere to the film in a metallic state (droplets), causing defects. Also, if C/Si exceeds 1.3, there is a risk of surface steps called bunching occurring, which may have a negative effect on device fabrication. More preferably, C/Si is 0.8 to 1.2.

The growth rate of the silicon carbide polycrystalline thin film is preferably 10 μm/hour to 70 μm/hour, and the silicon chloride gas in this case is preferably set to have a concentration of 1 volume % to 10 volume %, preferably 2 volume % to 4 volume %, as given above as a preferred example of silicon chloride gas. On the other hand, the carbon-based gas is preferably set to have a concentration of 0.01 volume % to 1 volume %, preferably 0.02 volume % to 0.06 volume %. Note that this concentration range is exemplified for C ₃ H ₈ as an example, and when using another carbon-based gas, this concentration range can be changed to an equivalent amount of carbon (C). For example, when using methane (CH ₄ ) as the carbon-based gas, the upper and lower limits of this concentration range can be tripled.

As with the growth temperature, the growth pressure of the silicon carbide polycrystalline thin film can be the same as the general conditions for growing silicon carbide thin films by CVD. For example, it is recommended that the growth pressure be in the range of 10,000 Pa to 110,000 Pa.

In addition, in the method for manufacturing a silicon carbide polycrystalline wafer of the present invention, a plurality of Si substrates or C substrates are used as the substrates 600, and a silicon carbide polycrystalline thin film can be grown on each of the film formation target surfaces 610. There is no particular limit to the number of substrates 600 in one film formation process, but films can be formed simultaneously on 5 to 10 substrates to 20 to 30 substrates or more.

The thickness of the silicon carbide polycrystalline thin film grown on each surface of the substrate 600 can be set appropriately and is not particularly limited, but can generally be set to a thickness in the range of 0.2 mm to 5 mm.

In addition, in the method for producing a silicon carbide polycrystalline wafer of the present invention, the growth temperature when forming a silicon carbide polycrystalline thin film by CVD is preferably in the range of 1400K to 1800K. In the present invention, the main purpose is to produce a silicon carbide polycrystalline wafer with a 3C crystal system. In general, when the growth temperature is higher than 1800K, epitaxial growth may occur in the formation of the silicon carbide film, and there is a risk that a hexagonal crystal with a 4H crystal system may be formed together with 3C. In addition, if the growth temperature is lower than 1400K, the growth rate of silicon carbide may be slow, and the conditions may not be suitable for forming a thick film. In the formation of a silicon carbide film, the growth rate increases as the temperature increases, so the growth temperature is preferably in the range of 1400K to 1800K as described above in order to form a silicon carbide polycrystalline film with a 3C crystal system at high speed (10 μm/Hr or more).

(Other processes)
The method for manufacturing a silicon carbide polycrystalline wafer of the present invention may include other steps in addition to the film formation step and exhaust gas treatment method described above, such as a step of stacking the substrates 600 on the substrate holder 500 at equal intervals without contacting each other and placing the substrates 600 on the substrate holder 500, a step of placing the substrate holder 500 on which the substrates 600 are placed in the film formation chamber 100, a step of setting up the manufacturing apparatus 1000 in a state in which a film can be formed, a step of cooling the film formation chamber 100 after the film formation step, and a step of removing the substrates after film formation from the film formation chamber 100.

The present invention will be described in more detail below based on examples and comparative examples. Note that the present invention is not limited to the following contents.

Example 1
Nine carbon substrates each having a diameter of 4 inches (100 mm) and a thickness of 1 mm were prepared as the substrate 600. Using the silicon carbide polycrystalline wafer manufacturing apparatus 1000 shown in FIG. 13, silicon carbide polycrystalline films were formed by thermal CVD on both sides of the substrate 600, which were to be the film formation target surfaces 610, to manufacture silicon carbide polycrystalline wafers. After manufacturing the silicon carbide polycrystalline wafers, the inside of the exhaust pipe 350 arranged downstream of the exhaust gas treatment device 900 was observed to confirm the presence or absence of deposits resulting from the chlorine-containing silicon source gas in the exhaust gas, such as higher-order chlorosilane polymers.

<Silicon carbide polycrystalline wafer manufacturing apparatus 1000>
The outer cylinder 1100 has a cylindrical shape formed from a double-ended graphite crucible, and is inserted into the ceramic furnace core tube 1300. Both ends of the ceramic furnace core tube 1300 and the outer cylinder 1100 are sealed with metal fixing flanges 1400, and Ar gas is introduced inside to prevent oxidation of the graphite material. The film formation chamber 100 is fixed inside the outer cylinder 1100 by a holding jig 1200. The graphite mixed gas introduction pipe 210 is inserted into the holding jig 1200 and the first surface 100 so that the mixed gas outlet 200 is located inside the film formation chamber 100. The graphite mixed gas exhaust pipe 310 is inserted into the second surface 120 so that the mixed gas outlet 300 is located inside the film formation chamber 100. The exhaust gas discharged from the film formation chamber 100 is introduced into the inside of the housing 930 of the exhaust gas processing device 900 through the mixed gas exhaust pipe 310 and the exhaust gas introduction pipe 910, and is discharged from the inside of the housing 930 to the exhaust pipe 350. In addition, a cylindrical graphite heater 400 surrounding the ceramic furnace core tube 1300 and a graphite heater 410 surrounding the exhaust gas processing device 900 are installed, and further, a housing 1500 is provided that houses the film formation chamber 100 together with the outer cylinder 1100 and the ceramic furnace core tube 1300. The mixed gas 810 supplied to the film formation chamber 100 can be discharged to the outside from the manufacturing apparatus 1000 by using a vacuum pump (not shown) connected to the exhaust pipe 350.

In the manufacturing apparatus 1000, the ceramic furnace core tube 1300 has an outer diameter of 210 mm, an inner diameter of 190 mm, a uniform thickness, and a length of 700 mm. The outer cylinder 1100 has an outer diameter of 180 mm, an inner diameter of 170 mm, a uniform thickness, and a length of 700 mm. The film formation chamber 100 has an outer shape of a rectangular parallelepiped with a square of 118 mm and a length of 320 mm, and an inner shape of a rectangular parallelepiped with a square of 110 mm and a length of 312 mm, and has a uniform thickness.

(Gas outlet 200)
14, four mixed gas outlets 200 with an inner diameter of 12 mm are arranged in a row on the first surface 110. The four mixed gas outlets 200 are arranged at equal intervals of 22 mm around the center of the tube. The row of mixed gas outlets 200 is arranged in the center of the first surface 110 in the width direction (direction perpendicular to the row).

In addition, a hydrogen chloride gas introduction pipe 320 having an inner diameter of 10 mm was connected to the exhaust gas introduction pipe 910 so that a mixed gas could be obtained by mixing the exhaust gas containing SiCl ₂ discharged from the film formation chamber with hydrogen chloride gas.

(Exhaust gas treatment device 900)
As shown in Fig. 13, the inside of the exhaust gas treatment device 900 was formed by combining cylindrical pipes 940 made of graphite with an inner diameter of 100 mm and a uniform thickness so that the flow path of the exhaust gas was in a serpentine shape. Four types of such exhaust gas treatment device 900 were prepared, each with a different flow path length from the hydrogen chloride gas introduction pipe 320 to the exhaust piping 350 of 500 mm, 1000 mm, 3500 mm, and 7000 mm. The temperature of the exhaust gas treatment device 900 was controlled by a heater 410, and the temperature inside the exhaust gas treatment device 900 was changed from 1100 K to 1600 K.

(Installation of the substrate 600)
As shown in FIG. 16, nine substrates 600 were placed on the substrate holder 500. The substrates 600 were placed in the film formation chamber 100 while being fixed to the substrate holder 500 by the grooves 511 and 521. As shown in FIG. 16(b), the upper holding rod 510 of the substrate holder 500 was in close contact with the upper side surface 130a so that the mixed gas 810 would not enter between the upper side surface 130a, and the lower holding rod 520 was in close contact with the lower side surface 130b so that the mixed gas 810 would not enter between the lower side surface 130b. The width 700 of the gap between the film formation target surface 610 of the substrate 600 and the left side surface 130c, the width 710 of the gap between the right side surface 130d, and the width 720 of each gap between the substrates 600 stacked at equal intervals were all 10 mm. The shortest distance between the mixed gas outlet 200 and the substrate holder 500 was 150 mm.

(Deposition of silicon carbide polycrystalline film)
In order to prevent oxidation of the graphite material, Ar gas was flowed between the outer cylinder 1100 and the ceramic furnace core tube 1300, and into the housing 1500. Then, after evacuating the inside of the film formation chamber 100 with a vacuum pump (not shown), the pressure in the film formation chamber 100 was adjusted to atmospheric pressure (101,325 Pa) while introducing hydrogen gas into the film formation chamber 100 at a flow rate of 200 cm ₃ per minute using the mixed gas introduction pipe 210. Then, while keeping the pressure constant, the temperature in the film formation chamber 100 was raised to 1500 K while maintaining the temperature of the first surface 110 at 1100 K or less and the temperature of the mixed gas outlet 200 at 1200 K or less. Then, the flow rate of hydrogen gas introduced into the film formation chamber 100 was increased to 3.0 liters per minute. After maintaining this state for 3 minutes, 0.3 liters per minute of _SiCl4 gas, 0.3 liters per minute of _CH4 gas, 1.0 liters per minute of Ar gas, and 1.0 liters per minute of hydrogen gas were mixed into this hydrogen gas to obtain a mixed gas 810, and formation of a silicon carbide polycrystalline film by thermal CVD was started on the substrate 600 in a state of Vg>Vd.

The exhaust gas after being heat-treated in the exhaust gas treatment device 900 was introduced into a cold trap 1700 (Yamato Scientific CA301, glass trap used), and _SiCl4 was liquefied at -20°C and recovered.

In addition, a sampling pipe 1610 for gas sampling was connected to the exhaust pipe 350 in front of the cold trap 1700, and differential pumping was performed to sample the exhaust gas, and the components of the exhaust gas were detected using a quadrupole mass spectrometer 1600 (PrismaPlus QMG220 mass ratio 1-200).

After the film formation process was performed for 4 hours, the supply of the mixed gas 810 and heating by the heater 400 were stopped, the substrate 600 was cooled to room temperature, and the substrate 600 on which the silicon carbide polycrystalline film was formed was removed from the substrate holder 500. The silicon carbide film was formed normally, and there were no problems with the film formation. In addition, the inside of the exhaust pipe 350 after film formation was observed to check for the presence or absence of deposits due to the chlorine-containing silicon source gas in the exhaust gas, such as higher-order chlorosilane polymers, and no deposits due to the chlorine-containing silicon source gas were found.

The amount of SiC precipitated inside the substrate 600 and the manufacturing apparatus 1000 was 36 mass% of the amount of SiC when the entire amount of the raw material used was SiC. Here, the number of moles of _SiCl4 when the raw material gas was supplied at 0.3 L/min for 4 hours was about 3.2 moles, and excluding the amount of precipitated SiC (36 mass%), the amount of exhausted Si-based gas was about 2 moles (molecular weight 169.9) in terms of _SiCl4 , about 348 g.

When the length of the flow path from the hydrogen chloride gas inlet pipe 320 to the exhaust pipe 350 was 500 mm, 1000 mm, 3500 mm, and 7000 mm, the residence time of the mixed gas at each length was 72 seconds at 500 mm, 144 seconds at 1000 mm, 504 seconds at 3500 mm, and 1008 seconds at 7000 mm. The temperature of the substrate 600 was set to 1500 K, and the temperature inside the exhaust gas treatment device 900 was changed in increments of 100 K from 900 K to 1400 K.

In the measurement of the exhaust gas by the quadrupole mass spectrometer 1600, the elements Ar, _H2 , _SiCl4 , and HCl were detected. Silicon chlorides such as _SiCl2 and _SiCl3 , which are the decomposition products of _SiCl4 , were not detected. The ratio of the peak of Ar (mass number 40) when _SiCl4 was detected in the measurement of the quadrupole mass spectrometer 1600 is shown in Table 5. In Table 5, ND indicates not detected. In Table 5, the units of 0, 0.2, 0.5, and 1.0 for HCl are L/min, and represent the amount of hydrogen chloride introduced into the exhaust gas from the hydrogen chloride gas introduction pipe 320. In addition, 3.1, 4.2, 5.7, and 8.3 for HCl/ _SiCl2 are the molar ratios of HCl/ _SiCl2 in the exhaust gas after hydrogen chloride is introduced from the hydrogen chloride gas introduction pipe 320.

In addition, since HCl is generated by the decomposition of the source gas _SiCl4 , HCl/ _SiCl2 does not become 0 even when the amount of HCl added is 0 ( _SiCl4 + _H2 → _SiCl2 + 2HCl). The HCl/ _SiCl2 ratio was obtained by calculating the amount of HCl from HCl/Ar based on the measurement results of the quadrupole mass spectrometer 1600, and the amount of _SiCl2 was calculated by subtracting the amount that became the SiC film from the amount of _SiCl4 (assuming that the entire amount became _SiCl2 ).

The amount of _SiCl4 (g) recovered in the cold trap 1700 is shown in Table 6. 36 mass % of _SiCl4 precipitated on the substrate, and about 10 mass % precipitated as SiC inside the exhaust gas treatment device 900. Precipitation of SiC in the piping of the exhaust gas treatment device 900 was observed when the heat treatment temperature was 1300 K or higher, and was particularly noticeable when the heat treatment temperature was 1500 K.

Taking these precipitations into consideration, the actual amount of _SiCl4 recovered agreed with the amount of recovery calculated on the assumption that all of the _SiCl4 in the feed gas was converted to _SiCl2 , and it was found that particularly large amounts of _SiCl4 could be recovered when the HCl/ _SiCl2 ratio was 2 or more and the temperature was 1000K to 1400K.

(Conventional example)
A silicon carbide polycrystalline wafer manufacturing apparatus 3000 (FIG. 12) having the same configuration as the manufacturing apparatus 1000 except that it does not include the exhaust gas treatment apparatus 900, the hydrogen chloride gas introduction pipe 320, the quadrupole mass spectrometer 1600, and the cold trap 1700, and the exhaust gas is discharged to the outside of the manufacturing apparatus through the mixed gas exhaust pipe 310 was used, and a film formation process was performed under the same conditions as in the example, and the inside of the mixed gas exhaust pipe 310 after the film formation was observed. Although the silicon carbide film was formed normally and there were no problems with the film formation, about 300 g of deposits due to the raw material SiCl ₂ gas were attached to the inside of the mixed gas exhaust pipe 310.

(summary)
From the results of the examples, it was confirmed that, according to the present invention, by adding hydrogen chloride gas to the exhaust gas, setting the heat treatment temperature to 1100 K or more and 1300 K or less, and setting the heat treatment time to 10 seconds or more and 3600 seconds or less, it is possible to convert SiCl2 into _SiC4 and efficiently recover _SiCl2 without causing chlorosilane-based polymers to adhere to exhaust piping, etc. inside the manufacturing equipment for silicon carbide polycrystalline wafers.

100 Film formation chamber 110 First surface 120 Second surface 130 Side surface 130a Upper surface 130b Lower surface 130c Left side surface 130d Right side surface 200 Mixed gas outlet 210 Mixed gas inlet pipe 300 Mixed gas outlet 310 Mixed gas outlet pipe 320 Hydrogen chloride gas inlet pipe 350 Exhaust pipe 400 Heater 410 Heater 500 Substrate holder 510 Upper holding rod 511 Groove 520 Lower holding rod 521 Groove 600 Substrate 610 Film formation target surface 700 Width 710 Width 720 Width 800 Mixed gas 810 Mixed gas
900K Low temperature 900 Exhaust gas treatment device 910 Exhaust gas introduction pipe 920 Reaction chamber 930 Case 940 Pipe 1000 Manufacturing device 1100 Outer cylinder 1200 Holding jig 1200 Holding jig 1300 Ceramic furnace core tube 1400 Fixing flange 1500 Case 1600 Quadrupole mass spectrometer 1600 Mass spectrometer 1610 Sampling pipe 1700 Cold trap 3000 Manufacturing device

Claims (2)

A mixing step of mixing hydrogen chloride gas with exhaust gas containing SiCl ₂ discharged from a film formation chamber in which silicon carbide polycrystalline is formed on a surface of a carbon substrate by chemical vapor deposition using silicon chloride gas and a carbon-based gas as raw material gases to obtain a mixed gas;
a heat treatment step of heat-treating the mixed gas for 1 second or more and 3600 seconds or less;
Including ,
The heat treatment temperature of the mixed gas is 1100K or more and 1300K or less,
The mixing ratio of SiCl ₂ in the exhaust gas to the hydrogen chloride gas in the mixing step is SiCl ₂ :HCl=1:3 to 8 in molar ratio;
When the heat treatment time is 1 second or longer, the heat treatment temperature is 1300K and the SiCl ₂ :HCl ratio is 1:8.
When the heat treatment time is 10 seconds or more, the ratio of SiCl ₂ :HCl is 1:5-8 at a heat treatment temperature of 1300K.
When the heat treatment time is 100 seconds or more, the heat treatment temperature is 1200K and the SiCl ₂ :HCl ratio is 1:3-8.
When the heat treatment time is 1000 seconds or more, the heat treatment temperature is 1100K and the SiCl ₂ :HCl ratio is 1:4-8.
Exhaust gas treatment method. A method for producing a silicon carbide polycrystalline wafer, comprising the exhaust gas treatment method according to claim 1 .

Images