KR102124766B1 - Plasma processing apparatus and manufacturing method of the same - Google Patents

Abstract

The present invention relates to a plasma processing device and a manufacturing method thereof. The plasma processing device comprises: a chamber providing reaction space for processing plasma; and a component mounted in the chamber and in contact with the plasma. The component or the inner wall of the chamber is made of a silicon carbide-based composite made of a plasma-resistant material. A silicon carbide-based composite has a relative density higher than 92% while including a SiC crystal phase and a B4C crystal phase, and has a specific resistance lower than 30Ω·cm. The component or the inner wall of the chamber used in the plasma processing device of the present invention is made of the silicon carbide-based composite made of the plasma-resistant material. The silicon carbide-based composite does not have a large difference in electrical resistance depending on a location of the material, exhibits low electrical resistance, and has excellent thermal conduction and mechanical properties.

Description

Plasma processing apparatus and manufacturing method of the same

The present invention relates to a plasma processing apparatus and a method for manufacturing the same, and more specifically, a component made of a low-resistance silicon carbide-based composite material exhibiting low electrical resistance and not showing a large difference in electrical resistance depending on the location of the material. Or it relates to a plasma processing apparatus including the inner wall of the chamber and a manufacturing method thereof.

Silicon carbide (SiC) is a representative non-oxide-based ceramics, and has attracted attention as a new functional material because it has better performance than oxide-based ceramics.

SiC has excellent mechanical properties such as strength, hardness, and abrasion resistance, exhibits low coefficient of thermal expansion, high thermal conductivity, and excellent corrosion resistance.

SiC sintered bodies having such properties are applied to (high temperature) structural materials, abrasives, and parts of semiconductor/display manufacturing equipment. However, the SiC sintered body is limited in its application due to its high electrical resistance.

There is a study to lower the electrical resistance of the SiC sintered body, but in the case of the existing low-resistance SiC sintered body, there is a problem that a difference in electrical resistance occurs depending on the location of the material.

Republic of Korea Registered Patent Publication No. 10-0637635 Republic of Korea Registered Patent Publication No. 10-0845219

The problem to be solved by the present invention is a plasma processing apparatus including a component or a chamber inner wall made of a low-resistance silicon carbide-based composite material that exhibits low electrical resistance, which does not have a large difference in electrical resistance depending on the location of the material, and has excellent thermal conductivity and mechanical properties. It is to provide the manufacturing method.

The present invention includes a chamber that provides a reaction space for plasma processing, and a component mounted in the chamber and in contact with the plasma, wherein the component or the inner wall of the chamber is made of a plasma-resistant silicon carbide-based composite, The silicon carbide-based composite provides a plasma processing apparatus comprising a SiC crystal phase and a B ₄ C crystal phase, and exhibiting a relative density higher than 92% and a specific resistance lower than 30 Pa·cm.

The part may be a susceptor, showerhead or edge ring.

The silicon carbide-based composite may further include an Al ₂ O ₃ crystal phase.

The silicon carbide-based composite may further include a Y ₂ O ₃ crystal phase.

The silicon carbide-based composite may further include a YAG (Yttrium aluminum garnet, Y ₃ Al ₅ O ₁₂ ) crystal phase.

The silicon carbide-based composite may exhibit a thermal conductivity higher than 50W/mK.

It is preferable that the SiC and B ₄ C form a weight ratio of 50:50 to 90:10 in the silicon carbide-based composite.

In addition, the present invention, in a method for manufacturing a plasma processing apparatus including a chamber for providing a reaction space for plasma processing and a component mounted in the chamber and in contact with the plasma, SiC powder and B ₄ C powder as starting materials Preparing and mixing to prepare a slurry, spray drying the starting material in a slurry state to obtain granular powder, and mounted in a chamber that provides a reaction space for plasma treatment to contact plasma. Preparing a mold for molding into the shape of a part or molding into the shape of the inner wall of the chamber, loading the granulated powder into the mold and charging the furnace, raising the temperature of the furnace and applying pressure to the granulated powder. Sintering while applying, and cooling the furnace to obtain the parts made of a silicon carbide-based composite made of a plasma-resistant material or an inner wall of the chamber, wherein the silicon carbide-based composite comprises a SiC crystal phase and a B ₄ C crystal phase. Provided is a method of manufacturing a plasma processing apparatus comprising a relative density higher than 92% and a specific resistance lower than 30 Pa·cm.

The starting material may further include aluminum nitrate hydrate, and the aluminum nitrate hydrate is preferably mixed in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total content of the SiC powder and the B ₄ C powder.

The starting material may further include yttrium nitrate hydrate, and the yttrium nitrate hydrate is preferably mixed in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total content of the SiC powder and the B ₄ C powder.

The starting material may further include aluminum nitrate hydrate and yttrium nitrate hydrate, and the aluminum nitrate hydrate and the yttrium nitrate hydrate are 0.1 to 100 parts by weight of the total content of the SiC powder and the B ₄ C powder. It is preferable to mix ∼10 parts by weight.

The starting material to mix Al (OH) may further comprise a _third powder, the Al (OH) ₃ powder, per 100 parts by weight of the total amount of the SiC powder and the B ₄ C powder, 0.1 to 10 parts by weight desirable.

The starting material may comprise Y ₂ O ₃ powder, further, the Y ₂ O ₃ powder, it is preferable to mix 0.1 to 10 parts by weight based on the total amount of 100 parts by weight of the SiC powder and the B ₄ C powder .

The starting material may further include liquid sodium silicate, and the liquid sodium silicate is preferably mixed in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the total content of the SiC powder and the B ₄ C powder. .

The SiC powder and the B ₄ C powder are preferably mixed in a weight ratio of 50:50 to 90:10.

The sintering temperature is preferably in the range of 1750 ~ 2100 ℃.

The pressure applied to the granulated powder is preferably in the range of 10 to 60 MPa.

The spray drying is preferably performed under conditions of an inlet temperature of 85 to 270°C, an outlet temperature of 60 to 120°C, and a rotation speed of 6000 to 15000 rpm.

The silicon carbide-based composite may exhibit a thermal conductivity higher than 50W/mK.

The part may be a susceptor, showerhead or edge ring.

The inner wall of the part or chamber used in the plasma processing apparatus of the present invention is made of a silicon carbide-based composite made of a plasma-resistant material, and the silicon carbide-based composite exhibits low electrical resistance without a large difference in electrical resistance depending on the location of the material. The SiC single sintered body exhibits high electrical resistance, and is formed of a composite so as to have a lower electrical resistance than the SiC single sintered body, and can be applied as a material for a plasma processing device or the like.

The silicon carbide-based composite applied to the parts of the plasma processing apparatus or the inner wall of the chamber of the present invention exhibits a relative density higher than 92%, and the spacing between particles is very dense and the pores are hardly formed, and the crystal state is excellent.

In addition, the silicon carbide-based composite applied to the parts of the plasma processing apparatus or the inner wall of the chamber of the present invention is excellent in thermal conductivity and mechanical properties.

1 and 2 are views showing a plasma processing apparatus according to a preferred embodiment of the present invention.
3 is a view showing the temperature increase rate, the holding time during sintering, and the pressure applied to the granulated powder according to the time of hot pressing sintering.
4 is a view showing an X-ray diffraction (XRD) pattern of a silicon carbide-based composite prepared by hot pressing sintering at 2000°C according to Experimental Examples 1 to 3.
5 is a view showing the relative density of the silicon carbide-based composite prepared according to Experimental Example 1 to Experimental Example 3.
6 is a view showing the hardness of the silicon carbide-based composite prepared according to Experimental Examples 1 to 3.
7 is a view showing the strength of the silicon carbide-based composite prepared according to Experimental Examples 1 to 3.
FIG. 8 is a scanning electron microscope (SEM) photograph of a silicon carbide-based composite prepared by mixing SiC powder and B ₄ C powder in a weight ratio of 70:30 according to Experimental Example 1 and hot pressing sintering at 2000°C. .
9 is a photograph of a kettle microscope (SEM) of a silicon carbide-based composite prepared by mixing SiC powder and B ₄ C powder in a weight ratio of 50:50 according to Experimental Example 2 and hot pressing and sintering at 2000°C.
10 is a scanning electron microscope (SEM) photograph of a silicon carbide-based composite prepared by mixing SiC powder and B ₄ C powder in a weight ratio of 30:70 according to Experimental Example 3 and hot pressing and sintering at 2000°C.
11 is a view showing the thermal conductivity of the silicon carbide-based composite prepared according to Experimental Example 1 to Experimental Example 3.
FIG. 12 shows a state in which 10 points (front (F) 5 point, rear (B) 5 point) were selected on a plate-type silicon carbide-based composite specimen having a width of 380 mm and a height of 380 mm to measure specific resistance. It is a drawing.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the following embodiments are provided to those of ordinary skill in the art to fully understand the present invention, and may be modified in various other forms, and the scope of the present invention is limited to the embodiments described below. It does not work.

In the description or claims of the present invention, when any one component "includes" another component, it is not limited to being interpreted as being composed of the component only, unless specifically stated otherwise, and other components are further added. It should be understood that it can be included.

A plasma processing apparatus according to a preferred embodiment of the present invention includes a chamber providing a reaction space for plasma processing, and a component mounted in the chamber and in contact with the plasma, wherein the component or the inner wall of the chamber is a plasma-resistant material It is made of a silicon carbide-based composite, and the silicon carbide-based composite includes a SiC crystal phase and a B ₄ C crystal phase, and has a relative density higher than 92% and a specific resistance lower than 30 Pa·cm.

The part may be a susceptor, showerhead or edge ring.

The silicon carbide-based composite may further include an Al ₂ O ₃ crystal phase.

The silicon carbide-based composite may further include a Y ₂ O ₃ crystal phase.

The silicon carbide-based composite may further include a YAG (Yttrium aluminum garnet, Y ₃ Al ₅ O ₁₂ ) crystal phase.

The silicon carbide-based composite may exhibit a thermal conductivity higher than 50W/mK.

It is preferable that the SiC and B ₄ C form a weight ratio of 50:50 to 90:10 in the silicon carbide-based composite.

A method of manufacturing a plasma processing apparatus according to a preferred embodiment of the present invention includes a chamber providing a reaction space for plasma processing, and a plasma processing apparatus including a component mounted in the chamber and in contact with the plasma, Preparing and mixing SiC powder and B ₄ C powder as a starting material to make a slurry, and spray drying the starting material in a slurry state to obtain granular powder, and a reaction space for plasma treatment. Preparing a mold for molding into a shape of a part that is mounted in a provided chamber and in contact with the plasma or forming the shape of the inner wall of the chamber, and loading the granulated powder into the mold and loading it into the furnace, And raising the temperature and sintering while applying pressure to the granular powder, and cooling the furnace to obtain the parts made of a silicon carbide-based composite of a plasma-resistant material or an inner wall of the chamber, wherein the silicon carbide-based The composite includes a SiC crystal phase and a B ₄ C crystal phase, and has a relative density higher than 92% and a specific resistance lower than 30 Pa·cm.

A method of manufacturing a silicon carbide-based composite according to a preferred embodiment of the present invention includes preparing and mixing SiC powder and B ₄ C powder as starting materials to make a slurry, and spray drying the starting materials in a slurry state (spray drying). ) To obtain granular powder, loading the granulated powder into a furnace, heating the temperature of the furnace and sintering while applying pressure to the granulated powder, and cooling the furnace to cool silicon carbide And obtaining the complex.

The starting material may further include aluminum nitrate hydrate, and the aluminum nitrate hydrate is preferably mixed in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total content of the SiC powder and the B ₄ C powder.

The starting material may further include yttrium nitrate hydrate, and the yttrium nitrate hydrate is preferably mixed in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total content of the SiC powder and the B ₄ C powder.

The starting material may further include aluminum nitrate hydrate and yttrium nitrate hydrate, and the aluminum nitrate hydrate and the yttrium nitrate hydrate are 0.1 to 100 parts by weight of the total content of the SiC powder and the B ₄ C powder. It is preferable to mix ∼10 parts by weight.

The starting material to mix Al (OH) may further comprise a _third powder, the Al (OH) ₃ powder, per 100 parts by weight of the total amount of the SiC powder and the B ₄ C powder, 0.1 to 10 parts by weight desirable.

The starting material may comprise Y ₂ O ₃ powder, further, the Y ₂ O ₃ powder, it is preferable to mix 0.1 to 10 parts by weight based on the total amount of 100 parts by weight of the SiC powder and the B ₄ C powder .

The starting material may further include liquid sodium silicate, and the liquid sodium silicate is preferably mixed in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the total content of the SiC powder and the B ₄ C powder. .

The SiC powder and the B ₄ C powder are preferably mixed in a weight ratio of 50:50 to 90:10.

The sintering temperature is preferably in the range of 1750 ~ 2100 ℃.

The pressure applied to the granulated powder is preferably in the range of 10 to 60 MPa.

The spray drying is preferably performed under conditions of an inlet temperature of 85 to 270°C, an outlet temperature of 60 to 120°C, and a rotation speed of 6000 to 15000 rpm.

The silicon carbide-based composite includes a SiC crystal phase and a B ₄ C crystal phase, and has a relative density higher than 92% and may have a specific resistance lower than 30 Pa·cm.

The silicon carbide-based composite may exhibit a thermal conductivity higher than 50W/mK.

The part may be a susceptor, showerhead or edge ring.

Hereinafter, a plasma processing apparatus according to a preferred embodiment of the present invention will be described in more detail.

1 and 2 are views showing a plasma processing apparatus according to a preferred embodiment of the present invention.

1 and 2, a plasma processing apparatus according to a preferred embodiment of the present invention includes a chamber 100 providing a reaction space for plasma processing, and a component mounted in the chamber 100 and contacting plasma. do.

The component may be a susceptor 110, a shower head 120, or an edge ring 130.

The susceptor 110 on which the plasma processing object 140 such as a silicon wafer is mounted may be provided to be movable up and down. 2 shows a state in which the susceptor 110 is moved upward.

The shower head 120 is positioned above the susceptor 110 and serves to inject reaction gas for a plasma shape toward the plasma treatment object 150. The shower head 120 is connected to a reaction gas supply pipe 160 for supplying a reaction gas. The shower head 120 includes a buffer part 124 for uniformly spreading the reaction gas supplied through the reaction gas supply pipe 160 and a plurality of through holes through which the reaction gas introduced into the buffer space 124 passes. It may include a provided nozzle unit 122.

The edge ring 130 may be installed on the inner wall 102 of the chamber in a form surrounding the plasma processing object 150.

An RF power source 170 for generating plasma may be provided outside the chamber. When the RF power supply 170 is applied and the reaction gas is injected through the nozzle unit 122 of the shower head 120, the injected reaction gas is converted into plasma used for etching, deposition, and the like.

During the plasma treatment process or after the plasma treatment process, unreacted or remaining reaction gas may be discharged to the outside of the chamber 100 through the outlet 150.

Among the components mounted in the chamber 100, the susceptor 110, the shower head 120, the edge ring 130 or the like, or the chamber inner wall 102 is a part in contact with plasma, and is preferably made of a blast-resistant material.

Components such as the susceptor 110, the shower head 120, the edge ring 130, or the inner wall 102 of the chamber 100 that are in contact with the plasma are made of a silicon carbide-based composite made of a plasma-resistant material.

The SiC sintered body has excellent mechanical properties such as strength, hardness, and wear resistance, exhibits low coefficient of thermal expansion, high thermal conductivity, and excellent corrosion resistance. However, the SiC sintered body is limited in its application due to its high electrical resistance. There is a study to lower the electrical resistance of the SiC sintered body, but in the case of the existing low-resistance SiC sintered body, there is a problem that a difference in electrical resistance occurs depending on the location of the material.

The silicon carbide-based composite, as a SiC-B ₄ C-based composite, includes a SiC crystal phase and a B ₄ C crystal phase, and exhibits a relative density higher than 92% and a specific resistance lower than 30 Pa·cm (eg, 4 to 25 Pa·cm). Have The silicon carbide-based composite does not have a large difference in electrical resistance depending on the location of the material and exhibits low electrical resistance.

It is preferable that the SiC and B ₄ C form a weight ratio of 50:50 to 90:10 in the silicon carbide-based composite.

The silicon carbide-based composite may further include an Al ₂ O ₃ crystal phase.

The silicon carbide-based composite may further include a Y ₂ O ₃ crystal phase.

The silicon carbide-based composite may further include a YAG (Yttrium aluminum garnet, Y ₃ Al ₅ O ₁₂ ) crystal phase.

The silicon carbide-based composite may exhibit a thermal conductivity higher than 50 W/mK (eg, 51 to 130 W/mK).

Hereinafter, a method of manufacturing a plasma processing apparatus according to a preferred embodiment of the present invention will be described in more detail.

To prepare a silicon carbide-based composite (SiC-B ₄ C-based composite), SiC powder and B ₄ C powder are prepared as starting materials and mixed to make a slurry.

B ₄ C lowers the electrical resistance by controlling the resistance of the composite, and has excellent strength and abrasion resistance, which can improve mechanical properties than pure SiC when forming a composite with SiC, and also serves as a sintering aid to lower the surface energy at the grain boundary. It can play a role in smoothing the movement of particles.

The SiC powder and the B ₄ C powder are mixed in a weight ratio of 50: 50 to 90: 10 (weight fraction of SiC powder to the B ₄ C powder (SiC / B ₄ C) is 50/50 to 90/10) It is preferred. Since the particle size of the SiC powder and the B ₄ C powder affects the density and mechanical properties of the silicon carbide composite, the particle size of the SiC powder and the B ₄ C powder is selected in consideration of this. Preferably, a spherical powder having a particle diameter of 10 µm or less, more preferably 3 µm or less, and most preferably 1 µm or less in view of the fact that the silicon carbide-based composite requires high strength, high hardness, high wear resistance, and low electrical resistance. It is preferred to use.

The starting material may further include aluminum nitrate hydrate. Examples of the aluminum nitrate hydrate include Al(NO ₃ ) ₃ · 9H ₂ O (aluminium nitrate nonahydrate). The aluminum nitrate hydrate is preferably mixed with 0.1 to 10 parts by weight, more preferably 1 to 7 parts by weight with respect to 100 parts by weight of the total content of the SiC powder and the B ₄ C powder. The aluminum nitrate hydrate forms a liquid phase in a subsequent sintering process to lower the sintering temperature, and also serves to improve the thermal conductivity and lower the specific resistance of the silicon carbide-based composite. In addition, the aluminum nitrate hydrate may also serve as a source for forming Al ₂ O ₃ crystal phase.

In addition, the starting material may further include yttrium nitrate hydrate. Examples of the yttrium nitrate hydrate include Y(NO ₃ ) ₃ ·6H ₂ O (yttrium nitrate hexahydrate). The yttrium nitrate hydrate is preferably mixed with 0.1 to 10 parts by weight, more preferably 1 to 7 parts by weight with respect to 100 parts by weight of the total content of the SiC powder and the B ₄ C powder. The yttrium nitrate hydrate forms a liquid phase in a subsequent sintering process to lower the sintering temperature, and also serves to improve the thermal conductivity and lower the resistivity of the silicon carbide-based composite. Also, the yttrium nitrate hydrate may act as a source for forming a Y ₂ O ₃ crystal phase.

In addition, the starting material may further include aluminum nitrate hydrate (aluminium nitrate hydrate) and yttrium nitrate hydrate (yttrium nitrate hydrate). The total content of the aluminum nitrate hydrate and the yttrium nitrate hydrate is 0.1 to 10 parts by weight, more preferably 1 to 7 parts by weight, based on 100 parts by weight of the total content of the SiC powder and the B ₄ C powder. desirable. In this case, the aluminum nitrate hydrate and the yttrium nitrate hydrate have a weight ratio of 1:9 to 9:1 (weight fraction of aluminum nitrate hydrate to yttrium nitrate hydrate (aluminum nitrate hydrate/yttrium nitrate hydrate)) 1/9 to 9/1), more preferably 2:8 to 8:2, and most preferably 3:7 to 7:3. The aluminum nitrate hydrate and the yttrium nitrate hydrate form a liquid phase in a subsequent sintering process to lower the sintering temperature, improve the thermal conductivity of the silicon carbide-based composite, and also serve to lower the specific resistance. In addition, the aluminum nitrate hydrate and the yttrium nitrate hydrate may also serve as a source for forming a YAG (Yttrium aluminum garnet, Y ₃ Al ₅ O ₁₂ ) crystal phase.

The starting material may further include Al(OH) ₃ powder. The Al(OH) ₃ powder may serve as a source for forming Al ₂ O ₃ crystal phase. The Al(OH) ₃ powder is preferably mixed with 0.1 to 10 parts by weight, more preferably 1 to 7 parts by weight with respect to 100 parts by weight of the total content of the SiC powder and the B ₄ C powder.

The starting material may further include Y ₂ O ₃ powder. The Y ₂ O ₃ powder may serve as a source for forming a Y ₂ O ₃ crystal phase. The Y ₂ O ₃ powder is preferably mixed with 0.1 to 10 parts by weight, more preferably 1 to 7 parts by weight with respect to 100 parts by weight of the total content of the SiC powder and the B ₄ C powder.

The starting material may further include liquid sodium silicate. When liquid sodium silicate is mixed, the fluidity of the obtained granulated powder may be increased, and the filling rate may be increased when the granulated powder is filled into a mold. In addition, the liquid silicate may form a liquid in a subsequent sintering process to lower the sintering temperature. The liquid sodium silicate is preferably mixed in an amount of 0.01 to 1 part by weight with respect to 100 parts by weight of the total content of the SiC powder and the B ₄ C powder. If it is less than 0.01 part by weight, the effect of improving the fluidity of the granular powder is weak and the sintering temperature The effect of lowering may also be weak, and when it exceeds 1 part by weight, thermal conductivity and mechanical properties may be deteriorated.

Liquid sodium silicate, called water glass, is a transparent solution showing viscous alkalinity, and liquid sodium silicate is a molar ratio of R ₂ O (where R is one or more substances selected from the group consisting of Li, Na and K) and SiO ₂ Therefore, it can have various compositions.

The liquid sodium silicate may include Li ₂ O·mSiO ₂ ·nH ₂ O (where m is 1 to 5 and n is 1 to 10).

The liquid sodium silicate may include Na ₂ O·mSiO ₂ ·nH ₂ O (where m is 1 to 5 and n is 1 to 10).

The liquid sodium silicate may include K ₂ O·mSiO ₂ ·nH ₂ O (where m is 1-5 and n is 0.1-10).

The liquid sodium silicate is Li ₂ O·mSiO ₂ ·nH ₂ O (where m is 1-5, n is 1-10), Na ₂ O·mSiO ₂ ·nH ₂ O (where m is 1-5, n is 1 to 10) and K ₂ O·mSiO ₂ ·nH ₂ O (where m is 1 to 5 and n is 0.1 to 10).

The mixing may use ball milling, attrition milling, or the like.

Hereinafter, the ball milling process will be described as an example.

The starting material is charged to a ball milling machine together with a solvent such as water or ethanol. It is mixed mechanically by rotating at a constant speed using a ball mill. The ball used for the ball milling is preferably a ceramic ball, such as alumina, zirconia, SiC, and more preferably, a SiC ball is used to suppress the content of impurities in the composite, and the balls are all It may be of the same size, or balls of two or more sizes may be used together. Adjust the ball size, milling time, and rotational speed of the ball mill per minute. For example, the size of the ball can be set in the range of about 1 mm to 50 mm, and the rotation speed of the ball mill can be set in the range of about 50 to 500 rpm. Ball milling is preferably performed for 10 minutes to 48 hours for uniform mixing and the like. The starting material that has been subjected to the wet mixing process as described above is micronized to form a slurry.

The starting material in a slurry state is spray dried to obtain granular powder. The spray drying is preferably set to a slurry input speed of 1 to 100 ml/min, an inlet temperature of 85 to 270°C, an outlet temperature of 60 to 120°C, and a rotation speed of about 6000 to 15000 rpm. The spray drying is generally well known, so detailed description thereof is omitted here.

It is mounted in a chamber 100 that provides a reaction space for plasma treatment, and a mold for molding into a shape of a part that comes into contact with plasma or a shape of the inner wall 102 of the chamber is prepared. The part may be a susceptor, showerhead or edge ring.

The granulated powder is put in the mold, charged into a furnace, and the temperature of the furnace is raised and sintered while applying pressure to the granulated powder. The sintering may use a method such as hot press sintering.

Hereinafter, hot pressing sintering will be described as an example.

The hot pressing sintering is a method of sintering while applying high pressure, and sintering is possible even at a lower temperature than normal pressure sintering, and the sintering time is shortened. The silicon carbide-based composite (sintered body) sintered by normal pressure sintering has a disadvantage in that its relative density is low and its mechanical properties are inferior to that of hot pressing sintering. In addition, when using atmospheric pressure sintering, sintering is required by raising the temperature to the vicinity of the melting points of SiC and B ₄ C, which results in high energy consumption and excessive thermal stress on the sintered specimen.

Therefore, in the present invention, by using hot pressing sintering, the gap between the particles becomes very dense, so that a high-density silicon carbide-based composite with little pores can be produced.

Hereinafter, a method of forming a silicon carbide-based composite (sintered body) using hot pressing sintering will be described.

The granulated powder is put in a mold, and the mold containing the granulated powder is charged into a furnace. The mold may be a mold for molding into a shape of a component mounted in the chamber 100 and in contact with the plasma, or a mold for molding into the shape of the inner wall 102 of the chamber.

After loading the granulated powder in the mold, it may be molded by performing one-way compression or the like on the mold top. At this time, the pressure applied to the granulated powder (the pressure compressed by the mold) is preferably about 10 to 60 MPa. When the pressure is too small, there are many voids between the granulated powder particles, so that the desired high density silicon carbide-based composite If it is difficult to obtain and the pressure is too large, further effects cannot be expected, and the design cost of the mold and the hydraulic device according to the high pressure may be added, thereby increasing the cost of manufacturing equipment. The mold is preferably made of a graphite material having a high hardness and a high melting point.

To remove and purge the impurity gas present in the furnace, the rotary pump is operated and exhausted until it becomes a vacuum (for example, about 1×10 ^{1 to} 1×10 ^-3 Torr). At this time, when power is supplied to the heating means surrounding the furnace to heat the furnace, the impurity gas remaining in the furnace can be efficiently exhausted.

The temperature of the furnace is raised to the target sintering temperature (for example, 1750 to 2100°C). At this time, in order to stabilize the atmosphere during sintering, nitrogen (N ₂ ) and argon (Ar) are supplied with an inert gas, and the gas atmosphere of the furnace is sufficiently supplied with an inert gas atmosphere, for example, at a flow rate of about 200 to 2000 sccm. It is preferred to supply an inert gas.

The sintering temperature is preferably about 1750 to 2100°C in consideration of diffusion of particles, necking between particles, etc. When the sintering temperature is too high, mechanical properties may deteriorate due to excessive particle growth, When the sintering temperature is too low, it is preferable to sinter at the sintering temperature in the above range because the properties of the sintered body may be poor due to incomplete sintering. At this time, the heating rate of the furnace is preferably about 1 ~ 50 ℃ / min, if the heating rate of the furnace is too slow, it takes a long time and productivity decreases. It is preferable to increase the temperature of the furnace at a heating rate in the above range because it may adversely affect the properties of.

When the temperature of the furnace rises to the target sintering temperature, it is sintered by maintaining a certain time (for example, 10 minutes to 6 hours). There is a difference in the microstructure of the sintered body depending on the sintering temperature, since the surface diffusion is dominant when the sintering temperature is low, but the lattice diffusion and grain boundary diffusion proceed when the sintering temperature is high. When using a furnace for general heat treatment, the sintering time is preferably about 10 minutes to 6 hours. When the sintering time is too long, energy consumption is high, so it is not only economical, but it is difficult to expect further sintering effects. The size of the sintered body becomes large, and when the sintering time is small, the characteristics of the sintered body may be poor due to incomplete sintering. When sintering, the pressure applied to the granulated powder is preferably about 10 to 60 MPa. When the pressure is too small, it is difficult to obtain a desired high density silicon carbide composite, and when the pressure is too large, cracks in the sintered body after the sintering process is completed. Back may occur.

After performing the sintering process, the furnace temperature is lowered to unload the inner wall of a component or chamber made of a silicon carbide-based composite (sintered body). The furnace cooling may be performed by shutting down the furnace power supply to cool it in a natural state, or by setting a temperature drop rate (for example, 10°C/min) to be cooled. It is preferable to keep the pressure inside the furnace constant while the furnace temperature is lowered.

A component mounted in the chamber 100 and contacting the plasma or the inner wall 102 of the chamber is made of a plasma-resistant silicon carbide-based composite. The component may be a susceptor 110, a shower head 120, or an edge ring 130.

The silicon carbide-based composite, as a SiC-B ₄ C-based composite, includes a SiC crystal phase and a B ₄ C crystal phase, has a relative density higher than 92%, and has a specific resistance lower than 30 Pa·cm. The silicon carbide-based composite may further include an Al ₂ O ₃ crystal phase. The silicon carbide-based composite may further include a Y ₂ O ₃ crystal phase. The silicon carbide-based composite may further include a YAG (Yttrium aluminum garnet, Y ₃ Al ₅ O ₁₂ ) crystal phase. The silicon carbide-based composite may exhibit a thermal conductivity higher than 50W/mK.

Hereinafter, experimental examples according to the present invention are specifically presented, and the present invention is not limited to the experimental examples presented below.

<Experimental Example 1>

As starting materials, SiC powder and B ₄ C powder were weighed at a weight ratio of 70:30, and mixed to prepare a slurry. As the SiC powder, a powder having an average particle diameter of 0.5 μm was used, and as the B ₄ C powder, a powder having an average particle diameter of 0.5 μm was used. The mixing was performed using a wet ball milling process. Specifically, ethanol was used as a solvent for 5 hours at a speed of 100 rpm using a SiC ball having a size of 5 mm for wet mixing.

The starting material in the slurry state was spray dried to obtain granular powder. During the spray drying, the slurry input speed was about 20 ml/min, the inlet temperature was 100° C., the outlet temperature was 70° C., and the rotation speed was 11000 rpm.

The granulated powder was placed in a cylinder-shaped mold, and the mold containing the granulated powder was charged to a furnace. As the mold, a mold made of graphite was used.

The rotary pump was purged to remove impurity gas present in the furnace. Power was supplied to a heating means surrounding the furnace to heat the furnace to increase the sintering temperature. At this time, the heating rate of the furnace was about 10℃/min from 1200℃ to 7℃/min from 1200℃ to 1800℃, and was about 3℃/min from 1800℃ to sintering temperature. During the heating process, a one-way pressure was applied at the top of the mold, and the pressure compressed by the mold was about 40 MPa. The sintering temperatures were set to 1900°C, 1950°C, and 2000°C, respectively.

After raising the temperature of the furnace to the sintering temperature, it was maintained for 1 hour to sinter. Even during sintering, the pressure applied to the granulated powder was kept constant at about 40 MPa. Fig. 3 shows a case where the sintering temperature is set to 2000°C, showing the temperature increase rate according to the time of hot pressing sintering, the holding time during sintering, and the pressure applied to the granulated powder.

After performing the sintering process, the furnace temperature was lowered to unload the silicon carbide-based composite (sintered body). The furnace cooling was performed by shutting off the furnace power so that the furnace was cooled in a natural state.

<Experimental Example 2>

As starting materials, SiC powder and B ₄ C powder were weighed in a weight ratio of 50:50 and mixed to make a slurry. As the SiC powder, a powder having an average particle diameter of 0.5 μm was used, and as the B ₄ C powder, a powder having an average particle diameter of 0.5 μm was used. The mixing was performed using a wet ball milling process. Specifically, ethanol was used as a solvent for 5 hours at a speed of 100 rpm using a SiC ball having a size of 5 mm for wet mixing.

The subsequent steps were performed in the same manner as in Experimental Example 1 to obtain a silicon carbide-based composite (sintered body).

<Experimental Example 3>

As starting materials, SiC powder and B ₄ C powder were weighed in a weight ratio of 30:70 and mixed to make a slurry. As the SiC powder, a powder having an average particle diameter of 0.5 μm was used, and as the B ₄ C powder, a powder having an average particle diameter of 0.5 μm was used. The mixing was performed using a wet ball milling process. Specifically, ethanol was used as a solvent for 5 hours at a speed of 100 rpm using a SiC ball having a size of 5 mm for wet mixing.

The subsequent steps were performed in the same manner as in Experimental Example 1 to obtain a silicon carbide-based composite (sintered body).

<Experimental Example 4>

Al(NO ₃ ) ₃ ·9H ₂ O (aluminium nitrate nonahydrate) as aluminum nitrate hydrate and Y(NO ₃ ) ₃ ·6H ₂ O (yttrium nitrate hexahydrate) as yttrium nitrate hydrate are prepared as additives, and Al(NO ₃ ) ₃ ·9H ₂ O and Y(NO ₃ ) ₃ ·6H ₂ O were mixed in a weight ratio of 62:38 and used as an additive.

SiC powder, B ₄ C powder, Al(NO ₃ ) ₃ · 9H ₂ O and Y(NO ₃ ) ₃ ·6H ₂ O were mixed as starting materials to prepare a slurry. The SiC powder and the B ₄ C powder were mixed in a weight ratio of 50:50. The Al(NO ₃ ) ₃ ·9H ₂ O and the Y(NO ₃ ) ₃ ·6H ₂ O were mixed in a weight ratio of 62:38. Additives (the Al(NO ₃ ) ₃ ·9H ₂ O and the Y(NO ₃ ) ₃ ·6H ₂ O) were mixed with 1 part by weight based on 100 parts by weight of the total content of the SiC powder and the B ₄ C powder. As the SiC powder, a powder having an average particle diameter of 0.5 μm was used, and as the B ₄ C powder, a powder having an average particle diameter of 0.5 μm was used. The mixing was performed using a wet ball milling process. Specifically, ethanol was used as a solvent for 5 hours at a speed of 100 rpm using a SiC ball having a size of 5 mm for wet mixing.

The starting material in the slurry state was spray dried to obtain granular powder. During the spray drying, the slurry injection rate was about 20 ml/min, the inlet temperature was 100°C, the outlet temperature was 70°C, and the rotational speed was 11000 rpm.

The granulated powder was placed in a cylinder-shaped mold, and the mold containing the granulated powder was charged to a furnace. As the mold, a mold made of graphite was used.

The rotary pump was purged to remove impurity gas present in the furnace. The furnace was heated to 1900°C by supplying power to a heating means surrounding the furnace. At this time, the heating rate of the furnace was about 10°C/min from 1200°C, about 7°C/min from 1200°C to 1800°C, and about 3°C/min from 1800°C to 1900°C. During the heating process, a one-way pressure was applied at the top of the mold, and the pressure compressed by the mold was about 40 MPa.

After the temperature of the furnace was raised to 1900°C, it was maintained for 1 hour to sinter. Even during sintering, the pressure applied to the granulated powder was kept constant at about 40 MPa.

After performing the sintering process, the furnace temperature was lowered to unload the silicon carbide-based composite (sintered body). The furnace cooling was performed by shutting off the furnace power so that the furnace was cooled in a natural state.

<Experimental Example 5>

Al(NO ₃ ) ₃ ·9H ₂ O (aluminium nitrate nonahydrate) as aluminum nitrate hydrate and Y(NO ₃ ) ₃ ·6H ₂ O (yttrium nitrate hexahydrate) as yttrium nitrate hydrate are prepared as additives, and Al(NO ₃ ) ₃ ·9H ₂ O and Y(NO ₃ ) ₃ ·6H ₂ O were mixed in a weight ratio of 62:38 and used as an additive.

SiC powder, B ₄ C powder, Al(NO ₃ ) ₃ · 9H ₂ O and Y(NO ₃ ) ₃ ·6H ₂ O were mixed as starting materials to prepare a slurry. The SiC powder and the B ₄ C powder were mixed in a weight ratio of 50:50. The Al(NO ₃ ) ₃ ·9H ₂ O and the Y(NO ₃ ) ₃ ·6H ₂ O were mixed in a weight ratio of 62:38. Additives (the Al(NO ₃ ) ₃ ·9H ₂ O and the Y(NO ₃ ) ₃ ·6H ₂ O) were mixed with 3 parts by weight based on 100 parts by weight of the total content of the SiC powder and the B ₄ C powder. As the SiC powder, a powder having an average particle diameter of 0.5 μm was used, and as the B ₄ C powder, a powder having an average particle diameter of 0.5 μm was used. The mixing was performed using a wet ball milling process. Specifically, ethanol was used as a solvent for 5 hours at a speed of 100 rpm using a SiC ball having a size of 5 mm for wet mixing.

The starting material in the slurry state was spray dried to obtain granular powder. During the spray drying, the slurry injection rate was about 20 ml/min, the inlet temperature was 100°C, the outlet temperature was 70°C, and the rotational speed was 11000 rpm.

The granulated powder was placed in a cylinder-shaped mold, and the mold containing the granulated powder was charged to a furnace. As the mold, a mold made of graphite was used.

The rotary pump was purged to remove impurity gas present in the furnace. The furnace was heated to 1850° C. by supplying power to a heating means surrounding the furnace. At this time, the heating rate of the furnace was about 10°C/min from 1200°C, about 7°C/min from 1200°C to 1800°C, and about 3°C/min from 1800°C to 1850°C. During the heating process, a one-way pressure was applied at the top of the mold, and the pressure compressed by the mold was about 40 MPa.

After the temperature of the furnace was raised to 1850°C, it was maintained for 1 hour to sinter. Even during sintering, the pressure applied to the granulated powder was kept constant at about 40 MPa.

After performing the sintering process, the furnace temperature was lowered to unload the silicon carbide-based composite (sintered body). The furnace cooling was performed by shutting off the furnace power so that the furnace was cooled in a natural state.

<Experimental Example 6>

Al(NO ₃ ) ₃ ·9H ₂ O (aluminium nitrate nonahydrate) as aluminum nitrate hydrate and Y(NO ₃ ) ₃ ·6H ₂ O (yttrium nitrate hexahydrate) as yttrium nitrate hydrate are prepared as additives, and Al(NO ₃ ) ₃ ·9H ₂ O and Y(NO ₃ ) ₃ ·6H ₂ O were mixed in a weight ratio of 62:38 and used as an additive.

SiC powder, B ₄ C powder, Al(NO ₃ ) ₃ · 9H ₂ O and Y(NO ₃ ) ₃ ·6H ₂ O were mixed as starting materials to prepare a slurry. The SiC powder and the B ₄ C powder were mixed in a weight ratio of 50:50. The Al(NO ₃ ) ₃ ·9H ₂ O and the Y(NO ₃ ) ₃ ·6H ₂ O were mixed in a weight ratio of 62:38. Additives (the Al(NO ₃ ) ₃ ·9H ₂ O and the Y(NO ₃ ) ₃ ·6H ₂ O) were mixed with 5 parts by weight based on 100 parts by weight of the total content of the SiC powder and the B ₄ C powder. As the SiC powder, a powder having an average particle diameter of 0.5 μm was used, and as the B ₄ C powder, a powder having an average particle diameter of 0.5 μm was used. The mixing was performed using a wet ball milling process. Specifically, ethanol was used as a solvent for 5 hours at a speed of 100 rpm using a SiC ball having a size of 5 mm for wet mixing.

The subsequent steps were performed in the same manner as in Experimental Example 5 to obtain a silicon carbide-based composite (sintered body).

<Experimental Example 7>

Al(NO ₃ ) ₃ ·9H ₂ O (aluminium nitrate nonahydrate) as aluminum nitrate hydrate and Y(NO ₃ ) ₃ ·6H ₂ O (yttrium nitrate hexahydrate) as yttrium nitrate hydrate are prepared as additives, and Al(NO ₃ ) ₃ ·9H ₂ O and Y(NO ₃ ) ₃ ·6H ₂ O were mixed in a weight ratio of 62:38 and used as an additive.

SiC powder, B ₄ C powder, Al(NO ₃ ) ₃ · 9H ₂ O and Y(NO ₃ ) ₃ ·6H ₂ O were mixed as starting materials to prepare a slurry. The SiC powder and the B ₄ C powder were mixed in a weight ratio of 50:50. The Al(NO ₃ ) ₃ ·9H ₂ O and the Y(NO ₃ ) ₃ ·6H ₂ O were mixed in a weight ratio of 62:38. Additives (the Al(NO ₃ ) ₃ ·9H ₂ O and the Y(NO ₃ ) ₃ ·6H ₂ O) were mixed with 7 parts by weight based on 100 parts by weight of the total content of the SiC powder and the B ₄ C powder. As the SiC powder, a powder having an average particle diameter of 0.5 μm was used, and as the B ₄ C powder, a powder having an average particle diameter of 0.5 μm was used. The mixing was performed using a wet ball milling process. Specifically, ethanol was used as a solvent for 5 hours at a speed of 100 rpm using a SiC ball having a size of 5 mm for wet mixing.

The subsequent steps were performed in the same manner as in Experimental Example 5 to obtain a silicon carbide-based composite (sintered body).

4 is a view showing an X-ray diffraction (XRD) pattern of a silicon carbide-based composite prepared by hot pressing sintering at 2000°C according to Experimental Examples 1 to 3.

Referring to FIG. 4, it was shown that SiC crystal phase and B ₄ C crystal phase coexist in a silicon carbide-based composite prepared by hot pressing sintering at 2000° C. according to Experimental Examples 1 to 3.

5 is a view showing the relative density of the silicon carbide-based composite prepared according to Experimental Examples 1 to 3, and FIG. 6 is a view showing the hardness of the silicon carbide-based composites prepared according to Experimental Examples 1 to 3 , Figure 7 is a view showing the strength of the silicon carbide-based composite prepared according to Experimental Examples 1 to 3. 5, 6 and 7 (a) is a silicon carbide-based composite prepared by mixing SiC powder and B ₄ C powder in a weight ratio of 70:30 according to Experimental Example 1, (b) is an experimental example According to 2, the SiC powder and the B ₄ C powder are mixed with a weight ratio of 50:50 to a silicon carbide-based composite, and (c) shows SiC powder and B ₄ C powder of 30:70 according to Experimental Example 3. It is for a silicon carbide-based composite prepared by mixing in a weight ratio.

5 to 7, it was found that as the sintering temperature increased, densification progressed and mechanical properties improved. It was found that at a sintering temperature of 2000°C, densification was achieved by more than 99.8% of the theoretical density. The strength of the silicon carbide-based composite prepared according to Experimental Example 2 (SiC powder and the silicon carbide-based composite prepared by mixing B ₄ C powder in a weight ratio of 50:50) was found to be the most excellent at about 645 MPa. All of the silicon carbide-based composites prepared according to Experimental Examples 1 to 3 under the conditions of sintering temperature of 2000°C showed hardness of 30 GPa or more.

FIG. 8 is a scanning electron microscope (SEM) photograph of a silicon carbide-based composite prepared by mixing SiC powder and B ₄ C powder in a weight ratio of 70:30 according to Experimental Example 1 and hot pressing sintering at 2000°C. , FIG. 9 is a kettle microscope (SEM) photograph of a silicon carbide-based composite prepared by mixing SiC powder and B ₄ C powder in a weight ratio of 50:50 according to Experimental Example 2 and hot pressing and sintering at 2000°C. This is a scanning electron microscope (SEM) photograph of a silicon carbide-based composite prepared by mixing SiC powder and B ₄ C powder in a weight ratio of 30:70 according to Experimental Example 3 and hot pressing sintering at 2000°C.

8 to 10, as the B ₄ C content increased, the SiC grains were fine, but the B ₄ C grain size increased.

11 is a view showing the thermal conductivity of the silicon carbide-based composite prepared according to Experimental Example 1 to Experimental Example 3. In Figure 11 (a) is a silicon carbide-based composite prepared by mixing the SiC powder and B ₄ C powder according to Experimental Example 1 in a weight ratio of 70:30, (b) is SiC powder and according to Experimental Example 2 B ₄ C powder is a silicon carbide-based composite prepared by mixing in a weight ratio of 50: 50, (c) is prepared by mixing SiC powder and B ₄ C powder in a weight ratio of 30: 70 according to Experimental Example 1 It relates to a silicon carbide-based composite.

Referring to FIG. 11, it was found that as the B ₄ C content increased, thermal conductivity and specific resistance decreased. The silicon carbide-based composite prepared according to Experimental Example 1 (SiC powder and B ₄ C powder is a silicon carbide-based composite prepared by mixing in a weight ratio of 70:30) had the highest thermal conductivity, and the silicone prepared according to Experimental Example 3 The carbide-based composite (silicon carbide-based composite prepared by mixing SiC powder and B ₄ C powder in a weight ratio of 30:70) showed the lowest thermal conductivity.

The silicon carbide-based composite prepared according to Experimental Example 1 (SiC powder and B ₄ C powder mixed at a weight ratio of 70:30 and hot pressed and sintered at 2000°C) had a specific resistance of about 24.1 mm 2 ·cm. Although it was shown, the silicon carbide-based composite prepared according to Experimental Example 2 (SiC powder and B ₄ C powder mixed in a weight ratio of 50:50 and hot pressed and sintered at 2000°C) was 10.4Ω It exhibited a specific resistance of about cm.

The relative density, the bending strength, the thermal conductivity and the specific resistance of the silicon carbide-based composites prepared according to Experimental Examples 2 and 4 to Experimental Example 7 were measured and are shown in Table 1 below.

Additive content
(Parts by weight) Sintering temperature
(℃) Relative density
(%) Bending strength
(MPa) Thermal conductivity
(W/mK) Resistivity
(Ω·㎝) Experimental Example 2 0 2000 99.8 645 67 10.4 Experimental Example 4 One 1900 99.7 634 87 7.9 Experimental Example 5 3 1850 99.8 620 101 4.8 Experimental Example 6 5 1850 99.9 596 118 4.3 Experimental Example 7 7 1850 99.9 573 123 4.5

Referring to Table 1, the silicon carbide-based composites prepared by mixing additives (Al(NO ₃ ) ₃ · 9H ₂ O and Y(NO ₃ ) ₃ · 6H ₂ O) according to Experimental Examples 5 to 7 are sintered. The densification was judged to be complete even at a temperature of 1850°C, but it was found that the bending strength was partially reduced.

As the content of additives (Al(NO ₃ ) ₃ ·9H ₂ O and Y(NO ₃ ) ₃ ·6H ₂ O) increased, the specific resistance decreased slightly and the thermal conductivity improved significantly.

The specific resistance of each silicon carbide-based composite prepared according to Experimental Example 1 and Experimental Example 5 was measured and is shown in Table 2 below. As shown in FIG. 12, the silicon carbide-based composite (measurement specimen) was targeted for a plate-type specimen having a width of 380 mm and a height of 380 mm, and using the MCA T7000 equipment, 10 points (front (F) 5 point) , (B) 5 points) were selected and specific resistivity was measured, and the average values are shown in Tables 2 to 4. Table 3 shows the specific resistivity for each part of the silicon carbide-based composite prepared according to Experimental Example 5, and Table 4 shows the specific resistivity for each part of the silicon carbide-based composite prepared according to Experimental Example 1.

density measuring equipment Measurement site Specific resistance (Ω·㎝) Remark range Average Experimental Example 5 2.809 MCA
T7000 10 Point 4.00×10 ⁰ ∼6.33×10 ⁰ 4.87×10 ⁰ 4.8 Ω·㎝ Experimental Example 1 2.950 2.00×10 ¹ ∼3.17×10 ¹ 2.41×10 ¹ 24.1 Ω·㎝

Item location No Specific resistance (Ω·cm) Remark Primary Secondary 3rd Average Experimental Example 5 Front (F) One 4.63 * 10 ⁰ 3.90 * 10 ⁰ 4.40 * 10 ⁰ 4.31 * 10 ⁰ 4.84 * 10 ⁰ 2 5.21 * 10 ⁰ 6.60 * 10 ⁰ 4.90 * 10 ⁰ 5.57 * 10 ⁰ 3 4.80 * 10 ⁰ 4.89 * 10 ⁰ 4.30 * 10 ⁰ 4.66 * 10 ⁰ 4 6.15 * 10 ⁰ 6.15 * 10 ⁰ 6.69 * 10 ⁰ 6.33 * 10 ⁰ 5 2.00 * 10 ⁰ 3.90 * 10 ⁰ 4.20 * 10 ⁰ 3.36 * 10 ⁰ Back (B) 6 6.69 * 10 ⁰ 3.00 * 10 ⁰ 5.93 * 10 ⁰ 5.20 * 10 ⁰ 4.90 * 10 ⁰ 7 4.71 * 10 ⁰ 2.00 * 10 ⁰ 4.85 * 10 ⁰ 3.85 * 10 ⁰ 8 4.00 * 10 ⁰ 6.20 * 10 ⁰ 6.55 * 10 ⁰ 5.58 * 10 ⁰ 9 3.90 * 10 ⁰ 9.00 * 10 ⁰ 4.67 * 10 ⁰ 5.85 * 10 ⁰ 10 3.80 * 10 ⁰ 4.20 * 10 ⁰ 4.00 * 10 ⁰ 4.00 * 10 ⁰

Item location No Specific resistance (Ω·cm) Remark Primary Secondary 3rd Average Experimental Example 1 Front (F) One 1.86 * 10 ¹ 3.22 * 10 ¹ 1.71 * 10 ¹ 2.26 * 10 ¹ 2.44* 10 ¹ 2 3.5 * 10 ¹ 3.80 * 10 ¹ 2.21 * 10 ¹ 3.17 * 10 ¹ 3 2.58 * 10 ¹ 2.35 * 10 ¹ 2.34 * 10 ¹ 2.42 * 10 ¹ 4 3.16 * 10 ¹ 1.64 * 10 ¹ 1.66 * 10 ¹ 2.15 * 10 ¹ 5 1.76 * 10 ¹ 1.74 * 10 ¹ 3.04 * 10 ¹ 2.18 * 10 ¹ Back (B) 6 1.88 * 10 ¹ 2.02 * 10 ¹ 2.1 * 10 ¹ 2.00 * 10 ¹ 2.38 * 10 ¹ 7 2.14 * 10 ¹ 2.12 * 10 ¹ 2.07 * 10 ¹ 2.11 * 10 ¹ 8 1.09 * 10 ¹ 1.85* 10 ¹ 5.19 * 10 ¹ 2.71 * 10 ¹ 9 2.7 * 10 ¹ 2.86 * 10 ¹ 3.18 * 10 ¹ 2.91 * 10 ¹ 10 1.76 * 10 ¹ 2.26 * 10 ¹ 2.45 * 10 ¹ 2.16 * 10 ¹

Referring to Table 3 to Table 5, the specific resistance measurement results for each position of the silicon carbide-based composite (measurement specimen) prepared according to Experimental Example 1 and Experimental Example 5 showed uniform measurement results.

As described above, the preferred embodiment of the present invention has been described in detail, but the present invention is not limited to the above embodiment, and various modifications can be made by those skilled in the art.

Claims (20)

A chamber providing a reaction space for plasma treatment; And
It includes a component mounted in the chamber and in contact with the plasma,
The part or the inner wall of the chamber is made of a plasma-resistant silicon carbide-based composite,
In the silicon carbide-based composite, SiC and B ₄ C form a weight ratio of 50:50 to 90:10,
The silicon carbide-based composite includes a SiC crystal phase and a B ₄ C crystal phase, and exhibits a relative density higher than 92% and has a specific resistance lower than 30 Pa·cm.
The plasma processing apparatus of claim 1, wherein the component is a susceptor, a shower head, or an edge ring.
The plasma processing apparatus of claim 1, wherein the silicon carbide-based composite further comprises an Al ₂ O ₃ crystal phase.
The plasma processing apparatus of claim 1, wherein the silicon carbide-based composite further comprises a Y ₂ O ₃ crystal phase.
The plasma processing apparatus of claim 1, wherein the silicon carbide-based composite further comprises a YAG (Yttrium aluminum garnet, Y ₃ Al ₅ O ₁₂ ) crystal phase.
The plasma processing apparatus of claim 1, wherein the silicon carbide-based composite exhibits a thermal conductivity higher than 50 W/mK.
delete In the method of manufacturing a plasma processing apparatus including a chamber for providing a reaction space for plasma processing, and a component mounted in the chamber and in contact with the plasma,
Preparing and mixing SiC powder and B ₄ C powder as starting materials to make a slurry;
Spray drying the starting material in a slurry state to obtain granulated powder;
Preparing a mold mounted in a chamber providing a reaction space for plasma treatment to form a part in contact with the plasma or to form a shape of the inner wall of the chamber;
Loading the granulated powder into the mold and loading it into a furnace;
Sintering while raising the temperature of the furnace and applying pressure to the granulated powder; And
Cooling the furnace to obtain the inner wall of the component or the chamber made of a plasma-resistant silicon carbide-based composite,
The SiC powder and the B ₄ C powder are mixed in a weight ratio of 50:50 to 90:10,
The silicon carbide-based composite includes a SiC crystal phase and a B ₄ C crystal phase, and has a relative density higher than 92% and has a specific resistance lower than 30 Pa·cm.
In the method of manufacturing a plasma processing apparatus including a chamber for providing a reaction space for plasma processing, and a component mounted in the chamber and in contact with the plasma,
Preparing and mixing SiC powder and B ₄ C powder as starting materials to make a slurry;
Spray drying the starting material in a slurry state to obtain granulated powder;
Preparing a mold mounted in a chamber providing a reaction space for plasma treatment to form a part in contact with the plasma or to form a shape of the inner wall of the chamber;
Loading the granulated powder into the mold and loading it into a furnace;
Sintering while raising the temperature of the furnace and applying pressure to the granulated powder; And
Cooling the furnace to obtain the inner wall of the component or the chamber made of a plasma-resistant silicon carbide-based composite,
The silicon carbide-based composite includes a SiC crystal phase and a B ₄ C crystal phase, has a relative density higher than 92%, and has a specific resistance lower than 30 Pa·cm,
The starting material further comprises aluminum nitrate hydrate,
The aluminum nitrate hydrate is a method of manufacturing a plasma processing apparatus characterized in that the mixing of 0.1 to 10 parts by weight based on 100 parts by weight of the total content of the SiC powder and the B ₄ C powder.
In the method of manufacturing a plasma processing apparatus including a chamber for providing a reaction space for plasma processing, and a component mounted in the chamber and in contact with the plasma,
Preparing and mixing SiC powder and B ₄ C powder as starting materials to make a slurry;
Spray drying the starting material in a slurry state to obtain granulated powder;
Preparing a mold mounted in a chamber that provides a reaction space for plasma treatment to form a part in contact with the plasma or to form a shape of the inner wall of the chamber;
Loading the granulated powder into the mold and loading it into a furnace;
Sintering while raising the temperature of the furnace and applying pressure to the granulated powder; And
Cooling the furnace to obtain the inner wall of the component or the chamber made of a plasma-resistant silicon carbide-based composite,
The silicon carbide-based composite includes a SiC crystal phase and a B ₄ C crystal phase, has a relative density higher than 92%, and has a specific resistance lower than 30 Pa·cm,
The starting material further comprises yttrium nitrate hydrate,
The yttrium nitrate hydrate is a method of manufacturing a plasma processing apparatus, characterized in that 0.1 to 10 parts by weight based on 100 parts by weight of the total content of the SiC powder and the B ₄ C powder.
In the method of manufacturing a plasma processing apparatus including a chamber for providing a reaction space for plasma processing, and a component mounted in the chamber and in contact with the plasma,
Preparing and mixing SiC powder and B ₄ C powder as starting materials to make a slurry;
Spray drying the starting material in a slurry state to obtain granulated powder;
Preparing a mold mounted in a chamber providing a reaction space for plasma treatment to form a part in contact with the plasma or to form a shape of the inner wall of the chamber;
Loading the granulated powder into the mold and loading it into a furnace;
Sintering while raising the temperature of the furnace and applying pressure to the granulated powder; And
Cooling the furnace to obtain the inner wall of the component or the chamber made of a plasma-resistant silicon carbide-based composite,
The silicon carbide-based composite includes a SiC crystal phase and a B ₄ C crystal phase, has a relative density higher than 92%, and has a specific resistance lower than 30 Pa·cm,
The starting material further includes aluminum nitrate hydrate and yttrium nitrate hydrate,
The aluminum nitrate hydrate and the yttrium nitrate hydrate is a method of manufacturing a plasma processing apparatus, characterized in that 0.1 to 10 parts by weight based on 100 parts by weight of the total content of the SiC powder and the B ₄ C powder.
In the method of manufacturing a plasma processing apparatus including a chamber for providing a reaction space for plasma processing, and a component mounted in the chamber and in contact with the plasma,
Preparing and mixing SiC powder and B ₄ C powder as starting materials to make a slurry;
Spray drying the starting material in a slurry state to obtain granulated powder;
Preparing a mold mounted in a chamber providing a reaction space for plasma treatment to form a part in contact with the plasma or to form a shape of the inner wall of the chamber;
Loading the granulated powder into the mold and loading it into a furnace;
Sintering while raising the temperature of the furnace and applying pressure to the granulated powder; And
Cooling the furnace to obtain the inner wall of the component or the chamber made of a plasma-resistant silicon carbide-based composite,
The silicon carbide-based composite includes a SiC crystal phase and a B ₄ C crystal phase, has a relative density higher than 92%, and has a specific resistance lower than 30 Pa·cm,
The starting material further includes Al(OH) ₃ powder,
The Al (OH) ₃ powder is a method of manufacturing a plasma processing apparatus characterized in that the mixing of 0.1 to 10 parts by weight based on 100 parts by weight of the total content of the SiC powder and the B ₄ C powder.
In the method of manufacturing a plasma processing apparatus including a chamber for providing a reaction space for plasma processing, and a component mounted in the chamber and in contact with the plasma,
Preparing and mixing SiC powder and B ₄ C powder as starting materials to make a slurry;
Spray drying the starting material in a slurry state to obtain granulated powder;
Preparing a mold mounted in a chamber that provides a reaction space for plasma treatment to form a part in contact with the plasma or to form a shape of the inner wall of the chamber;
Loading the granulated powder into the mold and loading it into a furnace;
Sintering while raising the temperature of the furnace and applying pressure to the granulated powder; And
Cooling the furnace to obtain the inner wall of the component or the chamber made of a plasma-resistant silicon carbide-based composite,
The silicon carbide-based composite includes a SiC crystal phase and a B ₄ C crystal phase, has a relative density higher than 92%, and has a specific resistance lower than 30 Pa·cm,
The starting material further includes Y ₂ O ₃ powder,
The Y ₂ O ₃ powder is 0.1 to 10 parts by weight based on the total content of the SiC powder and the B ₄ C powder 100 parts by weight of the plasma processing apparatus manufacturing method characterized in that.
In the method of manufacturing a plasma processing apparatus including a chamber for providing a reaction space for plasma processing, and a component mounted in the chamber and in contact with the plasma,
Preparing and mixing SiC powder and B ₄ C powder as starting materials to make a slurry;
Spray drying the starting material in a slurry state to obtain granulated powder;
Preparing a mold mounted in a chamber providing a reaction space for plasma treatment to form a part in contact with the plasma or to form a shape of the inner wall of the chamber;
Loading the granulated powder into the mold and loading it into a furnace;
Sintering while raising the temperature of the furnace and applying pressure to the granulated powder; And
Cooling the furnace to obtain the inner wall of the component or the chamber made of a plasma-resistant silicon carbide-based composite,
The silicon carbide-based composite includes a SiC crystal phase and a B ₄ C crystal phase, has a relative density higher than 92%, and has a specific resistance lower than 30 Pa·cm,
The starting raw material further comprises liquid sodium silicate (sodium silicate),
The liquid sodium silicate is a method of manufacturing a plasma processing apparatus characterized in that the mixing of 0.01 to 1 part by weight based on 100 parts by weight of the total content of the SiC powder and the B ₄ C powder.
delete In the method of manufacturing a plasma processing apparatus including a chamber for providing a reaction space for plasma processing, and a component mounted in the chamber and in contact with the plasma,
Preparing and mixing SiC powder and B ₄ C powder as starting materials to make a slurry;
Spray drying the starting material in a slurry state to obtain granulated powder;
Preparing a mold mounted in a chamber providing a reaction space for plasma treatment to form a part in contact with the plasma or to form a shape of the inner wall of the chamber;
Loading the granulated powder into the mold and loading it into a furnace;
Sintering while raising the temperature of the furnace and applying pressure to the granulated powder; And
Cooling the furnace to obtain the inner wall of the component or the chamber made of a plasma-resistant silicon carbide-based composite,
The silicon carbide-based composite includes a SiC crystal phase and a B ₄ C crystal phase, has a relative density higher than 92%, and has a specific resistance lower than 30 Pa·cm,
The sintering temperature is 1750 ~ 2100 ℃ range of the plasma processing apparatus manufacturing method characterized in that.
In the method of manufacturing a plasma processing apparatus including a chamber for providing a reaction space for plasma processing, and a component mounted in the chamber and in contact with the plasma,
Preparing and mixing SiC powder and B ₄ C powder as starting materials to make a slurry;
Spray drying the starting material in a slurry state to obtain granulated powder;
Preparing a mold mounted in a chamber that provides a reaction space for plasma treatment to form a part in contact with the plasma or to form a shape of the inner wall of the chamber;
Loading the granulated powder into the mold and loading it into a furnace;
Sintering while raising the temperature of the furnace and applying pressure to the granulated powder; And
Cooling the furnace to obtain the inner wall of the component or the chamber made of a plasma-resistant silicon carbide-based composite,
The silicon carbide-based composite includes a SiC crystal phase and a B ₄ C crystal phase, has a relative density higher than 92%, and has a specific resistance lower than 30 Pa·cm,
The pressure applied to the granular powder is a method of manufacturing a plasma processing apparatus, characterized in that in the range of 10 to 60MPa.
In the method of manufacturing a plasma processing apparatus including a chamber for providing a reaction space for plasma processing, and a component mounted in the chamber and in contact with the plasma,
Preparing and mixing SiC powder and B ₄ C powder as starting materials to make a slurry;
Spray drying the starting material in a slurry state to obtain granulated powder;
Preparing a mold mounted in a chamber that provides a reaction space for plasma treatment to form a part in contact with the plasma or to form a shape of the inner wall of the chamber;
Loading the granulated powder into the mold and loading it into a furnace;
Sintering while raising the temperature of the furnace and applying pressure to the granulated powder; And
And cooling the furnace to obtain the part made of a silicon carbide-based composite made of a plasma-resistant material or an inner wall of the chamber,
The silicon carbide-based composite includes a SiC crystal phase and a B ₄ C crystal phase, and has a relative density higher than 92% and a specific resistance lower than 30 Pa·cm,
The spray drying is a method of manufacturing a plasma processing apparatus characterized in that the inlet (Inlet) temperature of 85 to 270 ℃, the outlet (Outlet) temperature of 60 to 120 ℃, rotational speed of 6000 to 15000 rpm.
10. The method of claim 8, wherein the silicon carbide-based composite exhibits a thermal conductivity higher than 50 W/mK.
9. The method of claim 8, wherein the component is a susceptor, shower head or edge ring.

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