KR20180093814A - Plasma processing apparatus having boron carbide and method of manufacturing the apparatus - Google Patents

Abstract

Presented are a plasma treating apparatus including a boron carbide coating layer having excellent corrosion resistance on plasma, securing uniformity in plasma distribution, improving electrical conductivity and heat conductivity, and having a simple structure and a manufacturing method thereof. The apparatus and the method include a chamber forming a reactant space for plasma treatment and a component located in the chamber and contacting with plasma. The component has corrosion resistance and volume resistivity from 10^5 to 10^-5Ω·cm.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a plasma processing apparatus having boron carbide and a method of manufacturing the same,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasma processing apparatus and a manufacturing method thereof, and more particularly, to a plasma apparatus including a component made of boron carbide having high corrosion resistance to plasma and a manufacturing method thereof.

In the plasma processing apparatus, an upper electrode and a lower electrode are disposed in a chamber, and a substrate such as a semiconductor wafer or a glass substrate is mounted on the lower electrode, and electric power is applied between both electrodes. Electrons accelerated by an electric field between the electrodes, electrons emitted from the electrodes, or heated electrons collide with molecules of the process gas to generate a plasma of the process gas. Active species such as radicals and ions in the plasma are subjected to desired microfabrication, for example etching, on the substrate surface. 2. Description of the Related Art Recently, design rules for the production of microelectronic devices and the like are becoming finer and, in particular, plasma etching is required to have higher dimensional accuracy. In such a plasma processing apparatus, components such as an edge ring, a focus ring, and a shower head influenced by plasma are built in.

In the case of the above-mentioned edge ring, as the power increases, the central part becomes the maximum on the substrate and the edge part becomes the lowest by the wavelength effect where the standing wave is formed and the skin effect where the electric field concentrates on the central part on the electrode surface. The nonuniformity is increased. If the plasma distribution is uneven on the substrate, the plasma treatment is not constant and the quality of the fine electronic device is deteriorated. Korean Patent Laid-Open No. 2009-0101129 attempts to provide uniformity of plasma distribution by placing a dielectric between the susceptor and the edge portion. However, the above-mentioned patent has a complicated structure, and it is difficult to precisely design between the dielectric and the edge portion.

A problem to be solved by the present invention is to provide a plasma processing apparatus and a manufacturing method which have excellent corrosion resistance to plasma, ensure uniformity of plasma distribution, improve electric conductivity and thermal conductivity, and include boron carbide having a simple structure have.

A plasma processing apparatus including boron carbide to solve one problem of the present invention includes a chamber forming a reaction space for plasma processing and a part located inside the chamber and in contact with the plasma. At this time, the part is made of plasma corrosion resistant boron carbide, and the boron carbide has a volume resistivity of 10 ⁵ to 10 ^-5 Ω · cm.

In the apparatus of the present invention, the boron carbide is a boron and carbon based compound. The boron carbide may be single phase or complex phase. Said single phase may comprise a stoichiometric phase of boron and carbon and a non-stoichiometric phase deviating from said stoichiometric composition. The single phase or complex phase may include a solid solution added with impurities in the single phase or the composite phase. The part may be any one selected from an edge ring, a focus ring, or a showerhead. The part is an edge ring for pressing the edge of the substrate held in the susceptor, and the distribution of the plasma extends beyond the edge of the substrate.

In a preferred apparatus of the present invention, the part may be in the form of a sintered bulk and may be in a physical or chemical vapor deposited form. The part may be bonded to one side of the base material and include a boron carbide plate having a critical thickness of 0.3 mm. The part may include a boron carbide coating layer located on one side of the base material and having a critical thickness of 0.3 mm, and may include a boron carbide coating layer that seals the base material and has a critical thickness of 0.3 mm. The base material may be made of any one selected from metals, ceramics, and composites thereof.

According to another aspect of the present invention, there is provided a method of manufacturing a plasma processing apparatus including a boron carbide, the method including: forming a reaction space for plasma processing; In the manufacturing method, the part is a boron carbide having a plasma corrosion resistance and a volume specific resistance of 10 ⁵ to 10 ^-5 Ω · cm.

In the method of the present invention, the part can be produced by sintering and can be produced by physical or chemical vapor deposition. The part may be formed by bonding a boron carbide plate having a critical thickness of 0.3 mm to the base material. The boron carbide plate may be formed by machining a bulk boron carbide to a critical thickness of 0.3 mm. The bonding can be achieved by inducing diffusion at the interface by applying heat and pressure to the boron carbide and the base material, using a metal bonding agent, or applying a bonding tape. The part may be formed by forming a boron carbide coating layer having a critical thickness of 0.3 mm on the base material. The part may be formed by wrapping the base material with a boron carbide coating layer having a critical thickness of 0.3 mm. The boron carbide coating layer is preferably formed by a spraying method or a spraying method.

According to the plasma processing apparatus and the manufacturing method including the boron carbide of the present invention, by using a component including boron carbide which is excellent in plasma corrosion resistance and imparted with electrical conductivity, it is possible to provide a plasma processing apparatus that is excellent in corrosion resistance against plasma, And the structure is simple.

1 and 2 are views schematically showing a plasma processing apparatus equipped with a plasma part according to the present invention.
3 is a cross-sectional view showing a first part applied to the plasma apparatus according to the present invention.
4 is a cross-sectional view showing a second part applied to the plasma apparatus according to the present invention.
5 is a cross-sectional view showing a third part applied to the plasma apparatus according to the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The embodiments described below can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

An embodiment of the present invention proposes a plasma processing apparatus and a manufacturing method which are excellent in corrosion resistance against plasma, ensure uniformity of plasma distribution, and have a simple structure by using boron carbide. Such a plasma processing apparatus includes components such as an edge ring, a focus ring, and a shower head that are affected by a plasma. Here, an edge ring will be described as an example. To this end, a plasma component will be specifically described with reference to the edge ring of the present invention, and a method for manufacturing the plasma component will be described in detail.

1 and 2 are views schematically showing a plasma processing apparatus equipped with a plasma part according to an embodiment of the present invention. The present invention can be applied to a plasma processing apparatus having various structures in addition to the structure of the apparatus proposed within the scope of the present invention.

1 and 2, the treatment apparatus of the present invention comprises a chamber 10, a susceptor 20, a showerhead 30, and an edge ring 40. Here, the susceptor 20, the showerhead 30, the edge ring 40, and the like are the plasma components AP affected by the plasma. The chamber 10 defines a reaction space, and the susceptor 20 mounts the substrate 50 on its upper surface and moves up and down. In some cases, the susceptor 20 may be stationary and not move, but here, the case of vertically moving is taken as an example. The showerhead 30 is located above the susceptor 20 and injects the process gas into the substrate 50. The showerhead 30 is connected through a gas supply pipe 12 to the chamber 10 to introduce the process gas from the outside. The showerhead 30 has a buffer space 31 for uniformly diffusing the process gas introduced through the gas supply pipe 12 into the showerhead 30 before being injected into the showerhead 30 and a nozzle unit 32 composed of a number of through holes, . The edge ring 40 is mounted on the inner wall of the chamber 10 and is located above the ring support 41.

An RF power supply 16, which supplies RF power for generation of plasma, is connected to the plasma electrode or the antenna outside the chamber 10. As shown, a plasma electrode is integrally formed with the showerhead 30, and an RF power source 16 (not shown) is connected to the gas supply pipe 12 so that the RF power is applied to the center of the electrode. Can be connected. A separate RF power source is also applied to the susceptor 20 in order to control the energy of the plasma incident on the substrate 50. Although not shown, the susceptor 20 may include a heater for preheating or heating the substrate 50, a lift pin for mounting the substrate 50, and the like.

When the substrate 50 is placed on the susceptor 20, the susceptor 20 is raised to the position of the plasma treatment process. The edge ring 40 rises together while squeezing the edge of the substrate 50. Raising the susceptor 20 prevents the vent 14 from adversely affecting process uniformity. When the substrate 50 is in a process position, the process gas is injected through the showerhead 30, and RF power is applied to convert the process gas into a plasma reactive species having strong reactivity. The active paper substrate 50 may be subjected to a deposition process, an etching process, and the like, and the process gas may be discharged at a constant flow rate through the exhaust port 14 during the process. After the treatment process is performed for a predetermined period of time, the residual gas is discharged to the discharge port (14). Subsequently, the susceptor 20 is lowered and the substrate 50 is taken out from the chamber 10 to the outside.

The boron carbide used in the present invention is represented by B ₄ C and has the third highest strength following diamond and cubic boron nitride, and is excellent in chemical resistance and erosion resistance. On the other hand, the plasma corrosion resistance is influenced by the bonding force of the parts. That is, the stronger the bonding force, the higher the corrosion resistance, and the boron carbide has a high covalent bonding property, which is excellent in plasma corrosion resistance.

 In addition, other boron carbide compounds may be included within the scope of the present invention. That is, boron carbide refers to all compounds with boron and carbon as the base. The boron carbide of the present invention may be either a single phase or a composite phase. Here, the single boron carbide phase includes both the stoichiometric phase of boron and carbon and the non-stoichiometric phase deviating from the stoichiometric composition, and the complex phase includes boron and carbon in the base compound The boron carbide of the present invention is formed by adding impurities to a single phase or a composite phase of the boron carbide to form a solid solution or a boron carbide which is inevitably added in the process of producing boron carbide And the case where impurities are incorporated.

Hereinafter, the influence of plasma around the edge ring 40 among the plasma components AP will be examined. When the electric power for forming the plasma is increased, the central part of the substrate 50 becomes the maximum and the edge becomes the lowest by the wavelength effect in which the standing wave is formed in the chamber 10 and the skin effect where the electric field concentrates at the central part in the electrode surface. , The distribution of the plasma on the substrate 50 becomes uneven. If the plasma distribution on the substrate 50 is nonuniform, the plasma treatment is not constant and the quality of the fine electronic device is deteriorated. Herein, the plasma distribution refers to a state where plasma is applied on the substrate 50 and the boron carbide edge ring 40, and the distribution is the plasma density at each point of the substrate 50 and the boron carbide edge ring 40, And is related to the straightness toward the substrate 50.

The difference in volume resistivity with the boron carbide edge ring 40 at the edge ED of the substrate 50 greatly affects the plasma distribution uniformity. Here, the uniformity refers to the degree of change of the plasma distribution. If the uniformity is small, the plasma distribution abruptly changes, and if the uniformity is large, the plasma distribution changes slowly. For this purpose, it is preferable that the volume resistivity of the boron carbide edge ring 40 is similar to or lower than the volume resistivity of the substrate 50. In this way, the plasma distribution extends beyond the edge of the substrate 50 to the boron carbide edge ring 40, so that the edge of the substrate 50 has a relatively high uniformity. This uniformity means that the plasma density and the straightness toward the substrate 50 are excellent. In the drawing, the state of leaving the edge of the substrate 50 is represented by the edge ED.

The fact that the volume resistivity of the boron carbide edge ring 40 according to the embodiment of the present invention is similar to or smaller than the substrate 50 can be explained from the following viewpoints. If the volume resistivity of the boron carbide edge ring 40 is similar or smaller than the substrate 50, the plasma distribution extends beyond the edge of the substrate 50 to the boron carbide edge ring 40. The volume resistivity of the boron carbide edge ring 40 of the present invention extends from the edge of the substrate to the boron carbide edge ring 40 so that the plasma distribution over the entire substrate 50 is uniformly distributed to the edge of the substrate 50 . This volume resistivity can be defined as the expansion of the plasma distribution off the edge of the substrate 50 and the boron carbide edge ring 40.

The volumic resistivity 10 ⁵ to 10 ^-5 Ω · cm of the boron carbide edge ring 40 of the present invention is based on the technical idea for uniformizing the plasma distribution at the edge of the substrate 50. Accordingly, the volume resistivity can not be obtained through simple repetitive experiments without considering the technical idea. In the foregoing, the relationship between the volume resistivity of the boron carbide edge ring 40 and the substrate 50 has been described by taking the edge ring as an example. However, in the case of other parts such as a shower head, the volume resistivity of boron carbide is the same in terms of improving the plasma corrosion resistance.

Hereinafter, a method for manufacturing a plasma part AP including boron carbide (BC) will be described. The boron carbide plasma part (AP) is manufactured by sintering and physical or chemical vapor deposition, and is a first method in which it is itself a bulk type part, a second method of bonding to the base material, and a third method of coating the base material Lt; / RTI > Here, the bulk is separated from the coating layer of the third method which is coated on the surface of the base material. In addition, physical or chemical vapor deposition can be distinguished from other methods (e.g., sintering) by making boron carbide plasma parts (AP) utilizing the source material. The first to third methods presented here merely provide appropriate examples for each, and thus include other methods within the scope of the present invention.

<Boron carbide plasma part (AP) by sintering>

The sintering is performed by sintering the boron carbide powder or the boron-carbon mixed powder in a vacuum or an inert gas atmosphere. The inert gas may be any known inert gas, preferably argon, nitrogen, or the like. The boron carbide plasma component produced by sintering in this way is a sintered body in a bulk form.

<Boron Carbide Plasma Part (AP) by Physical or Chemical Vapor Deposition>

The chemical vapor deposition is a process in which a boron source and a carbon source are reacted and grown on a base material under a predetermined condition to grow the base material, and then the base material is removed. For example, B ₂ H ₆ as a boron precursor and CH ₄ as a carbon precursor can be deposited at a deposition temperature of 500 to 1500 ° C. by a chemical vapor deposition apparatus. In physical vapor deposition, the target is sputtered with boron carbide, and boron carbide is grown on the base material, and the base material is removed. The boron carbide parts produced by the physical or chemical vapor deposition are separated from the subsequent coating and are in a bulk form.

<Boron carbide plasma part (AP) by bonding>

The bonding is performed by bonding the boron carbide bulk of the above-described sintering or chemical vapor deposition to the base material, and the part AP is formed by polishing the boron carbide bulk into a plate having a thickness of 0.33 mm by polishing or the like. By the above processing, a boron carbide plate is formed. Although the bonding is not necessarily limited to this, it is possible to realize diffusion by inducing diffusion at the interface by applying pressure between the boron carbide and the base material at a temperature not higher than the melting point. The bonding may be performed by bonding a metal such as indium with a bonding agent, or by using other bonding tapes.

<Boron carbide plasma part (AP) by coating>

The plasma component AP by the coating can be variously modified. The plasma part produced by the coating can be considered as a modified example in which the plasma part AP described in Figs. 1 and 2 is modified. Accordingly, the plasma parts produced by the coating will be referred to as first to third parts AP1, AP2 and AP3. 3 is a cross-sectional view showing a first component AP1 applied to a plasma apparatus according to an embodiment of the present invention. Here, the plasma apparatus will be described with reference to FIGS. 1 and 2. FIG.

Referring to FIG. 3, the first component AP1 includes a base material 60 and a boron carbide coating layer 61 located on one side of the base material 60. As shown in FIG. The base material 60 is preferably a ceramic material that is corrosion resistant to plasma, but may be a metal or a combination thereof. This is because the base material 60 is located in an environment that is not affected by the plasma. The critical thickness of the boron carbide coating layer 61 of the present invention is a thick film of 0.3 mm. The coating of boron carbide to be specified in the present invention is composed of a corrosion resistant material only in the maximum thickness range in which the etching is allowed, rather than constituting the entirety of the base material 60 by a corrosion-resistant material. Through this, it is a coating which is carried out in order to reduce the manufacturing cost of the product and to facilitate the manufacturing process. That is, it is one of the examples of bonding two different bulk materials by coating method. As described above, the coating layer 61 having the maximum thickness range permitting etching is referred to as a thick film coating layer 61.

The retention plate 61 according to the embodiment of the present invention has a critical thickness. The reasons are as follows. First, when the edge ring 40 including the diaphragm 61 is first attached to the etching equipment, the surface of the diaphragm 61 is placed in line with the surface of the substrate 50. Substrate 50 is replaced for each subsequent etch process, but edge ring 40 remains the same. As such an etching process is repeated, a step is generated between the surface of the substrate 50 and the surface of the inner plate 61, and the step is continuously increased.

Second, the aspect ratio of the etch pattern has been increasing steadily as the device has been miniaturized. For etching corresponding to this aspect ratio, the plasma power must be increased. Plasma etching involves chemical etching by chemical reaction and physical etching by physical ion collision. However, as the plasma power increases, the intensity of the physical etching becomes relatively larger than the chemical etching, and becomes overwhelming at a predetermined power or higher. Therefore, it becomes more difficult to maintain the corrosion resistance of the plate 61.

Thirdly, when the step between the surface of the substrate 50 and the surface of the repellent plate 61 spreads beyond a predetermined thickness, the direction of the active ions pushed toward the edge of the substrate 50 is shifted from the direction perpendicular to the surface of the substrate 50 It gradually changes in an oblique direction. Etching patterns such as etching holes or trenches are also formed on the substrate 50 in the oblique direction by the etching ions in the oblique direction. Misalignment occurs in the oblique direction from the pattern of the underlying layer of the cornea, thereby reducing the yield of the device. Therefore, the minimum etch thickness limit to allow the misalignment to be tolerated and the minimum etch thickness limit to maintain the productivity of the device by etching the largest number of substrates 50 should be established.

Considering the reasons explained above, the thickness for general corrosion resistance should be 0.3mm or more. This thickness is called the critical thickness. Of course, the thickness of the plasma made of boron carbide bulk is usually within 3 mm, but more thickness can be applied if necessary. This is because the thickness of the plasma part AP requires a critical thickness which is the minimum thickness for corrosion resistance. The critical thickness is designed in consideration of the technical idea of the present invention, and can not be obtained by repeated experiments of the plasma part (AP).

The method of coating the boron carbide coating layer 61 with a thick film is not particularly limited and may be a chemical vapor deposition method, a physical vapor deposition method, a normal temperature spraying method, a low temperature spraying method, an aerosol spraying method, or a plasma spraying method. For example, B ₂ H ₆ may be used as a boron precursor, and the deposition temperature may be 500 to 1500 ° C., for example, using a chemical vapor deposition apparatus. In the physical vapor deposition method, for example, a boron carbide target can be sputtered in an argon (Ar) gas atmosphere. The coating layer 61 formed by the chemical vapor deposition method and the physical vapor deposition method can be referred to as a thick film CVD boron carbide coating layer 61 and a thick film PVD boron carbide coating layer 61, respectively.

In the normal-temperature spraying method, boron carbide powder is sprayed onto the base material 60 through a plurality of discharge ports at room temperature to form a boron carbide coating layer 61. At this time, the boron carbide powder may be in the form of a vacuum granule. In the low-temperature spray method, the boron carbide powder is sprayed onto the base material 60 through a plurality of discharge openings by the flow of the compressed gas at a temperature higher than about 60 ° C. than the normal temperature to form the boron carbide coating layer 61. In the aerosol spraying method, a boron carbide powder is mixed with a volatile solvent such as polyethylene glycol, isopropyl alcohol or the like to form an aerosol, and the aerosol is sprayed onto the base material 60 to form a boron carbide coating layer 61. In the plasma spraying method, a boron carbide powder is injected into a high-temperature plasma jet, and the powder melted in a plasma jet is sprayed onto the base material 60 at an ultra-high speed to form a boron carbide coating layer 61.

4 is a cross-sectional view showing a second component AP2 applied to a plasma apparatus according to an embodiment of the present invention. At this time, the second part AP2 is the same as the first part AP1, except that the shape of the boron carbide coating layer 62 covering the base material 60 is different. Here, the plasma apparatus will be described with reference to FIGS. 1 and 2, and the second component AP2 is one of the components affected by the plasma described above, such as an edge ring.

According to Fig. 4, the boron carbide coating layer 62 of the second component AP2 seals the base material 60. Fig. The sealing refers to plasma sealing in which the base material 60 covers the base material 60 to such an extent that the base material 60 can not be damaged by the plasma. For example, in the case where the base material 60 has a rectangular shape with an upper surface, a lower surface and a side surface, the upper surface is a plasma exposed surface that is directly exposed to plasma, the lower surface is a surface facing the upper surface, It can be regarded as a surface connecting the upper surface and the lower surface. The boron carbide coating layer 62 of the second component 4b covers the plasma exposed surface, the side surface, and the bottom surface. In this way, in the base material 60, a portion which can be damaged by the plasma is sealed. The base material 60 may be made of any one selected from metals, ceramics, and composites thereof.

On the other hand, if the base material 60 is sealed by the boron carbide coating layer 62, the base material 60 may not have plasma corrosion resistance. The base material 60 can be freely applied to a material having good electrical conductivity and thermal conductivity, for example, a metal material, irrespective of plasma corrosion resistance. Further, the base material 60 can be made of a material having a good shock absorbing property. For example, yttria that reacts with plasma to form solid state debris may be applied, and materials having good electrical conductivity and thermal conductivity such as aluminum or copper may be applied. Accordingly, in the case of a metal which is likely to be corroded by plasma, it can be employed as the base material 60 of the second component AP2 without being limited thereto. When the base material 60 is sealed with the boron carbide coating layer 62 as described above, the degree of freedom of selection of the base material 60 can be greatly increased as compared with the unsealed first part AP1.

5 is a cross-sectional view showing a third component AP3 applied to a plasma apparatus according to an embodiment of the present invention. The third part AP3 is the same as the first part AP1 and the second part AP2 except that the primer layer 63 is provided between the boron carbide coating layer 61 and the base material 60. [ Here, the plasma apparatus will be described with reference to FIGS. 1 and 2, and the third component AP3 is one of components affected by the plasma described above, such as an edge ring.

According to Fig. 5, the primer layer 63 of the third component AP3 enhances the bonding force between the boron carbide coating layer 61 and the base material 60. Fig. The primer layer 63 may be formed of a material containing tungsten, nickel, cobalt or the like in consideration of the relationship between the bonding strength between the boron carbide coating layer 61 and the base material 60. For example, the primer layer 63 is necessarily limited to this, but it may be a powder made of at least one selected from an alloy containing boron, a ceramic containing boron, and a mixture thereof and coated with the binder. The primer layer 63 is not limited thereto, but a material composed of at least one selected from an alloy including boron, a ceramic containing boron, and a mixture thereof may be a single layer or a multilayer.

As shown in the case of the first component AP1, the primer layer 63 exists between the base material 60 and the boron carbide coating layer 61. In the case of the second part AP2, the base material 60 and the boron carbide coating layer 61, (62). In this way, when the primer layer 63 is present, the bonding force between the boron carbide coating layers 61 and 62 and the base material 60 is increased so that the boron carbide coating layers 61 and 62 are not damaged by the impact caused by the plasma .

In order to explain the physical properties of the plasma part of the present invention in detail, the following embodiments are presented. However, the present invention is not particularly limited to the following examples. The electrical conductivity (? 占 ㎝ m) of the parts shown in Examples and Comparative Examples was measured with a model name LORESTA-GP MCP-T610 (manufactured by Mitsubishi) and the thermal conductivity ((W / m 占)) was model name LFA 467-TMA 402 F3 (Manufacturer, NETZSCH). The etch rate (%) was compared by changing the thickness after etching with CF ₄ gas plasma.

&Lt; Example 1 >

The sintered body having a thickness of? 50x10? Mm, which was prepared by sintering at a temperature of 2,200 占 폚 or more, was prepared by mixing a liquid phenolic resin with boron carbide powder in an amount of 0.1 to 60% by weight based on the weight of boron carbide. The electrical conductivity (Ω · cm) and the thermal conductivity ((W / m · k)) were measured by the apparatus described above and the relative density was measured.

&Lt; Comparative Example 1 &

Boron carbide was prepared in the same manner as in Example 1, and the electric conductivity (Ω · cm) and the thermal conductivity ((W / m · k)) of the liquid phenolic resin as the carbon supply source were increased to 40 wt% And relative density was measured.

&Lt; Comparative Example 2 &

The electric conductivity (Ω · cm) and the thermal conductivity ((W / m · k)) of the phenolic resin were measured by the above-described apparatus by mixing the phenol resin with 60% by weight with respect to the weight of boron carbide, Respectively.

Table 1 shows the electric conductivity (? And thermal conductivity (W / m? K) of Example 1 of the present invention and Comparative Examples 1 and 2. The electric conductivity (? 占 ㎝ m) and the thermal conductivity ((W / m · k) is an average value obtained by a plurality of measurements rather than a single measurement. For convenience, the electric conductivity is represented by a power of 10.

division Phenolic resin
Content (% by weight) Electrical conductivity
(Ω · cm) Thermal conductivity
(W / m? K) Relative density
(%) Etch rate
(%) Comparative Example 1 0.1 10 ^-1 22 63.8 76 Comparative Example 2 5.0 10 ^-1 23 65.3 75 Example 1 10 10 ^-1 27 77.4 71 Example 2 20 10 ^-1 29 85.0 68 Example 3 40 10 ⁰ 32 90.8 66 Example 4 60 10 ⁰ 32 98.0 57

Referring to Table 1, the electrical conductivity and the thermal conductivity of Examples 1 to 4 and Comparative Examples 1 and 2 were similar to each other, and there were no comparable elements. Specifically, the electrical conductivity of Example 1 was about 10 ^-1 , the thermal conductivity was 27, the electrical conductivities of Comparative Examples 1 and 2 were 10 ^-1 , and the thermal conductivity was 22. When the etching rate of Comparative Example 1 was 76%, the etching rates of Examples 1 to 4 of the present invention were 71%, 68%, 66%, and 57%, respectively. That is, it was confirmed that the etching rate is independent of the electric conductivity and the thermal conductivity, and is affected by the relative density. The relative density of the present invention was greater than 63% and less than 99%. As described above, the present invention improves the sintered compactness of boron carbide by adding phenol resin or the like, thereby realizing excellent corrosion resistance against plasma compared to conventional boron carbide. On the other hand, the difference in the etching rate becomes remarkable as the plasma power increases.

Although the embodiment of the present invention exemplifies phenol resin as a carbon source, since the carbon source is supplied as amorphous carbon by pyrolysis, other liquid or solid carbon sources besides the phenol resin within the scope of the present invention have the same technical idea . The difference in etch rate and relative density varies somewhat depending on the weight of the carbon source within the scope of the present invention.

Corrosion resistance of a component for a plasma device made of boron carbide according to an embodiment of the present invention increases as the relative density increases.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but many variations and modifications may be made without departing from the spirit and scope of the invention. It is possible.

10; Chamber 12; Gas supply pipe
20; A susceptor 30; Shower head
40; Edge ring 41; Ring support
50; A substrate 60; Base material
61, 62; Boron carbide coating layer
63; Primer layer AP; Plasma parts
AP1, AP2, AP3; The first to third plasma parts

Claims (22)

A chamber forming a reaction space for plasma processing:
And a component located within the chamber and in contact with the plasma,
Wherein the part is made of plasma corrosion resistant boron carbide, and the boron carbide has a volume resistivity of 10 ⁵ to 10 ^-5 Ω · cm. 2. The plasma processing apparatus according to claim 1, wherein the boron carbide is a compound based on boron and carbon. The plasma processing apparatus according to claim 1, wherein the boron carbide is a single phase or a composite phase. 4. The plasma processing apparatus of claim 3, wherein the single phase comprises a stoichiometric phase of boron and carbon and a non-stoichiometric phase out of the stoichiometric composition. 4. The plasma processing apparatus according to claim 3, wherein the single phase or the composite phase includes a solid solution added with an impurity in the single phase or the composite phase. The plasma processing apparatus according to claim 1, wherein the part is any one selected from the group consisting of an edge ring, a focus ring, and a showerhead. The plasma processing apparatus of claim 1, wherein the part is an edge ring for pressing the edge of the substrate held in the susceptor, and the distribution of the plasma extends beyond an edge of the substrate. The plasma processing apparatus according to claim 1, wherein the part is in the form of a sintered bulk. 2. The plasma processing apparatus of claim 1, wherein the part is in the form of a physical or chemical vapor deposited bulk. The plasma processing apparatus of claim 1, wherein the part comprises a boron carbide plate bonded to one side of the base material and having a critical thickness of 0.3 mm. The plasma processing apparatus of claim 1, wherein the part comprises a boron carbide coating layer located on one side of the base material and having a critical thickness of 0.3 mm. 2. The plasma processing apparatus of claim 1, wherein the part comprises a boron carbide coating layer having a critical thickness of 0.3 mm while sealing the base material. 13. The plasma processing apparatus according to any one of claims 11 to 12, wherein the base material is made of any one selected from the group consisting of metals, ceramics, and composites thereof. A chamber forming a reaction space for plasma processing:
The method comprising the steps of: (a)
Wherein the component is a boron carbide having a plasma resistivity and a volume specific resistance of 10 ⁵ to 10 ^-5 Ω · cm. 15. The method of claim 14, wherein the part is manufactured by sintering. 15. The method of claim 14, wherein the part is manufactured by physical or chemical vapor deposition. 15. The method of claim 14, wherein the part is formed by bonding a boron carbide plate having a critical thickness of 0.3 mm to the base material. 18. The method of claim 17, wherein the boron carbide plate is formed by processing a bulk boron carbide to a critical thickness of 0.3 mm. 18. The plasma processing apparatus according to claim 17, wherein the bonding is carried out by applying heat and pressure to the boron carbide and the base material to induce diffusion at the interface, bonding the bonding material with a metal bonding agent, or bonding the bonding material with a bonding tape. Gt; 15. The method according to claim 14, wherein the part is formed by forming a boron carbide coating layer having a critical thickness of 0.3 mm on a base material. 15. The method of claim 14, wherein the part is formed by wrapping a base material with a boron carbide coating layer having a critical thickness of 0.3 mm. The method according to any one of claims 20 and 21, wherein the boron carbide coating layer is formed by a spraying method or a spraying method.

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