KR102039798B1 - Method of manufacturing Parts for plasma processing apparatus having tungsten carbide - Google Patents

Abstract

The present invention provides a plasma device component and a method of manufacturing the same, which are made of tungsten carbide having excellent corrosion resistance to plasma, ensuring uniformity of plasma distribution, improving electrical conductivity and thermal conductivity, and having a simple structure. The parts and methods include a part located inside the chamber forming a reaction space for plasma treatment and in contact with the plasma, the part consisting of tungsten carbide bulk with plasma corrosion resistance, the tungsten carbide bulk having a volume resistivity 10 ³ ~. 10 ^{- 6} Ω · cm having the, grain size of the tungsten carbide grain size of the bulk has a corrosion resistance due to the carbon source in the liquid or solid phase in which the etching rate lower than the etching rate of the non-carbon source state.

Description

TECHNICAL FIELD The manufacturing method for plasma apparatus parts consisting of tungsten carbide

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a component for a plasma apparatus, and more particularly, to a method for manufacturing a component for a plasma apparatus comprising sintered bulk or sintered body bonding to tungsten carbide having high corrosion resistance to plasma.

The plasma processing apparatus arranges an upper electrode and a lower electrode in a chamber, mounts a substrate such as a semiconductor wafer or a glass substrate on the lower electrode, and applies electric power between both electrodes. Electrons accelerated by an electric field between the electrodes, electrons emitted from the electrodes, or heated electrons cause ionization collision with molecules of the processing gas, thereby generating a plasma of the processing gas. Active species such as radicals and ions in the plasma perform the desired microfabrication, for example etching, on the substrate surface. In recent years, design rules in the manufacture of microelectronic devices and the like have become increasingly finer, and in particular, plasma etch is required to have higher dimensional accuracy, and thus significantly higher power is used than in the prior art. The plasma processing apparatus includes components such as an edge ring, a focus ring, and a showerhead that are affected by plasma.

In the case of the edge ring, when the power is increased, the center part is maximized on the substrate and the edge part is the lowest on the substrate due to the wavelength effect in which standing waves are formed and the skin effect in which the electric field is concentrated at the center part of the electrode surface. Inhomogeneity deepens. If the plasma distribution is uneven on the substrate, the plasma processing becomes inconsistent and the quality of the microelectronic device is degraded. Korean Patent Publication No. 2009-0101129 seeks to achieve uniformity of plasma distribution by placing a dielectric between the susceptor and the edge portion. However, the patent has a problem in that the structure is complicated and precise design between the dielectric and the edge portion is difficult.

The problem to be solved by the present invention is to provide a method for manufacturing a component for a plasma device made of tungsten carbide excellent in corrosion resistance to the plasma, to ensure uniformity of the plasma distribution, improve the electrical conductivity and thermal conductivity, and simple structure have.

Plasma device components made of tungsten carbide for solving the problems of the present invention includes a chamber for forming a reaction space for plasma processing and a component located in the chamber and in contact with the plasma. In this case, the parts are made of a tungsten carbide bulk in the plasma corrosion resistance, the tungsten carbide bulk is the volume resistivity of 10 ³ to 10 ^- has a ⁶ Ω · cm, grain size of the tungsten carbide bulk etching without a carbon source state Corrosion resistance grain size by the liquid or solid carbon source is reduced compared to the rate.

In the part of the present invention, the corrosion resistance grain size is preferably 50 µm to 2,000 µm. The tungsten carbide bulk is a compound based on tungsten and carbon, and is a single phase or a complex phase, the single phase comprises a stoichiometric phase of tungsten and carbon and a nonstoichiometric phase outside of the stoichiometric composition, The single phase or complex phase includes a solid solution in which impurities are added to the single phase or complex phase.

In the part of the present invention, the liquid carbon source is a liquid hydrocarbon at room temperature, and is converted to amorphous carbon by pyrolysis. The liquid carbon source is a liquid thermoplastic resin at a temperature lower than the sintering temperature of the bulk, and is converted into amorphous carbon by pyrolysis. The liquid carbon source may be a phenol resin. The solid carbon source comprises carbon black.

In a preferred part of the invention, the bulk etch rate for the plasma is smaller as the grain size by the carbon source increases. The component can be any one selected from an edge ring, a focus ring or a showerhead. The component is an edge ring that squeezes the edge of the substrate seated in the susceptor, and the distribution of the plasma extends beyond the edge of the substrate. The part has a critical thickness of 0.3 mm. The component may include a tungsten carbide plate bonded to one surface of the base material and processed to bulk at a critical thickness of 0.3 mm.

In the method for manufacturing a plasma device part made of tungsten carbide for solving the problems of the present invention, first, a tungsten carbide powder is mixed with a liquid or solid carbon source to form a mixture. The mixture is then sintered in an atmosphere where the oxygen partial pressure is below atmospheric pressure to form a bulk. At this time, the tungsten carbide bulk is the volume resistivity of ^{10 3 ~ 10 - 6 Ω ·} cm to have the tungsten grain size of the carbide bulk carbon of liquid or solid in which the etching rate lower than the etching rate of the non-carbon source state Corrosion resistance grain size by source.

In the method of the present invention, in the sintering step, the carbon source removes tungsten oxide present on the surface of the tungsten carbide powder. The liquid carbon source is a liquid hydrocarbon at room temperature, and is converted to amorphous carbon by pyrolysis. The liquid carbon source is a liquid thermoplastic resin at a temperature lower than the sintering temperature of the bulk, and is converted into amorphous carbon by pyrolysis. The liquid carbon source is a phenol resin, and the phenol resin may include 0.1 to 0.8 wt% based on the tungsten carbide powder. The solid carbon source comprises carbon black.

In the method of the present invention, the bulk etch rate for the plasma decreases as the grain size by the carbon source increases.

According to the method of manufacturing a component for a plasma device made of tungsten carbide of the present invention, by using a liquid or solid carbon source to increase the size of the grains of tungsten carbide, it is excellent in corrosion resistance to plasma and uniformity of plasma distribution It is secured and the structure is simple.

1 and 2 are schematic views showing a plasma processing apparatus equipped with a plasma component according to the present invention.
3 is a cross-sectional view showing a first component applied to the plasma apparatus according to the present invention.
4 is a cross-sectional view showing a second component applied to the plasma apparatus according to the present invention.
5 is a cross-sectional view showing a third component applied to the plasma apparatus according to the present invention.
Figure 6 is an electron micrograph when the content of Example 3, Comparative Example 1 and the phenol resin of 1.0% of the invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. The embodiments described below may be modified in 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 more completely explain the present invention to those skilled in the art.

Embodiment of the present invention by producing a large grain size of tungsten carbide using a liquid or solid carbon source, excellent corrosion resistance to the plasma, ensures uniformity of the plasma distribution, simple components for the plasma device (Hereinafter, referred to as a plasma component) and a manufacturing method. Such a plasma processing apparatus includes components such as an edge ring, a focus ring, and a showerhead that are affected by plasma, and here, the edge ring will be described as an example. To this end, a plasma component will be described in detail with respect to the edge ring of the present invention, and a method of manufacturing the plasma component will be described in detail.

1 and 2 are diagrams schematically showing a plasma processing apparatus equipped with a plasma component according to an embodiment of the present invention. In addition to the structure of the apparatus presented within the scope of the present invention, it can be applied to the plasma processing apparatus of various structures.

1 and 2, the treatment apparatus of the present invention includes a chamber 10, a susceptor 20, a showerhead 30, and an edge ring 40. Here, the susceptor 20, the shower head 30, the edge ring 40, and the like are plasma components AP affected by the plasma. The chamber 10 defines a reaction space, and the susceptor 20 mounts the substrate 50 on the upper surface and moves up and down. In some cases, the susceptor 20 may be fixed and not move. Here, the vertical motion is taken as an example. The shower head 30 is positioned above the susceptor 20 and sprays a process gas onto the substrate 50. The shower head 30 has a gas supply pipe 12 connected through the chamber 10 to introduce the process gas from the outside. The shower head 30 includes a buffer space 31 for uniformly dispersing the inside of the shower head 30 before the process gas introduced through the gas supply pipe 12 is injected, and a nozzle part 32 composed of numerous through holes. It includes. The edge ring 40 is installed on the inner wall of the chamber 10 and is located on the ring support 41.

Outside the chamber 10, an RF power source 16 for supplying RF power for generating plasma is connected to a plasma electrode or an antenna. The connection scheme is various, and as shown, the plasma electrode is integrally formed with the shower head 30, and the RF power source 16 is provided to the gas supply pipe 12 so that the RF power is applied to the center of the electrode. ) Can be connected. In order to control energy of the plasma incident on the substrate 50, a separate RF power source may also be applied to the susceptor 20. 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 in the susceptor 20, the susceptor 20 is raised to the position of the plasma processing step. The edge ring 40 rises together while pressing the edges of the substrate 50. When the susceptor 20 is raised to place the substrate 50 in the process position, the process gas is injected through the shower head 30, and then RF power is applied to convert the process gas into plasma active species having strong reactivity. . The active paper may be deposited or etched on the substrate 50, 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 time, residual gas is discharged to the exhaust port 14. Subsequently, the susceptor 20 is lowered and the substrate 50 is carried out from the chamber 10 to the outside.

Tungsten carbide according to an embodiment of the present invention includes WC and W ₂ C. In addition to the above WC and W ₂ C, the tungsten carbide of the present invention may include other tungsten carbide compounds within the scope of the present invention. That is, tungsten carbide refers to all compounds based on tungsten and carbon. The tungsten carbide of the present invention may be either a single phase or a composite phase. Here, the tungsten carbide single phase includes both the stoichiometric phase of tungsten and carbon and the nonstoichiometric phase deviating from the stoichiometric composition, and the composite phase is, for example, based on the tungsten and carbon At least two of the tungsten carbide compounds referred to as ()) are mixed at a predetermined ratio. In addition, the tungsten carbide of the present invention includes all impurities such as impurities added to the single phase or composite phase of the tungsten carbide to form a solid solution or inevitably added in the process of manufacturing tungsten carbide.

Hereinafter, the influence of the plasma around the edge ring 40 in the plasma component AP will be described. When the power to form the plasma is high, the center of the substrate 50 is maximized and the edge is generally the lowest due to the wavelength effect in which standing waves are formed in the chamber 10 or the skin effect in which the electric field is concentrated at the center of the electrode surface. The plasma distribution on the substrate 50 becomes nonuniform. If the plasma distribution is uneven on the substrate 50, the plasma processing becomes inconsistent and the quality of the microelectronic device is degraded. Here, the plasma distribution refers to a state in which a plasma is applied on the substrate 50 and the tungsten carbide edge ring 40, and the distribution indicates a plasma density at each point of the substrate 50 and the tungsten carbide edge ring 40. It is associated with the straightness towards the substrate 50.

Near the edge of the substrate 50 (ED), the difference in volume resistivity with the tungsten carbide edge ring 40 has a great effect on the plasma distribution uniformity. Here, the uniformity refers to the degree of change in the plasma distribution. When the uniformity is small, the plasma distribution changes abruptly, and when the uniformity is large, the plasma distribution changes slowly. For this purpose, the volume resistivity of the tungsten carbide edge ring 40 is preferably similar or lower than the volume resistivity of the substrate 50. In this case, since the plasma distribution extends beyond the edge of the substrate 50 to the tungsten carbide edge ring 40, the edge of the substrate 50 has a relatively high uniformity. The uniformity means that the plasma density and the straightness toward the substrate 50 are excellent. In the drawing, the state that deviates from the edge of the substrate 50 is expressed as near edge ED.

The volume resistivity of the tungsten carbide edge ring 40 according to the embodiment of the present invention is similar to or smaller than the substrate 50 can be described in the following aspects. If the volume resistivity of the tungsten 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 tungsten carbide edge ring 40. Accordingly, the volume resistivity of the tungsten carbide edge ring 40 of the present invention extends from the edge of the substrate to the tungsten carbide edge ring 40 so that the plasma distribution over the entire substrate 50 is uniform even at the edge of the substrate 50. It can be said that. Such volume resistivity may be defined as extending the plasma distribution beyond the edge of the substrate 50 and extending the tungsten carbide edge ring 40.

Volume resistivity of 10 ³ to 10 tungsten carbide edge ring 40 of the present invention ^{- 6} Ω · cm is based on the technical idea for making uniform the plasma distribution in the edge of the substrate 50. Accordingly, the volume resistivity cannot be obtained through simple repeated experiments without considering the technical idea. In the above, the relationship between the volume resistivity of the tungsten carbide edge ring 40 and the substrate 50 has been described taking the edge ring as an example. However, in the case of other parts such as showerheads, the viewpoint that the volume resistivity of tungsten carbide improves the plasma corrosion resistance is the same.

On the other hand, plasma corrosion resistance is affected by the density (g / cm 3) of the part. In other words, as the density of the plasma component increases, the plasma corrosion resistance increases. The tungsten carbide (WC) of the present invention has a density of 15.63 (g / cm 3), which is 3.12 (g / cm 3) of silicon carbide (SiC) and 3.95 (g / cm ₃ ) of alumina (Al ₂ O ₃ ). More noticeably larger. As a result, the tungsten carbide of the present invention has higher corrosion resistance to plasma than conventional silicon carbide and alumina.

The plasma component AP including the edge ring 40 according to the embodiment of the present invention has a critical thickness. The reason is at least as follows. First, when the edge ring 40 is initially mounted on the etching equipment, the surface of the edge ring 40 is in line with the surface of the substrate 50. The substrate 50 is replaced for each subsequent etching process but the edge ring 40 remains the same. As the etching process is repeated, a step occurs between the surface of the substrate 50 and the surface of the edge ring 40 and the step continuously increases.

Second, as the pattern of the device becomes finer, the aspect ratio of the etching pattern continues to increase, and recently, it has almost reached its limit. For etching corresponding to this aspect ratio, the plasma power must be increased. In plasma etching, chemical etching by chemical reaction and physical etching by physical ion collision are mixed. However, as the plasma power increases, the strength of the physical etching becomes relatively larger than the chemical etching and becomes overwhelming at a predetermined power or more. Therefore, it becomes more difficult to maintain the corrosion resistance of the edge ring 40.

Third, when the level difference between the surface of the substrate 50 and the surface of the edge ring 40 extends beyond the predetermined thickness, the direction of active ions rushing to the edge of the substrate 50 is from the direction perpendicular to the surface of the substrate 50. Gradually the direction becomes oblique. By the diagonal etching ions, an etching pattern such as an etching hole or a trench is formed in the diagonal direction on the substrate 50. In the diagonal direction, misalignment occurs from the pattern of the underlying layer of the etching layer, thereby reducing the yield of the device. Therefore, the maximum etching thickness and the maximum number of substrates 50 that are the allowable misalignment should be etched to set the minimum etching thickness limit for maintaining the productivity of the equipment.

Considering the reasons mentioned above, the thickness for general corrosion resistance should be more than 0.3mm. This thickness is called the critical thickness. Of course, the thickness of the plasma component AP made of tungsten carbide is typically applied within a thickness of less than 3mm, but may be applied to more than the thickness if necessary. This is because the thickness of the plasma component AP requires only 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, which cannot be obtained by repeated experiments of the plasma component (AP).

Hereinafter, a method of manufacturing a sintered bulk including tungsten carbide (WC) and a plasma component AP of a sintered body joint will be described.

<Tungsten Carbide Plasma Component (AP) by Sintering>

The sintering is mixed with tungsten carbide powder in a liquid or solid carbon supply source and sintered in an atmosphere or reducing atmosphere where the oxygen partial pressure is lower than atmospheric pressure, such as vacuum or inert gas atmosphere. The inert gas may be any known inert gas, and preferably argon, nitrogen, and the like. The tungsten carbide plasma component produced by sintering in this way is a sintered body in bulk form. That is, the sintered bulk of the embodiment of the present invention refers to the bulk form of the plasma component itself without the involvement of the base material.

The liquid carbon source refers to a material that is liquid at the time of mixing with tungsten carbide powder but carbonizes at a temperature lower than the sintering temperature. The liquid phase may include an oil, and may be freely mixed with tungsten carbide powder, such as a liquid, having low viscosity. The liquid phase may be implemented at room temperature, or may be implemented at a temperature higher than the room temperature but lower than the sintering temperature.

The carbon source that is liquid at room temperature refers to a hydrocarbon, and includes a hydrocarbon in a chain and ring form. Hydrocarbons that are liquid at room temperature include paraffinic, olefinic, naphthenic and aromatic. For example, the paraffinic system has 5 or more carbon atoms. Among them, aromatic hydrocarbons that are stable carbon sources at the sintering temperature are preferable. Phenol resin is more preferable among the aromatic hydrocarbons. The phenol resin is an aromatic carbon compound in which a hydroxy group (-OH) is substituted in a benzene ring, and thus becomes a stable carbon source at the sintering temperature.

Preferably, the thermoplastic carbon is a carbon source that is liquid at a temperature higher than the normal temperature but lower than the sintering temperature. The thermoplastic resins include polyester, polylactic acid, polyethylene, polypropylene, polycarbonate, polymethylmethacrylate, polyvinylchloride, polyaramid, polyacrylonitrile, polyurethane, cellulose and the like. Such thermoplastic resin is mixed with tungsten carbide powder in the molten state. Accordingly, the temperature at which the tungsten carbide powder and the thermoplastic resin are mixed is higher than the melting point (Tm) of the thermoplastic resin.

Heating the carbon source undergoes pyrolysis to yield a carbon-rich material, ie amorphous carbon. For example, the carbonization temperature of the thermoplastic resin is lower than the sintering temperature, and depends on the type of the thermoplastic resin. For example, carbonization temperatures of 800 ° C to 1200 ° C for polyester, 400 ° C to 750 ° C for polyester, 1000 ° C to 1500 ° C for polyacrylonitrile, 600 ° C to 1000 ° C for polyurethane, and 1000 ° C to 3000 ° C for cellulose Has When the normal sintering temperature is about 2200 ° C, the carbon source is converted to amorphous carbon at 2200 ° C to become a carbon source.

The carbon may also be a solid carbon source. Solid carbon sources include carbon black. Of course, a liquid carbon source is more preferable in that the carbon source uniformly covers the surface of the tungsten carbide powder, but a solid carbon source may also contribute sufficiently to the improvement of corrosion resistance within the scope of the present invention.

When the liquid and solid carbon source is mixed with tungsten carbide powder, the carbon source covers the surface of the tungsten carbide powder, so that the carbon source can be distributed homogeneously with respect to the tungsten carbide powder. Carbon may be uniformly supplied to each of the tungsten carbide powders. This uniform supply of carbon may also directly supply solid carbon to the tungsten carbide powder surface using a powder mixing method. When the sintering by such a carbon supply is completed, the grain size of tungsten carbide can be made relatively large.

The reason why the grains are enlarged by the carbon uniformly supplied to the tungsten carbide surface is as follows. When sintering is performed only with tungsten carbide powder, tungsten oxide present as a natural oxide film on the surface of tungsten carbide interferes with grain growth. However, tungsten oxide on the surface is removed by uniformly distributed carbon supplied to the tungsten carbide surface during the sintering process, so that grain growth is smooth and large grains can be obtained. Tungsten carbide according to an embodiment of the present invention is larger than the grain size in the absence of a carbon source. The larger the size of the tungsten carbide grains, the greater the corrosion resistance of the components for plasma apparatus. This will be described in detail later through the embodiment.

On the other hand, when the carbon source is a phenol resin, it is preferably 0.1% or more and 0.8% or less by weight relative to the tungsten carbide powder. If it is less than 0.1%, the grain size is small and there is no improvement of plasma resistance. If it is more than 0.8%, the grain growth is overgrown or residual carbon is increased, which reduces the density of the product. Particularly, when the grain grows excessively, the grain is dropped when the component is processed, and the strength of the component is lowered. When the phenol resin is applied as a carbon source, the grain size is preferably 100 to 500 mu m.

The content of the carbon source is designed in consideration of the grain size, which is the technical idea of the present invention, which cannot be obtained by repeated experiments of the plasma component (AP). In addition, the carbonization temperature depends on the composition of the carbon supply source, the atmosphere gas, the temperature increase rate (° C./min), and the like. If necessary, the carbonization temperature can be adjusted in stages so that carbonization of the carbon source and sintering of tungsten carbide occur appropriately.

<Tungsten Carbide Plasma Component (AP) by Bonding>

Plasma component AP by the bonding of the embodiment of the present invention can be variously modified. The plasma component generated by the bonding can be seen as a modification of the plasma component AP described with reference to FIGS. 1 and 2. Accordingly, the plasma component manufactured by the bonding will be referred to as the first to third components AP1, AP2, and AP3. 3 is a cross-sectional view showing the first component AP1 applied to the plasma apparatus according to the embodiment of the present invention. In this case, the plasma apparatus will be described with reference to FIGS. 1 and 2.

According to FIG. 3, the first component AP1 includes a base material 60 and a tungsten carbide sintered plate 61 positioned on one surface of the base material 60. The base material 60 is preferably a ceramic material having corrosion resistance to the plasma, but may be a metal or a composite of metal and ceramic. This is because the base material 60 is located in an environment not affected by the plasma. The thickness of the sintered plate 61 of the present invention has a critical thickness of 0.3 mm described above. More preferably, it is a thick film of 0.3 mm-3 mm. Here, 0.3 mm is an essential requirement, but 3 mm is a thickness that can be appropriately modified by those skilled in the art.

The sintered plate 61 to be specified in the present invention is composed of a corrosion-resistant material only the maximum thickness range allowed for etching, rather than forming a plasma processing apparatus by configuring the entire base material 60 as a corrosion-resistant material. Through this, it is a method performed to reduce the manufacturing cost of the product and to facilitate the manufacturing process. As such, the sintered plate 61 having a thickness in the maximum range allowed for etching may be referred to as a thick film sintered plate 61. The tungsten carbide sintered plate 61 is formed by processing a tungsten carbide bulk in the form of a plate having a thickness of 0.3 mm to 3 mm by polishing or the like to bond tungsten carbide in the form of a plate made by sintering to the base material 60. By the above processing, the tungsten carbide sintered plate 61 is made.

The bonding may also be referred to as sintered body bonding, but is not necessarily limited thereto, and may be implemented by inducing diffusion at an interface by applying pressure between the sintered plate 61 and the base material 60 at a high temperature below the melting point.

4 is a cross-sectional view illustrating the second component AP2 applied to the plasma apparatus according to the embodiment of the present invention. In this case, the second component AP2 is the same as the first component AP1 except that the tungsten carbide sintered plate 62 is covered by the base material 60. In this case, 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 as described above.

According to FIG. 4, the tungsten carbide sintered plate 62 of the second component AP2 seals the base material 60. The sealing means plasma sealing that covers the base material 60 to such an extent that the base material 60 cannot be damaged by the plasma. For example, when the cross section of the base material 60 is a quadrangular shape having a top surface, a bottom surface and a side surface, the top surface is a plasma exposure surface directly exposed to plasma, and the bottom surface is a surface opposite to the top surface, and the side surface is It can be seen as a surface connecting the top and bottom surfaces. The sintered plate 62 of the second component 4b covers the plasma exposed surface, the side surface, and the bottom surface. This seals the portion of the base material 60 that may be damaged by the plasma. The base material 60 may be made of any one selected from metal, ceramic, or a composite thereof.

On the other hand, when the base material 60 is sealed by the sintered plate 62, the base material 60 does not need to have plasma corrosion resistance. The base material 60 may freely apply a material having good electrical conductivity and thermal conductivity, such as a metal material, regardless of plasma corrosion resistance. In addition, the base material 60 may be made of a material having good shock absorption. For example, yttria, which reacts with plasma to form solid residues, may be applied, or a material having good electrical and thermal conductivity such as aluminum or copper may be used. Accordingly, in the case of a metal which is likely to be corroded by the plasma, it can be used as the base material 60 of the second component AP2 without being limited thereto. Thus, when the base material 60 is sealed with the sintered board 62, the freedom degree of selection of the base material 60 can be improved significantly compared with the unsealed 1st component 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. In this case, the third part AP3 is the same as the first part AP1 and the second part AP2 except that the adhesive layer 63 is disposed between the tungsten carbide sintered plate 61 and the base material 60. In this case, the plasma apparatus will be described with reference to FIGS. 1 and 2, and the third component AP3 is one of the components affected by the plasma as described above, and includes an edge ring and the like.

Referring to FIG. 5, the adhesive layer 63 of the third component AP3 couples the tungsten carbide sintered plate 61 and the base material 60. The adhesive layer 63 is not necessarily limited thereto, but a metal such as indium may be bonded with a bonding agent, or other bonding tape may be used. In the case of the second part AP2, an adhesive layer 63 is present between the base material 60 and the sintered plate 61. As such, when the adhesive layer 63 is present, the bonding force between the sintered plates 61 and 62 and the base material 60 is increased, so that the tungsten carbide sintered plates 61 and 62 are not damaged by the impact of plasma.

Hereinafter, in order to explain in detail the physical properties of the plasma component of the present invention, the following examples are presented. However, the present invention is not particularly limited to the following examples. The electrical conductivity (Ω · cm) of the components shown in the examples and comparative examples was measured by the model name LORESTA-GP MCP-T610 (manufacturer, Mitsubish), and the thermal conductivity ((W / m · k) was the model name LFA 467-TMA 402 F3 In addition, the etching rate (%) was compared with the change in weight after etching with CF ₄ gas plasma.The size of the crystal grains was an average value, based on a large diameter.

<Examples 1 to 4>

The liquid phenolic resin was mixed with tungsten carbide powder by 0.1 wt%, 0.2 wt%, 0.4 wt% and 0.8 wt%, respectively, to prepare a sintered body having a thickness of 5 mm manufactured by sintering at 2,200 ° C. Electrical conductivity (Ω · cm) and thermal conductivity ((W / m · k) were measured by the apparatus presented above, and the grain size was presented.

Comparative Example 1

Tungsten carbide was prepared in the same manner as in Example 1 without supplying a liquid phenolic resin as a carbon source, and the electrical conductivity (Ω · cm) and thermal conductivity ((W / m · k) were measured by the above-mentioned apparatus, and the grain size Presented.

Comparative Example 2

The phenol resin was mixed 0.05% by weight with respect to the weight of tungsten carbide, and produced in the same manner as in Example 1, and the electrical conductivity (Ω · cm) and thermal conductivity ((W / m · k) were measured by the apparatus described above, and the grain size was measured. Presented.

Table 1 shows the electrical conductivity (Ω · cm) and the thermal conductivity ((W / m · k) of Examples 1 to 3 and Comparative Examples 1 and 2 of the present invention, wherein the electrical conductivity (Ω · cm) and thermal conductivity ((W / m · k) is an average value obtained by multiple measurements instead of one measurement, and the electrical conductivity is expressed as a square number of 10 for convenience. Is pointless.

division Phenolic resin
Content (% by weight) Electrical conductivity
(Ωcm) Thermal conductivity
(W / mk) Grain size
(Μm) Etching rate
(%) Example 1 0.1 10 ^-5 70 <100 94 Example 2 0.2 10 ^-5 85 <200 91 Example 3 0.4 10 ^-5 85 > 300 85 Example 4 0.8 10 ^-5 90 > 500 73 Comparative Example 1 0 10 ^-5 85 Not measurable 100 Comparative Example 2 0.05 10 ^-5 70 <35 99

Referring to Table 1, the electrical conductivity and the thermal conductivity of Examples 1 to 4 and Comparative Examples 1 to 2 are similar to each other, and there is no comparable element. Specifically, the embodiment electrical conductivity of 1 to 3 is 10 ^-5 or so, the thermal conductivity is 70 to 90, and comparing the electrical conductivity of Examples 1 and 2 from 10 ^-5, the thermal conductivity was 70 to 85. By the way, when the etching rate of Comparative Example 1 is 100%, the etching rates of Examples 1 to 4 of the present invention were 94%, 91%, 85% and 73%, respectively. In Comparative Example 2, the etching rate was 99%, and the improvement of the plasma resistance was insignificant. That is, it was confirmed that the etching rate is independent of the electrical conductivity and the thermal conductivity and is affected by the grain size. The grain size of the present invention was larger than 100 µm and smaller than 500 µm. As such, the tungsten carbide of the present invention controls the size of the crystal grains to implement excellent corrosion resistance against plasma compared to tungsten carbide. On the other hand, the difference in etching rate is remarkable as the plasma power increases.

In the embodiment of the present invention, a phenol resin is used as the carbon source, but the carbon source is supplied as amorphous carbon by pyrolysis, and thus, the same technical concept is applied to other liquid or solid carbon sources other than the phenol resin within the scope of the present invention. Apply. In connection with the etch rate, when the etch rate of tungsten carbide without a carbon source is 100%, as a result of confirming through a number of experiments in the case of phenol resin, the etch rate of the present invention is about 70 ~ 95%, for example It was. The grain size indicating the maximum etch rate, such as the etch rate of 95%, may be referred to as the minimum grain size, and the grain size indicating the minimum etch rate, such as the etch rate of 70%, may be defined as the maximum grain size. Such etching rate and grain size are slightly different depending on the type of carbon source within the scope of the present invention.

In terms of the minimum grain size and the maximum grain size, the phenol resin exhibited 100 to 500 μm, but in the case of other liquid or solid carbon sources, the minimum grain size was 50 μm and the maximum grain size was 2,000. [Mu] m. When the size of the maximum grain size was larger than 2,000 µm, the plasma resistance was improved. However, when the maximum grain size was larger than 2,000 µm, the grain size was dropped when the part was processed, and the strength of the component was lowered. Accordingly, the grain size existing between the minimum and maximum grain size can be defined as the corrosion resistance grain size by the carbon source.

The corrosion resistance of the tungsten carbide component for plasma apparatus according to the embodiment of the present invention increases as the grain size increases in the absence of excessive grains or residual carbon. If the grain size between the minimum grain size and the maximum grain size is defined as the grain size by the carbon source, the corrosion resistance by plasma increases as the grain size by the carbon source increases.

6 is an electron micrograph when the content of Example 3, Comparative Example 1 and the phenol resin of the present invention is 1.0%.

6, referring to Example 3 and Comparative Example 1 of the present invention, Comparative Example 1 has a very small size of the crystal grains and is impossible to measure, and the average grain size is approximately 10 µm or less. Example 3 had a grain size larger than 300 mu m. This difference in grain size affects the plasma resistance. By the way, when the content of the phenol resin is 1.0% which is larger than 0.8%, the residual carbon is more than necessary and the size of the crystal grains is too large. As a result, the density of the parts is lowered, the strength is lowered, and problems such as dust are caused, which makes them unsuitable for the parts according to the embodiments of the present invention.

As mentioned above, although the present invention has been described in detail with reference to preferred embodiments, the present invention is not limited to the above embodiments, and various modifications may be made by those skilled in the art within the scope of the technical idea of the present invention. It is possible.

10; Chamber 12; Gas supply pipe
20; Susceptor 30; Shower head
40; Edge ring 41; Ring support
50; Substrate 60; Base material
61, 62; Sintered Plate
63; Adhesive layer AP; Plasma components
AP1, AP2, AP3; First to third plasma components

Claims (19)

delete delete delete delete delete delete delete delete delete delete delete delete Mixing the tungsten carbide powder with a liquid or solid carbon source to form a mixture; And
Sintering the mixture in an atmosphere where the oxygen partial pressure is lower than atmospheric to form tungsten carbide bulk,
The tungsten carbide bulk has a thickness of 0.3 mm or more, and has a volume resistivity of 10 ³ to 10 ⁻⁶ Ω · cm,
Crystal grain size of the tungsten carbide bulk is a plasma device manufacturing method comprising a tungsten carbide bulk, characterized in that 50㎛ ~ 2000㎛. 15. The method of claim 13, wherein in the sintering step, the carbon source removes tungsten oxide present on the surface of the tungsten carbide powder. 14. The method of claim 13, wherein the liquid carbon source is a liquid hydrocarbon at room temperature and is converted to amorphous carbon by pyrolysis. 15. The method of claim 13, wherein the liquid carbon source is a thermoplastic resin that is a liquid at a temperature lower than the sintering temperature of the bulk, and is manufactured from a tungsten carbide bulk composed of tungsten carbide bulk, which is converted to amorphous carbon by pyrolysis. Way. 15. The method of claim 13, wherein the liquid carbon source is a phenol resin, and the phenol resin contains 0.1 to 0.8 wt% based on the tungsten carbide powder. . 15. The method of claim 13, wherein the solid carbon source comprises carbon black. The method of claim 13, wherein the bulk etch rate with respect to the plasma decreases as the grain size of the carbon source increases.

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