KR20200034686A - ceramic part for apparatus manufacturing a semiconductor device and method for manufacturing thereof - Google Patents

Abstract

A ceramic part of the present invention has excellent etching resistance at an etching rate of 1.2% or less when etching for an exposure time (300 minutes) with plasma power of 800 W and the chamber pressure of 100 mTorr. The ceramic part has relatively uniform etching characteristics when applied with a focus ring, etc., to help efficiently etching an object to be etched with excellent quality.

Description

Ceramic parts used in equipment for manufacturing semiconductor devices, and manufacturing methods thereof {ceramic part for apparatus manufacturing a semiconductor device and method for manufacturing thereof}

An embodiment relates to a ceramic component used in equipment for manufacturing a semiconductor device and a method of manufacturing the same.

In the plasma processing apparatus, an upper electrode and a lower electrode are disposed in the chamber, and a substrate such as a semiconductor wafer or a glass substrate is mounted on the lower electrode to apply electric power between both electrodes. Electrons accelerated by the electric field between both electrodes, electrons emitted from the electrodes, or heated electrons cause ionization collision with molecules of the processing gas, and plasma of the processing gas is generated. Active species such as radicals and ions in the plasma perform desired micromachining, for example, etching, on the substrate surface. In recent years, design rules in the manufacture of microelectronic devices have been increasingly refined, and in particular, higher dimensional accuracy is required in plasma etching, so that significantly higher power is used than in the past. The plasma processing apparatus includes a focus ring that is affected by plasma. The focus ring is also called an edge ring or a cold ring.

In the case of the focus ring, when the electric power is increased, the center portion is maximized on the substrate and the edge portion is lowest due to the wavelength effect in which the standing wave is formed and the skin effect in which the electric field is concentrated at the center of the electrode surface. Non-uniformity intensifies. If the plasma distribution on the substrate is non-uniform, the plasma treatment becomes unstable and the quality of the microelectronic device deteriorates. 1 is a photograph showing a general plasma chamber and a focus ring. The highly functional focus ring needs an extended period of replacement. When this occurs, the period of opening the plasma chamber is extended. When the period of opening the chamber is extended, an improvement in yield of the microelectronic device utilizing the wafer is realized.

Domestic Publication No. 10-1998-0063542 Domestic Publication No. 10-2006-0106865

Embodiments are to be used in equipment for manufacturing a semiconductor device and to provide a ceramic component that has improved corrosion resistance and prevents contamination by by-products and a method for manufacturing the same.

In order to achieve the above object, the ceramic component according to an embodiment includes boron carbide, and the etching rate according to Equation 1 below is 1.2% when etching for 300 minutes with a plasma power of 800 W and a chamber pressure of 100 mTorr. Is below.

[Equation 1]

The boron carbide may be 0.1 to 0.6 times the difference between the thermal conductivity measured at 200 ° C and the thermal conductivity measured at 25 ° C.

Etch improvement rate is represented by Equation 2 below.

[Equation 2]

When the reference sample is applied as a silicon ceramic component, the etching improvement rate of the ceramic component may be 45% or more.

When the reference sample is applied as a chemical vapor-deposited silicon carbide ceramic component, the etching improvement rate of the ceramic component may be 20% or more.

The ceramic component may have a difference between a thermal conductivity measured at 200 ° C and a thermal conductivity measured at 25 ° C of 6 W / (m * k) or more.

The ceramic component may have a difference between the thermal conductivity measured at 200 ° C and the thermal conductivity measured at 25 ° C, from 6 W / (m * k) to 20 W / (m * k).

The ceramic component may include necked particles containing boron carbide.

The boron carbide-containing particles may have a particle diameter (D ₅₀ ) of 1.5 um or less.

The ceramic component may include boron carbide having a porosity of 1% or less.

The ceramic part may contain boron carbide having an average diameter of 3 μm or less of pores observed on the surface or in cross section.

The ceramic component may include boron carbide containing 500 ppm or less of metallic by-products.

The ceramic component according to another embodiment includes a seating portion having a first height and a body portion having a second height, the seating portion includes a seating surface, the body portion includes a body floating surface, and the seating portion The surface includes a seating part exposed surface on which an etch object is not disposed, and the etched surface includes the seating part exposed surface and the main body floating surface, and a part or all of the etched surface includes boron carbide.

The boron carbide may have a difference between the thermal conductivity measured at 200 ° C and the thermal conductivity measured at 25 ° C, and may be 0.1 to 0.6 times the thermal conductivity measured at 25 ° C.

The etched surface is etched by etching, the height of the body portion after the etching is 0.85 to 0.92 times the second height, Pd is the lowest point of the etched seat exposed surface, Pt is the lowest point of the etched body injury surface, Htd is the height difference between the Pt and the Pd, H12 is the difference between the first height and the second height, and the Htd is 0.85 times or more of the H12.

P1 is a point on the exposed surface of the seating portion positioned closest to the body portion in cross section.

Pa1 is a point on the exposed surface of the etched portion positioned closest to the body portion etched in the cross section.

The height of Pa1 may be 0.85 times or more of the height of P1.

The ceramic component may have a thermal conductivity of 6 to 32 W / (m * k) measured at a temperature selected from 25 ° C to 800 ° C.

The boron carbide may have a thermal conductivity of 6 to 32 W / (m * k) measured at any temperature selected from 25 ° C to 800 ° C.

The etched surface may have a porosity of 1% or less, and an average diameter of pores observed on a surface or a cross section may be 3 μm or less.

It may include an inclined portion connecting the seating portion and the body portion.

The inclined portion may include an inclined portion that connects the upper surface of the seating portion and the upper portion of the main body.

The average etch rate of the inclined portion may be 2.2% or less.

The boron carbide may include deposited boron carbide or sintered boron carbide.

The ceramic component may be a focus ring.

Etch improvement rate is represented by Equation 2 below.

The seating portion exposed surface or the inclined surface may have an etching improvement rate of 20% or more, compared to the exposed surface or the inclined surface of the ceramic component including chemical vapor-deposited silicon carbide in the etching surface.

[Equation 2]

In Equation 2, the reference sample is a silicon carbide ceramic component deposited by chemical vapor deposition.

The etching apparatus according to another embodiment includes the ceramic component described above.

Another method of etching a substrate according to an embodiment includes a placement step of positioning an etch target on an etching apparatus in which the ceramic component described above is disposed with a focus ring; And an etching step of preparing a substrate by etching the object to be etched, wherein the etching includes an etching gas containing a chamber pressure of 500 mTorr or less, a fluorine-containing compound or a chlorine-containing compound, and 500 W to 15,000 W. It proceeds at plasma power.

The ceramic component according to the embodiment may have improved corrosion resistance in a deposition and / or etching process of a semiconductor wafer, including boron carbide having a controlled thermal conductivity and a dense microstructure. In addition, since the ceramic component according to the embodiment includes boron carbide, it is possible to prevent the formation of particulate by-products in the deposition and / or etching process, and to prevent contamination in the chamber. Accordingly, when the ceramic component or the like according to the embodiment is used, it is possible to impart improved productivity to the manufacture of a semiconductor device.

1 is a schematic view illustrating a view of a ceramic component according to an embodiment from above (arrows indicate measurement points).
2 is a schematic view illustrating a cross section of a ceramic component according to an embodiment.
FIG. 3 is a schematic view for explaining a position and an inclined angle of the ceramic component of FIG. 2 in which height or etch rate is evaluated.
4 is a view showing a etch degree of a ceramic component (CVD-SiC) according to a comparative example in cross section.
5 is a view showing a cross-sectional view of the etching degree of the ceramic component according to the embodiment.
6 is a view for explaining etching angles in Comparative Example (a) and Example (b), respectively.
7 is a view for explaining height difference values in Comparative Example (a) and Example (b), respectively.
8 is an electron microscope photograph of the surface of the focus ring prepared in Example 1, and the inserted photograph is an electron microscope photograph of granulated particles.
9 is an electron microscope photograph of the surface of the focus ring prepared in Comparative Example 1, and the inserted photograph is a photograph showing that a SiC deposition film is formed on a substrate in the manufacturing process.
10 (a) and 10 (b) are electron micrographs of the surfaces of the focus rings prepared in Examples 4 and 7, respectively.
11 (a) and 11 (b) are electron microscope photographs of the fractured surfaces of the focus rings prepared in Examples 7 and 8, respectively.
12 is a photo showing the results of the coupon test in Example 5. (# 1 Example, # 2 Comparative Example, upper real picture, scanning electron microscope picture of the lower surface)

Hereinafter, exemplary embodiments will be described in detail with reference to the accompanying drawings so that those skilled in the art to which the present invention pertains may easily practice. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. The same reference numerals are used for similar parts throughout the specification.

Throughout the present specification, the term “combination of these” included in the expression of the marki form means one or more mixtures or combinations selected from the group consisting of the elements described in the expression of the marki form, wherein the component It means to include one or more selected from the group consisting of.

Throughout this specification, terms such as “first”, “second” or “A” and “B” are used to distinguish the same terms from each other. In addition, a singular expression includes a plural expression unless the context clearly indicates otherwise.

In the present specification, a singular expression is interpreted to include a singular or plural number that is interpreted in context unless otherwise specified.

In this specification, the difference between the A value and the B value means that the smaller value is subtracted from the larger value among A and B, and is expressed as a positive number.

Boron carbide as used herein refers to all compounds based on boron and carbon. The boron carbide may or may not contain an additive and / or doping material in the boron carbide material, specifically, the sum of boron and carbon is 90 mol% or more, 95 mol% or more, 98 mol% It may be more than the above, it may be more than 99 mol%. In the present specification, the boron carbide may be a single phase or a complex phase, and these may be mixed. The boron carbide single phase includes both the stoichiometric phase of boron and carbon and the non-stoichiometric phase deviating from the stoichiometric composition, and the complex phase is at least 2 of the boron and carbon based compounds. It means that the dog is mixed in a predetermined ratio. In addition, boron carbide in the present specification includes all cases in which impurities are added in a single phase or a complex phase of the boron carbide to form a solid solution or impurities that are inevitably added in the process of manufacturing boron carbide. Examples of the impurities include metals such as iron, copper, chromium, nickel, and aluminum.

In the present specification, carbon fluoride, argon gas, and oxygen are applied at 50 sccm, 100 sccm, and 20 sccm, respectively, unless otherwise specified.

The ceramic component according to one embodiment disclosed in this specification is used in equipment for manufacturing a semiconductor. Examples of the ceramic component according to the present embodiment include a focus ring, a dummy wafer, a boat, a preview boat, a handling arm, or a PVD dome.

The ceramic component includes at least a portion of boron carbide.

The ceramic component may be coated with boron carbide.

The ceramic component may be made of boron carbide.

The inventors of the present invention have completed the present invention by confirming that the thermal conductivity characteristic is associated with corrosion resistance during various attempts to increase the corrosion resistance of boron carbide.

In addition, the inventors of the present invention also confirmed that different etching rates are exhibited depending on the relative position or height of the etched object during plasma etching of a ceramic component such as a focus ring. Accordingly, according to the partial etch rate difference, the replacement period of the ceramic parts may be shorter, and it is recognized that this is one of the main causes of deteriorating process efficiency. Thus, the inventors of the present invention have confirmed that it is possible to further reduce the etch rate at the position of the ceramic part that is etched more quickly with the configuration of the embodiment, and this feature improves process efficiency by lengthening the replacement cycle of the ceramic part. The present invention was completed by confirming that it is an important feature.

The ceramic component according to the embodiment disclosed in the present specification includes boron carbide.

The ceramic component applied to the plasma device helps to control the flow of plasma ions delivered to the etch target during the etching process. To this end, ceramic parts control properties such as resistance and thermal conductivity. In addition, the ceramic component applied to the plasma etching apparatus such as the focus ring has a high thermal conductivity value, so it is preferred that the heat transfer is relatively fast.

However, the inventors of the present invention can improve corrosion resistance by applying boron carbide having a low thermal conductivity value to a ceramic component, or by applying boron carbide having a characteristic of a change in thermal conductivity at low temperature, and flow of plasma ions. The present invention was completed after confirming that the efficiency of etching can be further improved because it can be maintained at an appropriate level or higher.

The ceramic component may have an etch rate of 1.2% or less, 1.1% or less, 1% or less, and 0.9% or less when etching for 300 minutes with a plasma power of 800 W and a chamber pressure of 100 mTorr. In addition, the etch rate may be greater than 0%, and may be 0.5% or more. This etch rate is excellent compared to the etch rate of the existing etch-resistant ceramic parts. When applied as a part of plasma equipment, the frequency of replacement of ceramic parts can be reduced and the efficiency of etching operations can be further improved. The etching is a result of applying carbon fluoride, argon, and oxygen as an etching gas at 50 sccm, 100 sccm, and 20 sccm, respectively.

One of the features is that the boron carbide has excellent corrosion resistance and is distinguished from the thermal conductivity characteristic of boron carbide, which is somewhat inferior in corrosion resistance.

The thermal conductivity of boron carbide can be controlled by controlling the applied trace elements, doping materials, additives, and the like. According to the confirmation of the inventors of the present invention, boron carbide, which has better corrosion resistance, has a characteristic that is distinguished from boron carbide, which is somewhat less resistant to corrosion in thermal conductivity change characteristics according to temperature, especially at low temperatures at 25 to 200 ° C. The distinction of the amount of change in thermal conductivity was more evident.

The difference between the thermal conductivity measured at 200 ° C and the thermal conductivity measured at 25 ° C may be 6 W / (m * k) or more.

The difference between the thermal conductivity measured at 200 ° C and the thermal conductivity measured at 25 ° C may be 8 W / (m * k) or more.

The difference between the thermal conductivity measured at 200 ° C and the thermal conductivity measured at 25 ° C may be 10 W / (m * k) or more.

The difference between the thermal conductivity measured at 200 ° C and the thermal conductivity measured at 25 ° C may be 11 W / (m * k) or more.

The difference between the thermal conductivity measured at 200 ° C and the thermal conductivity measured at 25 ° C may be 30 W / (m * k) or less.

The difference between the thermal conductivity measured at 200 ° C and the thermal conductivity measured at 25 ° C may be 20 W / (m * k) or less.

The difference between the thermal conductivity measured at 200 ° C and the thermal conductivity measured at 25 ° C may be 15 W / (m * k) or less.

The difference between the thermal conductivity measured at 200 ° C and the thermal conductivity measured at 25 ° C may be 0.1 to 0.6 times the thermal conductivity measured at 25 ° C.

The boron carbide may have a difference between a thermal conductivity measured at 200 ° C and a thermal conductivity measured at 25 ° C, 0.2 to 0.6 times the thermal conductivity measured at 25 ° C.

The boron carbide may have a difference between the thermal conductivity measured at 200 ° C and the thermal conductivity measured at 25 ° C, and may be 0.25 to 0.5 times the thermal conductivity measured at 25 ° C.

When boron carbide having such a thermal conductivity characteristic is applied to the ceramic component, corrosion resistance can be further improved.

For example, the boron carbide may have a thermal conductivity value of about 60 W / (m * k) or less measured at any temperature selected from 25 to 800 ° C, and may be about 40 W / (m * K) or less. The boron carbide may have a thermal conductivity value of about 30W / (m * K) measured at any temperature selected from 25 to 800 ° C, and may be about 27W / (m * K). The boron carbide may have a thermal conductivity of about 4 W / (m * K) or higher at any temperature selected from 25 to 800 ° C, and may be about 5 W / (m * K) or higher. In the case of boron carbide having such thermal conductivity, it can have a better corrosion resistance.

Illustratively, the thermal conductivity of the boron carbide may be about 80 W / (m * K) or less at 25 ° C, about 40 W / (m * K) or less, and about 31 W / (m * K) or less You can. In addition, the thermal conductivity of the boron carbide may be about 20 W / (m * K) or higher at 25 ° C, or about 22 W / (m * K) or higher. In the case of boron carbide having such thermal conductivity, it can have a better corrosion resistance.

Illustratively, the thermal conductivity of the boron carbide may be about 75 W / (m * K) or less at 200 ° C, about 30 W / (m * K) or less, and about 20 W / (m * K) or less You can. In addition, the thermal conductivity of the boron carbide may be about 7 W / (m * K) or higher at 200 ° C, or about 8 W / (m * K) or higher. In the case of boron carbide having such thermal conductivity, it can have a better corrosion resistance.

For example, the thermal conductivity of the boron carbide may be about 70 W / (m * K) or less at 400 ° C., or about 23 W / (m * K) or less. Further, the thermal conductivity of the boron carbide may be about 7 W / (m * K) or higher at 400 ° C, or about 8 W / (m * K) or higher. In the case of boron carbide having such thermal conductivity, it can have a better corrosion resistance.

Illustratively, the thermal conductivity of the boron carbide may be about 60 W / (m * K) or less at 600 ° C., may be about 30 W / (m * K), and about 21 W / (m * K) days. You can. Further, the thermal conductivity of the boron carbide may be about 5 W / (m * K) or higher at 600 ° C, or about 6 W / (m * K) or higher. In the case of boron carbide having such thermal conductivity, it can have a better corrosion resistance.

Illustratively, the thermal conductivity of the boron carbide may be about 50 W / (m * K) or less at 800 ° C., or about 16 W / (m * K) or less. Further, the thermal conductivity of the boron carbide may be about 5 W / (m * K) or higher at 800 ° C, or about 6 W / (m * K) or higher. In the case of boron carbide having such thermal conductivity, it can have a better corrosion resistance.

For example, the boron carbide may have a characteristic that the thermal conductivity value measured at 400 ° C. is 27 W / (m * k) or less. The ring-shaped component having this feature has a very low pore diameter and porosity, and can have relatively good corrosion resistance.

For example, the ratio (HC ₂₅ : HC ₈₀₀ ) of the thermal conductivity value measured at 25 ° C and the thermal conductivity value measured at 800 ° C may be 1: 0.2 to 3 in the boron carbide. Specifically, the ratio (HC ₂₅ : HC ₈₀₀ ) may be 1: 0.26 to 1, and 1: 0.26 to 0.6. Boron carbide having these characteristics may have improved corrosion resistance.

The boron carbide may have a substantially high relative density. Specifically, the boron carbide may have a relative density of about 90% or more, and about 97% or more. The boron carbide may have a relative density of about 97% or more, about 99% or more, and about 99.99% or more. The boron carbide may have a relative density of about 99.999% or less.

The boron carbide may have a porosity of about 10% or less, about 3% or less, and about 2% or less. The boron carbide may have a porosity of about 1% or less, about 0.5% or less, and about 0.1% or less. The boron carbide may have a porosity of 0.01% or more.

  The boron carbide having such a low porosity has characteristics such as less carbon regions and the like, and may have stronger corrosion resistance.

The boron carbide may have an average diameter of pores of 5 μm or less observed on its surface or cross section. The average diameter of the pores may be 3 μm or less. In more detail, the average diameter of the pores may be 1 μm or less. In addition, based on the total area of the pores, an area of a portion having a pore diameter of 10 μm or more may be 5% or less. The boron carbide may have improved corrosion resistance. At this time, the average diameter of the pores is derived as the diameter of the circle having the same area as the cross-sectional area of the pores.

The boron carbide may have high resistance, medium resistance, or low resistance properties.

Boron carbide having a high resistance property may have a specific resistance of about 10 Ω · cm to about 10 ³ Ω · cm. In this case, the high resistance boron carbide may include silicon carbide or silicon nitride as an additive.

Boron carbide having a medium resistance property may have a specific resistance of less than about 1Ω · cm to less than 10Ω · cm. In this case, the medium resistance boron carbide may include boron nitride as an additive.

Boron carbide having a low resistance property may have a specific resistance of about 10 ^-1 Ω · cm to about 10 ^-2 Ω · cm. At this time, the low-resistance boron carbide may include carbon as an additive.

The boron carbide may have a low resistance property of 5.0 Ω · cm or less, may have a low resistance property of 1.0 Ω · cm or less, and may have a low resistance property of 8 * 10 ^-1 Ω · cm or less.

The boron carbide may not form particles (particulate matter) even when it comes into contact with halogen ions in the plasma etching apparatus. In this case, the particle means a particulate matter having a diameter of 1 um or more. The meaning of not forming the particles (particulate matter) means that the boron carbide is substantially inactive with the halogen ions in a plasma atmosphere.

The ceramic component may have an inert characteristic that is not substantially reactive with halogen ions.

The boron carbide is disposed in an etching apparatus and is etched under the influence of plasma. That is, boron carbide is ionized from the elements exposed on the surface, and can react with an atmosphere element (for example, plasma gas) to form an unintended result in the reactor. When the resultant product is in the gas phase, it is discharged to the outside of the reactor through a duct or the like, so it does not significantly affect the quality of the etching target. However, when the resultant is a solid material such as particles (particulate matter), it may cause a great problem in the quality of etching or the quality of the semiconductor device to be etched.

This feature is distinguished from the fact that materials containing iridium and the like react with halogen ions to form particulate foreign matter.

That is, the ceramic component may have a substantially inert characteristic with less halogen ion reactivity as compared to iridium.

The boron carbide may have an excellent etch improvement rate.

The etching improvement rate is based on Equation 2 below.

[Equation 2]

The etch rate is i) comparing the result of etching a sample of the same size under the same conditions applying 420 hours of exposure time to 2,000 W of RF power in the plasma equipment, or ii) in the plasma equipment. The result of etching a sample of the same size under the same condition of applying an RF power of 800 W and an exposure time of 280 hours was evaluated by comparing the result with other materials. However, it is sufficient if the same etching conditions are applied to the reference sample and the ceramic component, and the etching conditions are applicable as long as they are within a range of conditions for plasma etching the etching target.

The etching improvement rate is evaluated by comparing the etching rate (height reduction rate) of each material after etching under the same conditions.

The etching rate is based on Equation 1 below.

[Equation 1]

The etch improvement rate is evaluated by comparing the etch rate of each material after etching under the same conditions (the ratio of the height after etching when the height of the etch is viewed as a whole).

The etching improvement rate of the ceramic component of the embodiment based on the silicon ceramic component may be 45% or more, 50% or more, 55% or more, and 62% or more. In addition, the etch rate of the ceramic parts of the embodiment based on the silicon ceramic parts may be 90% or less, and 80% or less. The silicon ceramic component is made of silicon (Si, single crystal silicon, manufactured by a drawing method) or is based on including the silicon on at least an etched surface.

Based on the chemical vapor-deposited silicon carbide (CVD-SiC) ceramic component, the etch improvement rate of the ceramic component of the embodiment may be 20% or more, 35% or more, and 37% or less. In addition, the etching rate of the ceramic component of the embodiment based on the chemical vapor-deposited silicon carbide (CVD-SiC) ceramic component may be 90% or less, and 80% or less. The CVD-SiC ceramic component is based on one made of CVD-SiC or including the CVD-SiC on at least an etched surface.

The boron carbide may contain metal by-products (impurities) of 500 ppm or less, 300 ppm or less, 100 ppm or less, 10 ppm or less, and 1 ppm or less It can contain.

The boron carbide may be deposited boron carbide and / or sintered boron carbide.

The boron carbide may have a form in which the boron carbide-containing particles are necked together.

The ceramic component may be at least one surface coated with boron carbide.

The ceramic component may be made of boron carbide.

In the ceramic component, the boron carbide coating layer may be disposed on a sintered body of boron carbide.

1 is a schematic view illustrating a ceramic component according to an embodiment viewed from above (arrows indicate measurement points), FIG. 2 is a schematic diagram illustrating a cross-section of a ceramic component according to an exemplary embodiment, and FIG. 3 is a schematic diagram of FIG. It is a schematic diagram explaining the position and the inclination angle of the ceramic parts where the height or etch rate is evaluated. 4 is a view showing the etching degree of the ceramic component according to the comparative example (CVD-SiC) in cross section, FIG. 5 is a view showing the etching degree of the ceramic component according to the embodiment in cross section, and FIG. 6 is a comparative example (a ) And Example (b) are views illustrating the etch angle, respectively. FIG. 7 is a diagram illustrating the height difference values in Comparative Examples (a) and (b), respectively. Hereinafter, the present invention will be described in more detail with reference to FIGS. 1 to 7.

The ceramic component according to another embodiment disclosed in the present specification may be a focus ring. When the wafer is placed in the chamber, the focus ring may serve as a support for supporting the wafer.

The ceramic component 10 includes a seating portion 200 having a first height and a body portion 100 having a second height. At least a part of the etching object 1 is disposed on the seating portion, and supports an etching object such as a wafer. The main body 100 smoothly regulates the flow of plasma ions delivered to the etch target to help the etch target to be etched evenly and without defects in an intended form.

The main body portion 100 and the seating portion 200 will be described separately from each other, but they may be provided separately from each other, or may be provided integrally without distinction of boundaries.

The seating portion 200 has a first height.

The body portion 100 has a second height.

The first height and the second height refer to the heights to the seating surface and the body surface, respectively, based on the reference surface (for example, the bottom surface of the main body part or the bottom surface of the seating part).

The first height and the second height may be different heights, and specifically, the second height may be higher than the first height.

The seating portion 200 includes a seating portion upper surface 206. The seating portion and the seating portion upper surface may be an integral type without separate layer separation, and when the seating portion and the seating portion upper surface are observed in cross-sections, the seating portion and the upper surface of the seating portion may be divided. In the case of the division type, the upper surface of the seating portion may be in the form of a deposition layer or a coating layer. When the seating surface is divided, the seating surface in the form of a deposition layer or a coating layer may have a thickness of 1 to 40% of the thickness of the seating portion based on before etching, and may have a thickness of 5 to 25%. have.

The seating surface 206 may include a seating non-exposure surface on which the etching object 1 is disposed and a seating part exposure surface on which the etching object is not disposed. The non-exposed surface of the seating portion and the exposed surface of the seating portion are separated from each other based on an outline Pw of an etched object disposed on the upper surface of the seating portion (see FIG. 3).

The body portion 100 includes a body portion upper surface 106. The body portion and the body portion upper surface may be an integral type without separate layer separation, and when the body portion and the body portion upper surface are observed in cross-section, layers may be separated from each other. In the case of the division type, the body surface may be in the form of a deposition layer or a coating layer. When the main body surface is divided, the main body surface in the form of a deposition layer or a coating layer may have a thickness of 1 to 40% of the thickness of the body part based on before etching, and may have a thickness of 5 to 25%. have.

The ceramic component 10 may further include an inclined portion 150 connecting the seating portion 200 and the body portion 100.

The seating portion 200 and the body portion 100 have different heights from each other, and the inclined portion 150 may connect different heights of these.

The main body portion 100, the seating portion 200, and the inclined portion 150 are described separately from each other, but they may be provided separately from each other or may be provided integrally without distinction of their boundaries.

The inclined portion 150 includes an inclined portion upper surface 156 connecting the seating portion upper surface 206 and the main body floating surface 106.

The inclined portion 150 and the inclined portion upper surface 156 may be an integral type without separate layer separation, and when the inclined portion and the inclined portion upper surface are observed in a cross section, the divided type is separated from each other. You can. In the case of the division type, the inclined surface may be in the form of a deposition layer or a coating layer. When the inclined surface is divided, the inclined surface in the form of a deposition layer or a coating layer may have a thickness of 1 to 40% of the thickness of the inclined part based on before etching, and may have a thickness of 5 to 25%. have.

The inclined upper surface 156 is disposed to have an inclined angle (As).

The angle of inclination (As) may be measured based on the non-exposed surface of the seating portion, and may have an angle of greater than about 0 degrees and less than about 110 degrees.

When the length of the inclined portion 150 is 0 mm, the angle of the seating portion and the body portion may be about 90 degrees or more and about 110 degrees or less. When the length of the inclined portion 150 is greater than about 0 mm and less than about 90 degrees, the inclined portion may have a length greater than 0 mm.

The angle of inclination may be linear or non-linear when observed in cross section over the inclined surface, and the angle of inclination may be P1 of the seating surface and the inclined surface where P1 meets and the inclined surface and P2 where the inclined surface meets. Measure based on an imaginary line connecting two points in a straight line.

For example, the inclined angle (As) may be from about 30 degrees to about 70 degrees, and from about 40 degrees to about 60 degrees based on the non-exposed surface of the seating portion. In the case of having such an inclined angle, the flow of plasma ions can be more stably controlled.

The seating portion 200, the inclined portion 150, and the main body portion 100 may each be in the form of a ring, but are not limited thereto, and the seating portion, the inclined portion and the The shape of the body portion can be modified.

The ceramic component 10 has an etching surface.

The etched surface includes the exposed surface of the seating portion and the upper surface of the main body. When the ceramic component 10 has an inclined portion, the etched surface is the seating portion exposed surface, the inclined upper surface, and the main body floating surface.

It is preferable that an etch-resistant material is applied to some or all of the etched surfaces.

Some or all of the etched surface may include the boron carbide, and may be made of the boron carbide.

The etched surface may have an average etch rate of 1.2% or less when etched for an exposure time of 300 minutes with a plasma power of 800 W and a chamber pressure of 100 mTorr. The etched surface may have an average etch rate of 1.1% or less, 1% or less, and 0.9% or less. In addition, the etch rate may be greater than 0%, and may be 0.5% or more.

This etch rate is superior to that of the existing etch-resistant ceramic parts, and is an excellent property that can reduce the replacement frequency of ceramic parts when applied as a part of plasma equipment.

The etching surface may have a different degree of etching depending on the position relative to the object to be etched, and the etching rate is evaluated as the average etching rate of the etching surface. The average etch rate of the etched surface is evaluated by the average etch rate of the etch rate evaluated at least three points on the etched surface at a predetermined distance.

The detailed description of the properties of the boron carbide is omitted because it overlaps with the above description.

The etched surface is etched by etching, and specifically is a surface etched by a method such as plasma etching.

After etching, a portion of the etched surface is lost compared to the etched surface before etching.

The etching degree of the ceramic component may vary depending on the etching conditions to be applied. Hereinafter, unless otherwise specified, features of the embodiment will be described based on ceramic parts etched such that the height of the body portion after etching based on the height of the body portion falls within a range of 0.85 to 0.92 times the height of the body portion before etching.

That is, the height of the etched surface after etching is lower than the height of the etched surface before etching (initial height, the first height in the case of the seat exposed portion or the second height in the case of the body floating surface). At this time, the degree of disappearance of the etched surface may be slightly different for each location of the etched surface, and in particular, the etched degree of the exposed portion of the seating portion may be larger than the etched degree of the body floating surface.

This does not mean that the etched surface of the ceramic component 10 is entirely lost at a constant speed during the continuous etching process, but a part such as the exposed portion of the seating part is lost more quickly than other parts, which causes a change in the overall plasma flow. It may be difficult to etch the object to be etched at a predetermined level. In addition, this is one of the important reasons for speeding up the replacement cycle of ceramic parts and lowering the etching efficiency of the etching target.

The ceramic component 10 of the embodiment has a feature that the entire etched surface is lost at a relatively constant speed compared to the conventional ceramic component.

The seating upper surface 206 directly contacts the inclined upper surface 156 or the body upper surface 106, and P1 is a boundary line thereof.

The body floating surface 106 directly contacts the inclined floating surface 156 or the seating floating surface 206, and P2 is a boundary line thereof.

When the seating upper surface 206 and the body upper surface 106 directly contact each other, P1 and P2 mean the same line.

Pw means the seating surface 206 of the end point where the etching target 1 is located.

The region in which the etching object is disposed with respect to the Pw as a boundary is referred to as a seating non-exposed surface, and an area where the etching object is not disposed is referred to as a seating non-exposed surface.

The distance between Pw and P1 is Lw1, and if there is an inclined portion 150, the distance between P1 and P2 is called L12.

In the case of the main body 100, its length may vary depending on the design of the ceramic component 10.

In the present invention, a line that is separated by a distance of a reference width from P2 is referred to as P3, using a larger value among the Lw1 and L12 values as a reference width.

A line that is separated from the P2 by a distance twice the reference width by using the larger of the Lw1 and L12 values as a reference width is referred to as P4.

A line that is separated by a distance three times the reference width from P2 is referred to as P5, using a larger value among the Lw1 and L12 values as a reference width.

The distance between P2 and P3 is L23, the distance between P3 and P4 is L34, and the distance between P4 and P5 is referred to as L45.

The sections of P1 and P2 are divided into four equal parts on the upper surface of the inclined portion and are referred to as P1-1, P1-2, P1-3 and P1-4, respectively, starting from the point close to P1.

In the present specification, a position corresponding to P2 to P4 is treated as the main body when the main body 100 is described.

Pa1 is a boundary line between the etched seat exposed surface and the etched sloped surface. Further, Pa2 is a boundary line between the etched inclined surface and the etched body surface (see FIG. 6).

The Pa1 and the Pa2 are lost by etching and compared to P1, which is the boundary line between the seating surface and the inclined surface before etching, and P2, which is the boundary line between the surface of the inclined surface before etching and the body surface, before being etched. do.

The plane connecting Pa1 and Pa2 has an etch plane angle (Ae). The etch plane angle can be measured by using the seating portion non-exposed surface as a reference plane, and it is sufficient if the same reference plane as the inclined plane angle is applied.

The height of Pa1 may be 0.85 times or more of the height of P1. The height of Pa1 may be 0.87 times or more of the height of P1. In addition, the height of the Pa1 may be 0.89 times or more the height of the P1. The height of Pa1 may be less than 1 times the height of P1. This feature of the height of the Pa1 means that it has a substantially reduced etch rate compared to the previously applied ceramic parts, and the silicon ceramic parts or chemical vapor deposited silicon carbide confirmed by the inventors of the present invention at this point Compared, it shows a significantly improved etch rate.

The etch plane angle (Ae) of the ceramic component 10 may be 0.83 to 1.05 times the inclined angle (As). This means that a ceramic component having such characteristics is etched relatively evenly throughout etching. This feature can further stabilize the plasma flow, thereby improving the quality after etching of the object to be etched, prolonging the replacement time of the ceramic component, and further improving the etch yield.

The etched ceramic component 10 has a lowest point Pd of the etched seat exposed surface.

The etched ceramic component 10 has the lowest point Pt of the etched body surface.

As described above, the lowest point among the points located at P2 to P4 is applied. In the case of the main body floating surface, more etching is performed at the outermost point of the ceramic component, and the visually visible main body floating surface may have a shape that gradually decreases in height (see FIG. 6 (a)). In this case, the lowest point of the body floating surface is applied in the range of P2 to P4 described above, not the outermost point.

Htd is the difference between the height of the Pt and the height of the Pd.

H12 is the difference between the first height and the second height.

The Htd may be 0.85 times or more of the H12. The Htd may be 0.88 times or more of the H12. The Htd may be 0.91 times or more of the H12. The Htd may be 1 time or less of the H12. The Htd may be 0.99 times or less of the H12. This feature is that the difference in height before and after the etching is relatively small compared to the case where other ceramic materials such as CVD-SiC are applied, and that the etching proceeds more evenly over the entire etching surface compared to the conventional material. .

The upper surface of the inclined portion 156 is etched by the etching, and the height of the inclined portion before etching may be reduced than the height of the inclined portion after etching. The height of the inclined portion is evaluated by averaging the results evaluated at least three points except P1 and P2.

The etch rate of the inclined portion may be 2.2% or less. The etch rate of the inclined portion may be 2.0% or less. The etch rate of the inclined portion may be 1.8% or less. The etch rate of the inclined portion may be 1.6% or less. The etch rate of the inclined portion may be 0.1% or more. The etch rate of the inclined portion is superior to that of the conventional ceramic component having the inclined portion. The ceramic component of the embodiment having such characteristics has better etch resistance, and the shape deformation of the ceramic component may be relatively small during the etching process.

The porosity of the etched surface may be 1% or less. The average diameter of pores observed on the surface of the etched surface may be 3 μm or less. For the description related to the porosity and the average diameter of the pores, the description of the above boron carbide is applied.

Etch improvement rate is represented by Equation 2 below.

[Equation 2]

When the reference sample is applied based on chemical vapor-deposited silicon carbide, the etch rate of the ceramic component may be 20% or more. When the reference sample is applied on the basis of chemical vapor-deposited silicon carbide, the etching improvement rate of the ceramic component may be 35% or more. When the reference sample is applied on the basis of chemical vapor-deposited silicon carbide, the etching improvement rate of the ceramic component may have an etching improvement rate of 37% or more. In addition, when the reference sample is applied on the basis of chemical vapor-deposited silicon carbide, the etching improvement rate of the ceramic component of the embodiment may be 90% or less, and 80% or less.

When the reference sample is applied based on a single crystal silicon ceramic component, the etch improvement rate of the ceramic component may be 45% or more, and 50% or more. When the reference sample is applied based on a single crystal silicon ceramic component, the etching improvement rate of the ceramic component may be 55% or more. When the reference sample is applied based on a single crystal silicon ceramic component, the etching improvement rate of the ceramic component may have an etching improvement rate of 62% or more. When the reference sample is applied based on a single crystal silicon ceramic component, the etch improvement rate of the ceramic component may be 90% or less, and 80% or less.

The etching improvement rate is evaluated based on the etching rate of the etching surface.

The ceramic component 10 may be a focus ring.

The ceramic component 10 may include the boron carbide in the etch layer.

In the ceramic component 10, the etch layer may be formed of the boron carbide.

The ceramic component 10 may include the boron carbide.

The ceramic component 10 may be made of the boron carbide.

The boron carbide may be deposited boron carbide or sintered boron carbide.

The ceramic component may have a difference between a thermal conductivity measured at 200 ° C and a thermal conductivity measured at 25 ° C of 6 W / (m * k) or more.

The difference between the thermal conductivity measured at 200 ° C and the thermal conductivity measured at 25 ° C may be 8 W / (m * k) or more.

The ceramic component may have a difference between a thermal conductivity measured at 200 ° C and a thermal conductivity measured at 25 ° C of 10 W / (m * k) or more.

The ceramic component may have a difference between a thermal conductivity measured at 200 ° C and a thermal conductivity measured at 25 ° C of 11 W / (m * k) or more.

The ceramic component may have a difference between a thermal conductivity measured at 200 ° C and a thermal conductivity measured at 25 ° C of 30 W / (m * k) or less.

The difference between the thermal conductivity measured at 200 ° C and the thermal conductivity measured at 25 ° C may be 20 W / (m * k) or less.

The ceramic component may have a difference between a thermal conductivity measured at 200 ° C and a thermal conductivity measured at 25 ° C of 15 W / (m * k) or less.

The ceramic component may have a difference between a thermal conductivity measured at 200 ° C and a thermal conductivity measured at 25 ° C, 0.1 to 0.6 times the thermal conductivity measured at 25 ° C.

The ceramic component may have a difference between a thermal conductivity measured at 200 ° C and a thermal conductivity measured at 25 ° C, 0.2 to 0.6 times the thermal conductivity measured at 25 ° C.

The ceramic component may have a difference between the thermal conductivity measured at 200 ° C and the thermal conductivity measured at 25 ° C, and may be 0.25 to 0.5 times the thermal conductivity measured at 25 ° C.

The thermal conductivity is based on the measurement on the etching surface.

A ceramic component having such thermal conductivity characteristics and including boron carbide on an etched surface may have improved etch resistance.

The ceramic component 10 is mounted on a plasma etching equipment or the like to support a wafer or the like to be etched (1), and helps to stabilize the flow of plasma ions and the like transferred to the etching target. In addition, a part of it is etched together during the etching process of the object to be etched.

The second height, which is the height of the main body, is greater than the first height, which is the height of the seat.

Specifically, the second height may be 1.2 times or more of the first height, 1.4 times or more, and 1.5 times or more. Further, the second height may be 3.5 times or less of the first height, or 3 times or less. When having such a height difference, it is possible to help a more stable process progress to the device to which the ceramic component is applied.

The ceramic component 10 may have a replacement time, which is a time in which the height of the etched body portion is reduced to 10% or more based on the height of the original body portion, and may be twice or more compared to the ceramic component applied to the etched portion. If the ceramic component of the embodiment is etched slowly, this means that the interval between opening the chamber of the etching equipment for the purpose of replacing the component is increased, and eventually, the etching efficiency of the etching apparatus is improved. In addition, it is possible to reduce the possibility of toxic substances that may occur in the process of opening the chamber, and also has the advantage of lowering the possibility of contamination in the chamber.

The etching apparatus according to another embodiment includes the ceramic component described above.

The etching device may be, for example, a plasma etching device.

The etching device includes a chamber (not shown) having an accommodation space and a housing therein, and a gas supply pipe (not shown) for supplying gas into the chamber, a shower head connected to the gas supply pipe and supplying gas to the accommodation space ( (Not shown). A susceptor (not shown) is positioned at a position facing the shower head, and the susceptor supports an etch target. The chamber is provided with a gas discharge pipe (not shown) for discharging gas supplied to the accommodation space or evacuating the accommodation space, and an edge ring supported by a ring support (not shown) between the shower head and the susceptor. (Not shown) may be located further.

The etch device etches an etch target disposed on the susceptor, and the etch target is supported integrally with the susceptor or by a focus ring disposed on the susceptor.

The shower head supplies plasma gas or the like and the etching target is etched in a plasma separator formed in the accommodation space.

When the ceramic component of the embodiment is applied as the focus ring, the frequency of chamber opening can be reduced with improved etch resistance, thereby improving the process efficiency and controlling the flow of plasma more easily by maintaining the shape of the focus ring during the etching process. can do.

The etching method of the substrate according to another embodiment includes a placement step and an etching step, and applies the ceramic component described above as a focus ring.

The arranging step is a step of positioning an etch target on an etch device in which ceramic parts are disposed with a focus ring. The etching device may be applied without limitation as long as it is a device for etching a substrate applied to an electronic product or the like, and for example, a plasma visual device may be applied. The substrate may be applied to the etching device as an etch target, and for example, a substrate utilized in a semiconductor device such as a silicon substrate may be applied.

The description of the focus ring and the ceramic component overlaps with the above description, and thus description thereof is omitted.

The etching step is a step of preparing the substrate by performing etching of the etching target. The etching may be performed in a normal process applied to etching processes such as depressurization and heating, plasma gas supply, etching, and washing.

The etching may be performed at a chamber pressure of 500 mTorr or less, an etching gas containing a fluorine-containing compound or a chlorine-containing compound, and a power of 500 W to 15,000 W. The chamber pressure may be 100 mTorr or less, and 10 mTorr or more.

The power may be 500 W to 15,000 W of RF power, and may be 500 to 8000 W of RF power.

The etching time may be 100 hours or more, 200 hours or more, 400 hours or more, and 800 hours or more. The etching time may vary depending on power applied, etching gas, and the like.

Hereinafter, a method of manufacturing the ceramic component will be described.

The ceramic component is a method such as a cold isostatic pressing (CIP) processing process, a hot press sintering process, a spark plasma sintering process, a chemical vapor deposition process, or a physical vapor deposition process. Can be manufactured.

In order for the ceramic component to be manufactured, first, a raw material is provided. The raw material may include boron and carbide, or boron carbide.

Boron carbide is represented by B ₄ C, and is the third highest strength material after diamond and cubic boron nitride, and has excellent chemical and corrosion resistance. On the other hand, plasma corrosion resistance is affected by the bonding force of the ceramic parts. That is, the stronger the bonding force, the higher the corrosion resistance, and the boron carbide has a high covalent bonding property, so that the bonding force is large and thus the plasma corrosion resistance is excellent.

The raw material may include boron carbide particles. That is, the boron carbide has a powder form and may be used as the raw material.

The boron carbide powder may have an average particle diameter of about 1.5 μm or less, an average particle diameter of about 0.3 μm to about 1.5 μm, and an average particle diameter of about 0.4 μm to about 1.0 μm based on D ₅₀ . have. In addition, the boron carbide powder may have an average particle diameter of about 0.4 μm to about 0.8 μm based on D ₅₀ . In the case of applying boron carbide powder having an average particle size that is too large, the density of the manufactured sintered body may be lowered and corrosion resistance may be lowered, and if the particle size is too small, workability may decrease or productivity may be lowered.

As the raw material, boron carbide powder may be applied, and the boron carbide powder may have high purity (boron carbide content of 99.9% by weight or more) and low purity (boron carbide content of 95% by weight or more and less than 99.9% by weight). Can be applied.

The raw material may further include additives other than the boron carbide. The additive may be introduced in a process of manufacturing the ceramic component in powder form, liquid phase or gas phase.

Examples of the material used as the additive include carbon, boron oxide, silicon, silicon carbide, silicon oxide, boron nitride, boron or silicon nitride. The additive may be included in an amount of about 0.1 wt% to about 30 wt% based on the raw material.

Specifically, the additive may be a sintering property improving agent. The sintering property improving agent is included in the raw material to improve the physical properties of boron carbide. The sintering property improving agent may be any one selected from the group consisting of carbon, boron oxide, silicon, silicon carbide, silicon oxide, boron nitride, boron nitride, silicon nitride, and combinations thereof. The sintering property improving agent may be contained in an amount of about 30% by weight or less based on the entire raw material. Specifically, the sintering property improving agent may be contained in an amount of about 0.001% to about 30% by weight, 0.1 to 25% by weight, and 5 to 25% by weight based on the entire raw material. have. When the sintering property improving agent is contained in an amount of more than 30% by weight, the strength of the sintered body may be reduced.

The raw material may include boron carbide raw materials such as boron carbide powder in a residual amount other than the sintering property improving agent. The sintering property improving agent may include boron oxide, carbon, and combinations thereof.

When carbon is applied as the sintering property improving agent, the carbon may be added in the form of a resin such as a phenol resin, or the resin may be applied in a carbonized form through a carbonization process. In the carbonization process of the resin, a process for carbonizing the polymer resin may be applied.

When carbon is applied as the sintering property improving agent, the carbon may be applied at 1 to 30% by weight, 5 to 30% by weight, 8 to 28% by weight, and 13 to 23% by weight Can be applied. When carbon is used as the sintering property improving agent in this amount, the necking phenomenon between the particles is increased, the particle size is relatively large, and a boron carbide having a relatively high relative density can be obtained. However, when the carbon is included in an amount of more than 30% by weight, the degree may be reduced due to generation of a carbon region due to residual carbon.

Boron oxide may be applied to the sintering property improving agent. The boron oxide is represented by B ₂ O ₃ , and the boron oxide is applied to generate boron carbide through chemical reaction with carbon present in the pores of the sintered body, and helps to discharge residual carbon to provide a more compact sintered body. Can provide.

When the boron oxide and the carbon are applied together as the sintering characteristic improving agent, the relative density of the sintered body can be further increased, which reduces the carbon area present in the pores and can improve the sintered body with improved density.

The boron oxide and the carbon may be applied in a weight ratio of 1: 0.8 to 4, may be applied in a weight ratio of 1: 1.2 to 3, and may be applied in a weight ratio of 1: 1.5 to 2.5. In this case, a sintered body with improved relative density can be obtained. More specifically, the raw material may contain the boron oxide in an amount of 1 to 9% by weight, and the carbon in an amount of 5 to 15% by weight, and in this case, a sintered body having excellent density and less defects can be manufactured. .

Further, the sintering property improving agent may have a melting point of about 100 ° C to about 1000 ° C. More specifically, the melting point of the additive may be about 150 ℃ to about 800 ℃. The melting point of the additive may be about 200 ℃ to about 400 ℃. Accordingly, the additive can be easily spread between the boron carbide in the process of sintering the raw material.

The additive can improve the thermal conductivity of the ceramic component. In addition, the additive can control the electrical resistance of the ceramic component. In addition, the additive can improve the sinterability of the ceramic component.

In addition, the melting point of the additive may be about 100 ℃ to about 1000 ℃. More specifically, the melting point of the additive may be about 150 ℃ to about 800 ℃. The melting point of the additive may be about 200 ℃ to about 400 ℃. Accordingly, the additive can be easily diffused between the boron carbide in the process of sintering the raw material.

In addition, when carbon is used as the additive, the carbon may be added in the form of a resin. The resin may be added to the carbon through a carbonization process.

The raw material does not contain a substance that can generate a by-product in a solid state during a semiconductor process, or a very low content. For example, examples of the material capable of generating the by-products include metals such as iron, copper, chromium, nickel or aluminum. The content of the material capable of generating the by-product may be 500 ppm or less based on the raw material. More details on by-products are as described above.

CIP (Cold Isostatic Pressing) processing process will be described.

The ceramic component 10 is generally manufactured by manufacturing boron carbide having a shape of a ceramic component and processing the manufactured boron carbide finished product.

The boron carbide material is difficult to process, so it can be processed in a special method such as wire discharge processing and surface discharge processing to produce a finished product form.

The manufacturing method of the ceramic component 10 includes a primary molding step and a component forming step. The manufacturing method may further include a granulation step prior to the primary molding step. The manufacturing method may further include a processing step after the component forming step.

The granulation step is a slurrying process of mixing the raw material containing boron carbide with a solvent to prepare a slurryed raw material, and drying the slurryed raw material to form a spherical granular raw material. Process.

In the granulation step, alcohol or water, such as ethanol, may be applied as the solvent applied for slurrying. The solvent may be applied in an amount of about 60% to about 80% by volume based on the entire slurry.

A ball mill method may be applied to the slurrying process. In the ball mill method, specifically, a polymer ball may be applied, and the slurry mixing process may be performed for about 5 hours to about 20 hours.

In addition, the granulation process may be performed in a manner that the raw material is granulated while the slurry is sprayed and the solvent contained in the slurry is removed by evaporation. The granulated raw material particles produced in this way have a characteristic that the particles themselves have a round shape as a whole and a relatively constant particle size.

The diameter of the raw material particles may be from about 0.3 to about 1.5 um based on D50, from about 0.4 μm to about 1.0 μm, and from about 0.4 μm to about 0.8 μm.

When the granulated raw material particles are applied in this way, the filling of the mold is easy and the workability can be further improved when the green body is manufactured in the first molding step described later.

The first forming step is a step of forming a green body by molding a raw material containing boron carbide. Specifically, in the molding, a method in which the raw material is put into a mold (rubber, etc.) and pressurized may be applied. More specifically, the molding may be applied by cold isostatic pressing (CIP).

When the first forming step is performed by applying a cold isostatic pressing method, it is more efficient to apply the pressure at about 100 MPa to about 200 MPa.

The green body may be manufactured in consideration of a size and shape suitable for the use of the sintered body to be manufactured.

The green body is preferably formed to be slightly larger than the size of the final sintered body to be manufactured, and since the strength of the sintered body is stronger than that of the green body, the green body is painted after the first molding step for the purpose of reducing the processing time of the sintered body. The shape processing process of removing unnecessary parts from the body may be further performed.

The component forming step is a step of carbonizing and sintering the green body to produce boron carbide.

The carbonization may be performed at a temperature of about 600 ° C to about 900 ° C, and in this process, a binder or unnecessary foreign substances in the green body may be removed.

The sintering may be performed in a manner of maintaining a sintering time of about 10 hours to about 20 hours at a sintering temperature of about 1800 ° C to about 2500 ° C. In this sintering process, growth and necking between the raw material particles are progressed to obtain a compacted sintered body.

The sintering may be specifically performed with temperature profiles of temperature increase, maintenance, and cooling, and specifically, temperature of primary temperature-1 primary temperature maintenance-2 secondary temperature-secondary temperature maintenance-3 tertiary temperature-3 tertiary temperature maintenance-cooling You can proceed to the profile.

The rate of temperature increase in the sintering may be about 1 ° C / min to about 10 ° C / min. More specifically, the rate of temperature increase in the sintering may be about 2 ° C / min to about 5 ° C / min.

In the sintering, a temperature of about 100 ° C to about 250 ° C can be maintained for about 20 minutes to about 40 minutes. Further, in the sintering, a temperature range of about 250 ° C to about 350 ° C may be maintained for about 4 hours to about 8 hours. In addition, in the sintering, a temperature range of about 360 ° C to about 500 ° C may be maintained for about 4 hours to about 8 hours. When maintained for a certain period of time in the temperature range as described above, the additive can be more easily diffused, it is possible to prepare a more uniform phase boron carbide.

The sintering may be maintained in a temperature range of about 1800 ° C to about 2500 ° C for about 10 hours to about 20 hours. In this case, a more robust sintered body can be produced.

The cooling rate in the sintering may be about 1 ° C / min to about 10 ° C / min. More specifically, the cooling rate in the sintering may be about 2 ° C / min to about 5 ° C / min.

The boron carbide produced in the component forming step may further be subjected to a processing step including surface processing and / or shape processing.

The surface processing is an operation to flatten the surface of the sintered body, and a method of flattening the ceramic may be applied.

The shape processing is a process of removing a portion of the sintered body or cutting it to have a desired shape. The shape processing may be performed in a discharge processing method in consideration of the fact that the boron carbide has excellent density and strong strength, and may be specifically performed in a discharge wire processing method.

When processing the discharge wire, the power source may be a DC power source, the voltage may be about 100 volts to about 120 volts, and the processing speed may be about 2 mm / minute to about 7 mm / minute. In addition, the wire speed during processing may be about 10 rpm to about 15 rpm, the tension of the wire may be about 8 g to about 13 g, and the diameter of the wire may be about 0.1 mm to about 0.5 mm.

The ceramic component 10 processed in this way may further undergo a surface processing process such as polishing.

A method of manufacturing the ceramic component 10 by a hot press sintering process or a spark plasma sintering process will be described.

The manufacturing method includes a preparation step, a batch step and a molding step.

The preparation step is a step of loading the raw material containing boron carbide into a mold (not shown). The mold can manufacture a ceramic component of a predetermined shape.

The raw material is located in the mold.

The preparation step is a process of introducing a raw material into the mold.

The mold may be made of a graphite-like material having high strength at a high temperature so that a strong sintering pressure can be applied, and may be applied by reinforcing the mold with graphite fibers or the like as necessary. This reinforcement serves to prevent the mold from being damaged or changed in shape at high temperature and high pressure so that the ceramic component does not have the intended shape.

The arrangement step is a step of charging the mold containing the raw material in a sintering furnace (or chamber) and setting a pressurizing device. The sintering furnace or chamber applied in the arrangement step may be applied without limitation as long as it is a device capable of manufacturing the boron carbide in a high-temperature atmosphere.

The forming step is a step of forming a ceramic component from the raw material by applying a sintering temperature and a sintering pressure to the mold.

The sintering temperature may be about 1800 to about 2500 ℃, may be about 1800 to about 2200 ℃. The sintering pressure may be about 10 to about 110 MPa, may be about 15 to about 60 MPa, and may be about 17 to about 30 MPa. When the forming step is performed under such sintering temperature and sintering pressure, it is possible to more efficiently manufacture high-quality ceramic parts.

The sintering time may be applied to 0.5 to 10 hours, 0.5 to 7 hours may be applied, and 0.5 to 4 hours may be applied.

The sintering time is a considerably shorter time compared to a sintering process performed at normal pressure, and even if such a short time is applied, a ceramic component having equal or better quality can be manufactured.

The forming step may be performed in a reducing atmosphere. When the forming step is carried out in a reducing atmosphere, boron carbide powder may be prepared by reacting with oxygen in the air to reduce substances such as boron oxide which can form boron carbide with a higher boron carbide content.

The forming step may be performed while generating sparks in the gaps between particles in the sintering furnace (or chamber). In this case, a method of applying electrical energy on the pulse to the mold may be applied to the mold by an electrode connected to the pressing part. When the forming step is performed while applying the electric energy in the pulse, the dense sintered body can be obtained in a shorter time by the electric energy.

When the forming step is performed in the spark plasma sintering apparatus, when the raw material is placed in the mold in the chamber, the temperature in the chamber is increased by the heating unit, and the sintering may be performed with or separately from the pressurization. have. At this time, electrical energy is applied to the chamber to promote sintering of the raw material, for example, a DC pulse current can be applied.

In the forming step, the maximum temperature section of the sintering temperature may be about 1800 ° C to about 2200 ° C, and may be maintained for about 2 hours to about 5 hours. At this time, the pressure applied to the mold may be about 50MPa to about 80MPa. More specifically, the pressure applied to the mold may be from about 55 MPa to about 70 MPa.

When the above manufacturing method is applied, a boron carbide-containing ceramic component of substantially the same form as the finished product form can be manufactured by introducing the raw material in powder form directly into a molding die and sintering it, thereby simplifying the manufacturing process. It is efficient. In addition, in addition to the advantages of simplifying the process, there is also an advantage that the properties of boron carbide produced are excellent.

Describe the processing process by deposition or coating

The ceramic component 10 may be manufactured by a deposition process. For example, the vapor deposition bulk may form the surface or all of the ceramic component 10 by a vapor deposition method such as CVD. Specifically, when the ceramic component 10 is applied by a CVD method (CVD vapor deposition bulk production method), the ceramic component 10 is deposited by CVD boron carbide (BC), substrate removal, shape processing, polishing, measurement, and It can be produced including the process of cleaning.

The CVD boron carbide deposition process is a process of forming a boron carbide deposition film on a substrate (mainly graphite). The substrate may be removed after the deposition is sufficiently performed in such a way that the gaseous material is physically deposited on the substrate.

The shape processing process is a process of completing the shape of the ceramic component 10 by mechanical processing. The polishing process is a process of smoothing the surface roughness, and then checking the quality and removing contaminants. Within the scope of the examples, some of the above processes may be omitted, or other processes may be added.

In the CVD process, a boron source gas and a carbon source gas may be used as gaseous materials. The boron source gas applied to the CVD process may contain any one selected from the group consisting of B ₂ H ₆ , BCl ₃ , BF ₃ and combinations thereof. In addition, the carbon source gas used in the CVD process may contain CF ₄ .

For example, boron carbide applied to the ceramic component 10 may be deposited with a chemical vapor deposition apparatus using B ₂ H ₆ as a boron precursor, and a deposition temperature of 500 to 1500 ° C.

For the formation of the ceramic component 10, various deposition or coating processes other than those described above may be applied. The method of coating the boron carbide coating layer with a thick film is not limited, and there are physical vapor deposition, room temperature spraying, low temperature spraying, aerosol spraying, plasma spraying, and the like.

In the physical vapor deposition method, for example, a boron carbide target may be sputtered in an argon (Ar) gas atmosphere. The coating layer formed by the physical vapor deposition method may be referred to as a thick film PVD boron carbide coating layer.

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

8 is an electron microscope photograph observing the surface of the focus ring prepared in Example 1, the inserted photograph is an electron microscope photograph observing granulated particles, and FIG. 9 is the surface of the focus ring prepared in Comparative Example 1 Is an electron microscope photograph, and the inserted photograph is a photograph showing that a SiC deposition film is formed on a substrate during the manufacturing process. 10 (a) and (b) are electron micrographs of the surfaces of the focus rings prepared in Examples 4 and 7, respectively, and FIGS. 11 (a) and (b) are shown in Examples 7 and 10, respectively. This is an electron microscope photograph of a fractured surface of a focus ring prepared in Example 8. 12 is a photo showing the results of the coupon test in Example 5. (# 1 Example, # 2 Comparative Example, upper real picture, scanning electron microscope picture of the lower surface). Hereinafter, the present invention will be described in more detail through specific examples. The following examples are only examples to aid the understanding of the present invention, and the scope of the present invention is not limited thereto.

1. Preparation of focus rings of Preparation Examples 1 to 8

Boron carbide particles (particle size D ₅₀ = 0.7 μm), raw materials such as carbon and a solvent were put in a slurry mixer and mixed in a ball mill method to prepare a slurryed raw material. The slurryed raw material was spray dried to granulate to prepare a granulated raw material. The electron micrograph of the granulated particles is presented as the inserted picture in FIG. 8.

Each of these raw materials was filled into a rubber mold having a disc-shaped hollow prepared for forming a green body of a focus ring, and then loaded into a CIP machine and then pressed to prepare a green body. After the green body was processed to have a size similar to that of the focus ring, the green body was subjected to a carbonization process. The green body undergoing the carbonization process was sintered at normal pressure in a sintering furnace. After the sintered body thus prepared, the surface of the sintered body is flattened. The shape processing was performed in the form of a focus ring by a wire discharge method to prepare a focus ring of each example. Table 1 below summarizes the content of raw materials applied to each production example, and the sintering temperature and time.

2. Preparation of focus rings of Preparation Examples 9 to 14

After filling boron carbide particles (particle size D ₅₀ = 0.7 μm) into a molding die, charging the molding die into a sintering equipment, and sintering it at the temperature, pressure and time shown in Table 1 below, the focus rings of Preparation Examples 9 to 14 Was prepared.

3. Focus rings of Comparative Examples 1 to 3

Polycrystalline SiC was prepared by a CVD method and applied as a focus ring of Comparative Example 1. Specifically, a SiC deposition film was formed on a graphite substrate, and after removing the graphite substrate, a focus ring of Comparative Example 1 was manufactured through a shape processing and polishing process. A cross-sectional photograph of a sample in which SiC is deposited on a graphite substrate is an insertion photograph of FIG. 9, and a surface photograph after plasma resistance test described later is illustrated in FIG. 9.

The Si focus ring was applied as single crystal Si (100,111) to the focus ring of Comparative Example 2.

WC Focus Ring applied its own product (for specific manufacturing method, see our patent registration 10-1870051).

Manufacturing example # Additive 1 Additive 2 Boron carbide powder (% by weight) Sintering temperature Sintering time pressure Remark (weight%) (weight%) (℃ (time) (Mpa) One 20 0 Balance 2380 10 Atmospheric pressure B ₄ C 2 20 0 Balance 2380 15 Atmospheric pressure B ₄ C 3 10 0 Balance 2380 15 Atmospheric pressure B ₄ C 4 0 5 Balance 2380 15 Atmospheric pressure B ₄ C 5 0 10 Balance 2380 15 Atmospheric pressure B ₄ C 6 0 15 Balance 2380 15 Atmospheric pressure B ₄ C 7 10 5 Balance 2380 15 Atmospheric pressure B ₄ C 8 20 0 Balance 2380 15 Atmospheric pressure B ₄ C 9 10 0 Balance 1950 5 25 B ₄ C 10 0 5 Balance 1950 5 25 B ₄ C 11 0 10 Balance 1950 5 25 B ₄ C 12 0 15 Balance 1950 5 25 B ₄ C 13 10 5 Balance 1950 5 25 B ₄ C 14 0 0 100 1950 5 25 B ₄ C Comparative Example 1 - - - - - - CVD-SiC Comparative Example 2 - - - - - - Si Comparative Example 3 - - - - - - WC

* Additive 1 is carbon as additive 1.

** Additive 2 is boron oxide as additive 2.

4. Evaluation of physical properties

(1) Relative density evaluation and surface observation

The relative density (%) was measured by the Archimedes method. The results are shown in Table 2 below. In addition, surface properties were observed with an electron microscope, and each surface property was presented in the accompanying drawings. The "-" sign means no measurement.

(2) Thermal conductivity, resistance characteristic and etch rate characteristic

The thermal conductivity [W / (m * k)] was measured by Laser Flash Apparatus (LFA457).

The resistance characteristics (Ω · cm) were measured with a specific resistance surface resistance meter (MCP-T610).

(3) Etch rate characteristics and particle formation

The etching improvement rate (%) was performed under the same temperature and atmosphere by applying 2000 W of RF power to the plasma equipment. The calculation of the etch improvement rate (%) was based on Equation 2 below. The ceramic parts are shown in Table 3 below by evaluating the etching improvement rate of the samples of the examples.

[Equation 2]

Particle formation was evaluated by evaluating the presence or absence of particles remaining in the equipment chamber after evaluating the etch rate characteristics. O was indicated when particles were formed, X was not formed, and "-" was not identified.

The evaluation results are given in Tables 2 and 3 (The unit of thermal conductivity is W / (m * k), and description is omitted in the table.)

Manufacturing example # (1) 25 degree heat conductivity (2) 200 degrees C thermal conductivity 400 degrees
Thermal conductivity 600 degrees
Thermal conductivity 800 degrees
Thermal conductivity (1)-(2) {(1)-(2)} / (1) * surface
observe One - - - - - - - Fig. 8 2 31.665 26.764 22.481 19.2 16.625 4.901 0.1548 - 3 30.269 25.29 21.144 18.162 15.684 4.979 0.1645 - 4 - - - - - - - Fig. 10 (a) 7 - - - - - - - Fig. 10 (b) 14 23.659 13.307 9.419 7.497 6.315 10.352 0.4376 - Comparative Example 1 265.526 165.251 116.373 85.045 68.312 100.275 0.3776 Figure 9

* It indicates how many times the difference between the thermal conductivity measured at 200 ℃ and the thermal conductivity measured at 25 ℃ is the thermal conductivity measured at 25 ℃.

Manufacturing example # Relative density Etch improvement rate (%) Etch improvement rate (%) Fluoride ion
Particle formation Patan-myeon
Confirm One 90.76 - - - - 2 93.11 13.78 - X - 3 94.14 - - - - 4 94.32 - - - - 5 95.42 - - - - 6 94.35 - - - - 7 97.43 38.46 60 X Fig. 11 (a) 14 99.9 40.61 64 X Fig. 11 (b) Comparative Example 1 - Reference sample 38 X - Comparative Example 2 - - Reference sample X - Comparative Example 3 - - 49 O -

Referring to the above experimental results, it was also confirmed that the samples of Preparation Examples 1 to 14 have excellent state density properties as a whole, and the distribution of the carbon region is relatively evenly distributed even when the surface property results are observed. Particularly, in the case of Production Example 14, it was confirmed that the relative density was considerably high, and even when comparing the results of checking the fracture surface, it was quite dense and had a dense structure in which pores were hardly observed.

In the case of Production Example 5, in which boron oxide was applied as an additive, the relative density was higher than in Production Example 3, in which the same amount of carbon was applied, and in the case of Production Example 7 in which carbon and boron oxide were applied together, the sintering conditions were the same. Compared to those applied, it has a superior relative density value.

The samples thus prepared were found to have excellent etch resistance compared to silicon carbide in Comparative Example 1, and exhibited superior etch rates compared to silicon carbide, tungsten carbide, and single crystal silicon, and were also evaluated to have excellent etch resistance. In addition, it has been evaluated that it has an inert property that substantially forms particles by combining with fluorine ions in a plasma environment, so that more high-precision etching processing can proceed with fewer defects.

5. Comparison of etching rate

1) Coupon test

Preparation Example 7 and Comparative Example 1 to prepare a sample in a rectangular coupon shape (19 * 19 T, height 2 T, T = mm) having substantially the same size and height, respectively, and # 1 (Coupon Example) and Etching # 2 (Comparative Example of Coupon), respectively, and measuring the height before and after etching are shown in Table 4 below.

Etching conditions were applied with an exposure time of 420 hours with a plasma power of 800 W and a chamber pressure of 100 mTorr, and CF ₄ 50 sccm, Ar 100 sccm and O ₂ 20 sccm were applied as etching gas. In addition, pictures before and after etching are shown in FIG. 12.

# 1 (Example) # 2 (comparative example) Height before etching (mm) 2.011 2.009 Height after etching (mm) 1.994 1.983 Etch rate (%) * 0.85 1.29

* The etch rate is calculated using Equation 1 below.

[Equation 1]

Referring to Table 4, the case of the example showed an etch improvement rate of about 34% compared to the comparative example (reference sample). The etching improvement rate was calculated according to Equation 2 below. Samples of the examples were applied as ceramic parts.

[Equation 2]

2) Focus ring etching test

Comparative Examples 1 and 7 were manufactured, and Comparative Example 1 and Focusing Examples having substantially the same shape and size, respectively, were prepared to test the etching degree in the plasma equipment.

The etching conditions were applied with a plasma power of 2,000 W of RF, but the conditions such as chamber pressure and etching gas were all applied.

The focus ring is in the form shown in FIG. 1, and after etching, the heights of the four places indicated by the arrows in FIG. 1 are measured and the average values are shown in Table 5 below.

In addition, the measurement of the height was measured using a three-dimensional measuring device, and the inclined portion was evaluated by the value measured at each point P1-1, P1-2, and P1-3 shown in FIG. 3. The evaluation point was measured based on the point shown in FIG. 3.

The height and angle measurement results of each point are shown in Table 5 and FIG. 6 below.

Measurement position P1 P1-1 P1-2 P1-3 Comparative example Before etching, mm 2.50 3.03 3.55 4.08 After etching, mm 2.09 2.97 3.46 3.97 Etch rate *,% 16.4 1.98 2.54 2.7 Example Before etching, mm 2.50 3.03 3.55 4.08 After etching, mm 2.24 2.99 3.49 4.01 Etch rate *,% 10.4 1.32 1.69 1.72 Etch improvement rate *,% 36.6 33.3 33.3 36.4 Measurement position P2 P3 P4 P5 Comparative example Before etching, mm 4.6 4.6 4.6 4.6 After etching, mm 3.94 4.08 4.1 4.02 Etch rate *,% 14.35 11.30 10.87 12.61 Example Before etching, mm 4.58 4.58 4.58 4.58 After etching, mm 3.99 4.09 4.11 4.04 Etch rate *,% 12.88 10.7 10.26 11.79 Etch improvement rate *,% 10.2 5.4 5.6 6.5

* Etch rate was calculated according to Equation 1 below.

[Equation 1]

* Etch improvement rate is calculated according to Equation 2 below, and the sample of the example is used as the ceramic component and the sample of the comparative example is used as the reference sample.

[Equation 2]

H12, mm Htd, mm H12: Htd Comparative example 2.1 1.74 1: 0.83 Example 2.08 1.94 1: 0.93 Average reduction height of slope, mm Etch rate of slope **,% - Comparative example 0.08 2.41 _ Example 0.05 1.58 _

** The etch rate of the slope is the average value of the etch rate measured at the slopes of at least 3 points.

The preferred embodiments of the present invention have been described in detail above, but the scope of the present invention is not limited to this, and various modifications and improvements of those skilled in the art using the basic concept of the present invention defined in the following claims are also provided. It belongs to the scope of rights.

1: etch target 10: ceramic parts
100: body portion 200: seating portion
106: body top 206: seating top surface
150: slope 156 slope upper surface

Claims (12)

Contains boron carbide,
When etching for 300 minutes of exposure time with a plasma power of 800 W and a chamber pressure of 100 mTorr, the etching rate according to Equation 1 below is 1.2% or less,
The boron carbide is a ceramic component, the difference between the thermal conductivity measured at 200 ℃ and the thermal conductivity measured at 25 ℃ is 0.1 to 0.6 times the thermal conductivity measured at 25 ℃;
[Equation 1]

.
According to claim 1,
Etch improvement rate is represented by Equation 2 below,
A ceramic component having an etching improvement rate of 45% or more;
[Equation 2]

In Equation 2, the reference sample is a silicon ceramic component.
According to claim 1,
Etch improvement rate is represented by Equation 2 below,
Ceramic parts having an etch improvement rate of 20% or more;
[Equation 2]

In Equation 2, the reference sample is a chemical vapor-deposited silicon carbide ceramic component.
According to claim 1,
The ceramic component is a ceramic component, the difference between the thermal conductivity measured at 200 ℃ and the thermal conductivity measured at 25 ℃ 6 W / (m * k) or more.
According to claim 1,
The ceramic component is a focus ring, a ceramic component.
According to claim 1,
A ceramic component containing less than 500 ppm of metallic by-products.
It includes a seating portion having a first height and a body portion having a second height,
The seating portion includes a seating surface,
The body portion includes a body portion upper surface,
The upper surface of the seating portion includes a surface of the seating portion where an etch target is not disposed,
The etched surface includes the exposed surface of the seating portion and the upper surface of the main body,
Some or all of the etched surface includes boron carbide,
The boron carbide is a ceramic component, the difference between the thermal conductivity measured at 200 ℃ and the thermal conductivity measured at 25 ℃ is 0.1 to 0.6 times the thermal conductivity measured at 25 ℃.
The method of claim 7,
The boron carbide comprises a deposited boron carbide or sintered boron carbide, ceramic parts.
The method of claim 7,
It includes an inclined portion connecting the seating portion and the body portion,
The inclined portion is a ceramic component, including an inclined portion surface connecting the upper surface of the seating portion and the main body.
The method of claim 9,
The average etch rate of the inclined portion is 2.2% or less, ceramic parts.
The method of claim 9,
Etch improvement rate is represented by Equation 2 below,
The seating part exposed surface or the inclined wounded surface has an etch improvement rate of 20% or more compared to a reference sample,
The reference sample may include a ceramic component, which is an exposed surface or an inclined surface of a ceramic component including chemical vapor-deposited silicon carbide on an etched surface;
[Equation 2]

In Equation 2, the reference sample is a silicon carbide ceramic component deposited by chemical vapor deposition.
A placement step of positioning an etch target on an etching apparatus in which the ceramic component according to claim 1 or 7 is arranged with a focus ring; And an etching step of preparing the substrate by performing etching of the etching target;
The etching is carried out at a chamber pressure of 500 mTorr or less, an etching gas containing a fluorine-containing compound or a chlorine-containing compound, and a power of 500 W to 15,000 W.

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