KR102216815B1 - Semiconductor manufacturing parts including boron carbide resistant plasma members - Google Patents

Abstract

The present invention relates to a component for manufacturing a semiconductor including a boron carbide-resistant plasma member. According to one aspect of the present invention, the component includes boron carbide formed by a chemical vapor deposition (CVD) method. In X-ray diffraction analysis, a preferential growth peak is a plane (021).

Description

Components for semiconductor manufacturing including a plasma member for boron carbide resistance {SEMICONDUCTOR MANUFACTURING PARTS INCLUDING BORON CARBIDE RESISTANT PLASMA MEMBERS}

The present invention relates to a component for semiconductor manufacturing comprising a boron carbide-resistant plasma member, and more particularly, to a component for semiconductor manufacturing including a boron carbide-resistant plasma member including boron carbide formed by a chemical vapor deposition (CVD) method. .

In recent years, as the integration of semiconductor chips increases, the number of layers to be stacked increases and a three-dimensional structure is formed. Accordingly, the number of layers to be etched at one time increases, and at the same time, precise etching is required. Accordingly, high RF power is required in a semiconductor process, and equipment aimed at using RF power of 10,000 W or more, and recently up to 20,000 W, has been developed.

Currently, as plasma-resistant materials used in semiconductor manufacturing equipment, there are silicon (Si) or silicon carbide (CVD SiC) formed by chemical vapor deposition, but these materials do not exhibit sufficient durability required at high power. During the semiconductor process, there are problems due to generation of particles due to dropping of crystal grains from the surface of a material and occurrence of pitting due to a difference in partial etching degree of crystal grains according to crystal directions.

In particular, in the case of the existing CVD SiC material, partial overetching occurs due to micro cracks generated during processing in the initial use, and in this process, pre-sputtering is performed to control the particles generated by separation of crystal grains. The process proceeds after the stabilization is achieved, which acts as a factor that hinders productivity.

Accordingly, there is a need to develop a novel plasma-resistant member that has sufficient durability at high RF power and can prevent the occurrence of fittings due to differences in particle generation and partial etching.

The above-described background technology is possessed or acquired by the inventor in the process of deriving the disclosure content of the present application, and is not necessarily known as a known technology disclosed to the general public before the present application.

The present invention is to solve the above-described problems, and an object of the present invention is a boron carbide-resistant plasma member capable of securing uniformity of an etched surface while having sufficient durability even at high RF power, and a semiconductor manufacturing component including the same And it is to provide a manufacturing method thereof.

However, the problem to be solved by the present invention is not limited to the problems mentioned above, and other problems that are not mentioned will be clearly understood by those skilled in the art from the following description.

One aspect of the present invention includes a boron carbide formed by a chemical vapor deposition (CVD) method, and the preferential growth peak is (021) plane in X-ray diffraction analysis, a semiconductor manufacturing component comprising a boron carbide-resistant plasma member Provides.

According to an embodiment, the boron carbide may have a crystal grain size of 1 nm to 55 nm.

According to an embodiment, the size of the crystal grains is measured using the Scherrer equation based on the half width (FWHM) of the preferential growth peak in X-ray diffraction analysis, and the half width (deg) of the preferential growth peak May be 0.2 or more.

According to an embodiment, the crystal grains may have an atomic ratio of boron and carbon of 4:1.

According to an embodiment, the boron carbide may be formed at a temperature of 1,000 °C to 1,700 °C.

According to an embodiment, the boron carbide is any one or more selected from the group consisting of B ₄ C, B ₂ C, B ₃ C, B ₅ C, B ₁₃ C ₂ , B ₁₃ C ₃ and B ₅₀ C ₂ It may be included.

According to an embodiment, the boron carbide may have a purity of 99% or more.

According to an embodiment, the boron carbide may have an impurity content of 0.01 ppm to 30 ppm.

According to one embodiment, the impurity is any one or more selected from the group consisting of Al, Ca, Cr, Co, Cu, Fe, Li, Mg, Mn, Mo, Ni, K, Na, Ti, Zn, and Si. It may be included.

According to an embodiment, the boron carbide may have a pore-free crystal structure.

According to an embodiment, the boron carbide may have a relative density of 99% or more.

According to an embodiment, the boron carbide supplies 10 sccm to 50 sccm of CF ₄ gas and 1 sccm to 30 sccm of Ar gas, maintains a vacuum pressure of 1 mtorr to 20 mtorr, and maintains an RF power of 300 W to 1,000. In the plasma etching condition applied with W, the plasma etching amount may be 20% to 40% compared to the silicon etching amount.

According to an embodiment, the boron carbide supplies 10 sccm to 50 sccm of CF ₄ gas and 1 sccm to 30 sccm of Ar gas, maintains a vacuum pressure of 1 mtorr to 20 mtorr, and maintains an RF power of 300 W to 1,000. In the plasma etching condition applied to W, the plasma etching amount may be 60% to 70% compared to the silicon carbide (SiC) etching amount formed by chemical vapor deposition (CVD) method.

According to an embodiment, the component may include any one of an edge ring, a susceptor, and a showerhead.

Another aspect of the invention, the step of preparing a base material; And forming a boron carbide layer on the base material by a chemical vapor deposition (CVD) method. It provides a method of manufacturing a semiconductor manufacturing component including a plasma member for boron carbide resistance.

According to an embodiment, the step of forming the boron carbide layer may be performed at a temperature of 1,000° C. to 1,700° C.

The boron carbide-resistant plasma member according to the present invention includes boron carbide formed by a chemical vapor deposition method, thereby improving plasma resistance and uniform etching.

In addition, the semiconductor manufacturing component according to the present invention includes a boron carbide-resistant plasma member including boron carbide formed by a chemical vapor deposition method, thereby preventing particle generation and fitting phenomena caused by particle separation or partial etching in a semiconductor etching process. Can be prevented, and ultimately contribute to the improvement of integration and productivity of the semiconductor process.

Further, the method of manufacturing a component for semiconductor manufacturing according to the present invention has an effect of implementing a pore-free crystal structure, high purity, and high density of boron carbide by forming boron carbide by chemical vapor deposition by controlling the temperature.

In addition, by forming boron carbide in a chemical vapor deposition method, the ratio of boron and carbon can be precisely controlled by controlling the process conditions, and through this, the microstructure, hardness, and plasma resistance properties of boron carbide can be optimized. .

1 is a SEM image showing a microstructure of a surface of boron carbide according to an embodiment of the present invention.
2 is a SEM image showing the microstructure of the surface of sintered boron carbide (B ₄ C).
3 is an SEM image showing the microstructure of the surface of silicon carbide (SiC) formed by CVD.
4 is an AES analysis result showing the B/C ratio of boron carbide according to an embodiment of the present invention.
5 is a graph showing the etch rate of CVD boron carbide according to an embodiment of the present invention compared to silicon carbide (SiC) and silicon (Si) formed by CVD.
6 is a SEM image of a surface of boron carbide having a half width (deg) of 0.2 or more according to an embodiment of the present invention after plasma etching.
7 is a SEM image of a surface of boron carbide having a half width (deg) of less than 0.2 according to an embodiment of the present invention after plasma etching
8 is a SEM image of a surface of silicon, a commercial material, after plasma etching.
9 is a SEM image of the surface of sintered boron carbide (B4C), which is a commercial material, after plasma etching.
10 is a SEM image of a surface of a CVD silicon carbide (SiC) material after plasma etching.
11 is an XRD graph of boron carbide according to an embodiment of the present invention.
12 is a graph showing a change in grain size according to a change in half width (deg) of a preferred growth peak in the XRD analysis of boron carbide according to an embodiment of the present invention.
13 is a graph showing the change in the cross-sectional microstructure of boron carbide according to the B/C composition change.
14 is a graph showing changes in plasma resistance characteristics of boron carbide according to a change in B/C composition.
15 is a graph showing a change in hardness of boron carbide according to a change in B/C composition.

Hereinafter, exemplary embodiments will be described in detail with reference to the accompanying drawings. However, since various changes may be made to the embodiments, the scope of the rights of the patent application is not limited or limited by these embodiments. It should be understood that all changes, equivalents, or substitutes to the embodiments are included in the scope of the rights.

The terms used in the examples are used for illustrative purposes only and should not be interpreted as limiting. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present specification, terms such as "comprise" or "have" are intended to designate the presence of features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, but one or more other features. It is to be understood that the presence or addition of elements or numbers, steps, actions, components, parts, or combinations thereof, does not preclude in advance.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the embodiment belongs. Terms as defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related technology, and should not be interpreted as an ideal or excessively formal meaning unless explicitly defined in this application. Does not.

In addition, in the description with reference to the accompanying drawings, the same reference numerals are assigned to the same components regardless of the reference numerals, and redundant descriptions thereof will be omitted. In describing the embodiments, when it is determined that a detailed description of related known technologies may unnecessarily obscure the subject matter of the embodiments, the detailed description thereof will be omitted.

In addition, in describing the constituent elements of the embodiment, terms such as first, second, A, B, (a) and (b) may be used. These terms are only used to distinguish the component from other components, and the nature, order, or order of the component is not limited by the term. When a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected or connected to that other component, but another component between each component It should be understood that may be “connected”, “coupled” or “connected”.

Components included in one embodiment and components including common functions will be described using the same name in other embodiments. Unless otherwise stated, descriptions in one embodiment may be applied to other embodiments, and detailed descriptions in the overlapping range will be omitted.

One aspect of the present invention includes a boron carbide formed by a chemical vapor deposition (CVD) method, and the preferential growth peak is (021) plane in X-ray diffraction analysis, a semiconductor manufacturing component comprising a boron carbide-resistant plasma member Provides.

The boron carbide formed by the chemical vapor deposition method according to the present invention can control the size of the boron carbide crystal grains formed through temperature control during deposition, and has a pore-free and dense crystal structure.

In addition, the components for semiconductor manufacturing including the plasma member for boron carbide-resistant by the CVD method of the present invention do not include the sintering process in the manufacturing process, so that pores due to the sintering process are not generated, and impurities due to the addition of a sintering aid It does not have high density and high purity characteristics.

The chemical vapor deposition method may mean depositing a product on the surface of the base material by reacting a gaseous compound on the surface of the heated base material.

For example, by spraying a gaseous carbon precursor and a boron precursor on the base material, respectively or by mixing, it may be to form boron carbide by a thermochemical reaction on the base material.

According to an embodiment, the boron carbide may include a bulk form or a coating layer form formed on a base material.

According to an embodiment, the boron carbide may have a crystal grain size of 1 nm to 55 nm.

Preferably, the boron carbide may have a grain size of 1 nm to 50 nm or 19 nm to 55 nm, more preferably, 20 nm to 50 nm, and even more preferably, 30 nm To 50 nm.

If the size of the boron carbide grains exceeds the above range, uniform etching is not performed, and during the semiconductor etching process, particles are generated due to separation of grains or partial etching due to strong plasma, or pitting phenomenon occurs. I can.

In addition, when the size of the boron carbide crystal grains is less than the above range, the crystal grains may be separated or etched when the plasma is exposed to etch into the material.

In the boron carbide according to the present invention, since the size of the grains is controlled to be 55 nm or less, uniform etching at a level similar to that of single crystal silicon can be achieved by controlling partial etching or separation of grains during plasma etching.

According to an embodiment, the size of the crystal grains may be measured using the Scherrer equation based on the half width (FWHM) of the preferential growth peak in X-ray diffraction analysis.

The half width may mean the half width of the preferential growth peak shown in X-ray diffraction analysis, and the Scherrer equation may mean an equation represented by Reaction Formula 1.

[Scheme 1]

Scherrer equation: grain size (nm) = 0.9 x (λ/ (B x cosθ))

Here, λ is the measurement wavelength of the X-ray diffraction analysis, B is the half width (rad) of the priority growth peak, and θ is the angle value (rad) of the priority growth peak.

According to an embodiment, the preferential growth peak may be a (021) plane.

The size of the crystal grains can be clearly and precisely controlled using X-ray diffraction analysis and Scheller's method, thereby increasing process productivity and reducing cost.

According to an embodiment, the half width (deg) of the preferential growth peak may be 0.2 or more.

Preferably, the half width (deg) of the preferential growth peak may be 0.2 to 0.5, more preferably 0.2 to 0.4.

When the half value width (deg) of the preferential growth peak increases, the size of the crystal grains decreases, and when the half value width (deg) of the priority growth peak decreases, the size of the crystal grain increases.

If the half-width (deg) of the dominant growth peak is less than the above range, large crystal grains are formed in the boron carbide and particles are generated due to separation of grains or partial etching due to strong plasma during the semiconductor etching process, or a fitting phenomenon. This can happen.

In addition, when the above range is exceeded, fine grains are formed, and thus, when exposed to plasma, the grains may be separated or etched to penetrate into the material.

According to an embodiment, the crystal grains may have an atomic ratio of boron and carbon of 4:1.

According to an embodiment, the atomic ratio of boron and carbon may be controlled by controlling the CVD process conditions.

The CVD process conditions include the content ratio, temperature, time, etc. of the carbon source and the boron source.

Boron carbide B ₄ C stoichiometrically, the ratio of B:C should be 4: 1, but since the atomic structure of B ₄ C has a chain structure, there is a case where C exists at the B position or B exists at the C position. There are many, so it does not have a crystal structure with accurate stoichiometry. Due to the characteristics of B ₄ C, boron-rich boron carbide and carbon-rich boron carbide exist, and the microstructure, plasma resistance, and hardness of boron carbide change according to the composition ratio of B and C.

In general, the boron carbide formed by sintering can partially control the content of carbon and boron by using an additive in the sintering process, but the composition cannot be changed in the crystallization step. This is because the composition of the powder to be used in the initial stage is determined, so that the composition of the B/C is determined at an early stage, so that change during the process is impossible.

In comparison, since the boron carbide according to the present invention is formed by chemical vapor deposition, the composition of the boron carbide crystal structure can be controlled by adjusting the ratio and process conditions of the carbon source and the boron source in the CVD process.

That is, by controlling the CVD process conditions, boron carbide having different crystal structures having a dense bulk structure can be formed, the atomic ratio of boron and carbon can be controlled to be 4:1, and the microstructure of the boron carbide material can be controlled. Plasma characteristics and hardness can be optimized.

According to an embodiment, the boron carbide may be formed at a temperature of 1,000 °C to 1,700 °C.

If the boron carbide is formed at a temperature exceeding the temperature range, the size of the crystal grains increases to form a large grain, and a gap may occur at the grain boundary, so that particles may be generated in the etching process or a pitting phenomenon may occur.

In addition, when formed at a temperature less than the above temperature range, the formation rate of boron carbide is lowered, a number of pores are generated in the tissue, and particles may be generated due to separation of fine grains in the etching process by plasma.

According to one embodiment, the boron carbide may mean a compound consisting of B and C.

According to an embodiment, the boron carbide is any one or more selected from the group consisting of B ₄ C, B ₂ C, B ₃ C, B ₅ C, B ₁₃ C ₂ , B ₁₃ C ₃ and B ₅₀ C ₂ It may include, and preferably, may include B ₄ C.

According to an embodiment, the boron carbide may be B ₄ C.

According to an embodiment, the boron carbide may have a purity of 99% or more.

Preferably, the boron carbide may have a purity of 99.99% or more.

The boron carbide-resistant plasma member according to the present invention may contain high-purity boron carbide and suppress generation of reactive particles that may occur during a semiconductor process.

The purity of the boron carbide may be measured through glow discharge mass spectrometry (GDMS).

The boron carbide according to the present invention has high purity characteristics compared to that of sintered boron carbide having a purity of 98% or less, thereby suppressing the generation of reactive particles that may occur during a semiconductor process.

According to an embodiment, the boron carbide may have an impurity content of 0.1 ppm to 30 ppm.

Preferably, the boron carbide may have an impurity content of 0.1 ppm to 26 ppm, and more preferably, an impurity content of 0.1 ppm to 25.5 ppm.

The impurities may mean all compounds except carbon and boron.

According to one embodiment, the impurity is any one or more selected from the group consisting of Al, Ca, Cr, Co, Cu, Fe, Li, Mg, Mn, Mo, Ni, K, Na, Ti, Zn, and Si. It may be included.

The boron carbide according to the present invention is formed by a chemical vapor deposition method so that a separate material such as a sintering aid is not added, and thus has a high purity characteristic with a very low content of impurities. This high purity characteristic not only suppresses generation of reactive particles in the semiconductor process, but also enables uniform etching.

According to an embodiment, the boron carbide may have a pore-free crystal structure.

The boron carbide has a pore-free crystal structure, that is, a dense structure without pores in the structure, and has improved plasma resistance because there is no gap between crystal grain boundaries.

According to an embodiment, the boron carbide may have a relative density of 99% or more.

The relative density may mean a density value expressed based on the standard boron carbide density.

Since the boron carbide has a relative density of 99% or more, mechanical properties and plasma resistance are improved due to a compact structure in which almost no pores exist in the structure.

According to an embodiment, the boron carbide supplies 10 sccm to 50 sccm of CF ₄ gas and 1 sccm to 30 sccm of Ar gas, maintains a vacuum pressure of 1 mtorr to 20 mtorr, and maintains an RF power of 300 W to 1,000. In the plasma etching condition applied to W, the plasma etching amount may be 20% to 40% compared to silicon.

That is, under the above conditions, the etching amount of the boron carbide may be 20% to 40% of the silicon etching amount, and preferably, the plasma etching amount may be 25% to 35%.

The plasma etching amount may be measured after performing the etching process for 5 hours under the above conditions.

According to an embodiment, the boron carbide supplies 10 sccm to 50 sccm of CF ₄ gas and 1 sccm to 30 sccm of Ar gas, maintains a vacuum pressure of 1 mtorr to 20 mtorr, and maintains an RF power of 300 W to 1,000. In the plasma etching condition applied with W, the plasma etching amount may be 60% to 70% compared to silicon carbide (SiC) formed by a chemical vapor deposition (CVD) method.

That is, under the above conditions, the etching amount of the boron carbide may be 60% to 70% of the etching amount of silicon carbide (SiC) formed by a chemical vapor deposition (CVD) method, and preferably, 64% to 68% It may represent a plasma etching amount of.

According to an embodiment, the surface of the boron carbide may be uniformly etched by plasma.

The boron carbide is uniformly etched like silicon and exhibits an etching amount of 20% to 40% compared to the silicon etching amount, and thus has significantly improved plasma resistance compared to silicon.

In addition, there is no particle generation or fitting phenomenon due to large grains, and thus, it is suitable for use as a plasma-resistant material in a high RF power condition, that is, a harsh etching environment.

According to an embodiment, the component may be used to be exposed to plasma inside the chamber.

According to an embodiment, the component may include any one of an edge ring, a susceptor, and a showerhead.

Another aspect of the invention, the step of preparing a base material; And forming a boron carbide layer on the base material by a chemical vapor deposition (CVD) method. It provides a method of manufacturing a semiconductor manufacturing component including a plasma member for boron carbide resistance.

The base material may include metal, ceramic, or a mixture thereof.

According to one embodiment, the base material may further include a silicon carbide (SiC) coating layer.

According to an embodiment, the step of forming the boron carbide layer may include forming a boron carbide layer by a chemical vapor deposition (CVD) method by reacting a gaseous carbon precursor and a boron precursor on the base material.

According to one embodiment, the carbon precursor may include any one or more selected from the group consisting of CH ₄ , C ₂ H ₆ and C ₃ H ₈ .

According to one embodiment, the boron precursor may include any one or more selected from the group consisting of BCl ₃ , B ₂ H ₆ and BF ₃ .

According to an embodiment, the step of forming the boron carbide layer may be performed at a temperature of 1,000° C. to 1,700° C.

The crystal grain size of the boron carbide layer formed in the above temperature range is controlled, so that the pore-free crystal structure, high density, and high purity characteristics of the boron carbide layer can be realized.

According to an embodiment, in the step of forming a boron carbide layer on the base material by a chemical vapor deposition (CVD) method; in the atomic ratio of carbon and boron in the boron carbide crystal by controlling the content ratio of the carbon source and the boron source It may be to control.

That is, by forming boron carbide by a chemical vapor deposition method, the ratio of boron and carbon can be precisely controlled, thereby optimizing the microstructure, hardness, and plasma resistance of boron carbide.

Hereinafter, the present invention will be described in more detail by examples and comparative examples.

However, the following examples are for illustrative purposes only, and the contents of the present invention are not limited to the following examples.

<Example> Formation of boron carbide by chemical vapor deposition method

Carbonization by chemical vapor deposition (CVD) method by reacting gaseous carbon precursors CH ₄ , C ₂ H ₆ , C ₃ H ₈ and boron precursors BCl ₃ , B ₂ H ₆ and BF ₃ at a temperature of 1,000 ℃ to 1,700 ℃ Boron (B ₄ C) was formed.

<Experimental Example 1> Structure analysis of boron carbide

The microstructure of the surface of the boron carbide prepared in Examples was observed using a scanning electron microscope.

In addition, in order to clearly grasp the difference in surface structure, the surfaces of sintered boron carbide (B ₄ C) and silicon carbide (SiC) formed by CVD were observed.

1 is a SEM image showing a microstructure of a surface of boron carbide according to an embodiment of the present invention.

2 is a SEM image showing the microstructure of the surface of sintered boron carbide (B ₄ C).

3 is an SEM image showing the microstructure of the surface of silicon carbide (SiC) formed by CVD.

Referring to Figure 1, it can be seen that the boron carbide according to an embodiment of the present invention has a dense structure without pores.

On the other hand, referring to FIGS. 2 and 3, it can be seen that a number of pores exist on the surface of sintered boron carbide (B ₄ C), and impurities (white portions) such as Fe and Ti used as sintering aids are found. In addition, it can be seen that large crystal grains and crystal interfaces exist on the surface of silicon carbide (SiC) formed by CVD.

Table 1 is a value obtained by measuring the density value of sintered boron carbide which is actually used in practice, and Table 2 is a value obtained by measuring the density value of the CVD boron carbide of the present invention.

Referring to Tables 1 and 2, the average bulk density of boron carbide according to the present invention was 2.5031 g/cc, showing a relative density of 99.2%, but the average bulk density of sintered boron carbide (B ₄ C) was 2.4787 g. It shows a relative density of 98.4% in /cc, so it can be seen that in the case of sintered boron carbide (B ₄ C), a number of pores are not removed during the sintering process.

Impurities contained in the material generate reactive particles in the semiconductor process, and in the case of large crystal grains, when the RF power is increased, particles are generated by partial etching or rapid etching of the surface according to the crystal direction of the large crystal grains. In addition, the large number of pores present in the material weakens the mechanical properties, thereby lowering the plasma corrosion resistance.

Considering this, the boron carbide according to the present invention does not contain impurities due to sintering aids, and has a dense structure without large crystal grains or pores, thereby improving plasma corrosion resistance and preventing the generation of particles in the semiconductor process. Can be seen.

<Experimental Example 2> Analysis of the composition of boron carbide

In order to confirm the composition of the boron carbide generated in the examples, the depth profile was analyzed with an Auger Electron Spectroscope (AES) for the B/C ratio, and the electron beam was sputtered for 30 minutes so that the quantitative values of B and C were constant. By scanning, the depth profile of the boron carbide was analyzed.

AES Nanoprobe (PHI 700) manufactured by ULVAC-PHI was used as the AES analysis equipment.

The AES analysis is an equipment that analyzes the Auger electron energy generated by sputtering with an ion beam to etch the surface of the specimen and at the same time scanning the electron beam to the specimen, and quantitative and qualitative analysis of each element can be performed.

4 is an AES analysis result showing the B/C ratio of boron carbide according to an embodiment of the present invention.

Referring to FIG. 4, it can be seen that the ratio of boron carbide B:C according to an embodiment of the present invention is 4:1, and it can be seen that the boron carbide formed through this is B ₄ C.

<Experimental Example 3> Purity measurement of boron carbide

In order to measure the purity of the boron carbide produced in the examples, boron carbide was subjected to GDMS (Glow Discharge Mass Spectrometry) analysis based on a total of 16 elements.

Table 3 is a GDMS analysis result of boron carbide according to an embodiment of the present invention.

wt. ppm wt. ppm Al 0.024 Mn 0.003 Ca 0.04 Mo One Cr 0.69 Ni 1.3 Co 0.025 K 0.03 Cu 0.01 Na 0.003 Fe 0.55 Ti 0.65 Li 0.003 Zn 0.055 Mg 0.02 Si 20.7 Sum 25.103

Referring to Table 3, it can be seen that the impurity content of boron carbide according to an embodiment of the present invention is 25.1 ppm in total, and when converted to purity, it can be confirmed that it has a high purity of 99.9975%.

In particular, it can be seen that sintered boron carbide (B ₄ C), which is a commercial material, exhibits a very high purity compared to having a purity of 98% or less due to a sintering additive or the like.

Through this, it can be seen that the boron carbide according to the present invention has a high purity characteristic, so that the generation of reactive particles that may occur during a semiconductor process can be suppressed.

<Experimental Example 4> Measurement of etching amount by plasma

Prepare the boron carbide prepared in the example and the commercially available sintered boron carbide (B ₄ C), silicon carbide (SiC) and silicon (Si) formed by CVD, RF Power 500 W, gas is CF ₄ 30 sccm, Ar Etching amount was analyzed by performing an etching test for 5 hours under the etching condition of 10 sccm and 10 mtorr of vacuum pressure.

5 is a graph showing the etch rate of CVD boron carbide according to an embodiment of the present invention compared to silicon carbide (SiC) and silicon (Si) formed by CVD.

Referring to FIG. 5, it can be seen that the boron carbide according to the present invention exhibits an etching amount of 31.1% compared to the etching amount of silicon and 66.0% of the etching amount of CVD SiC.

That is, it can be seen that the boron carbide according to the present invention exhibits an etching improvement rate of 69% compared to the amount of silicon etching and 34% compared to the amount of CVD SiC etching.

In addition, it can be seen that the etch improvement rate improved than that of sintered boron carbide (B ₄ C).

Through this, it can be seen that the boron carbide according to the present invention has superior plasma resistance properties than commercial materials such as silicon, silicon carbide (SiC), and sintered boron carbide (B ₄ C).

<Experimental Example 5> Surface analysis after etching by plasma

After etching of the boron carbide, sintered boron carbide (B ₄ C), and silicon prepared in the plasma-etched example in Experimental Example 4, the surfaces were observed using a scanning electron microscope.

6 is a SEM image of a surface of boron carbide having a half width (deg) of 0.2 or more according to an embodiment of the present invention after plasma etching.

7 is a SEM image of a surface of boron carbide having a half width (deg) of less than 0.2 according to an embodiment of the present invention after plasma etching.

8 is a SEM image of the surface of silicon, a commercial material, after plasma etching.

9 is a SEM image of the surface of sintered boron carbide (B ₄ C), which is a commercial material, after plasma etching.

10 is an SEM image of a surface of a CVD silicon carbide (SiC) material after plasma etching.

Referring to FIGS. 6 to 10, it can be seen that the boron carbide according to the present invention is uniformly etched to exhibit an etching surface substantially the same as that of silicon.

On the other hand, in the case of sintered boron carbide (B ₄ C), which is a commercial material, it can be confirmed that a number of crystal grains are eliminated by etching of the crystal interface.

That is, in the case of sintered boron carbide (B ₄ C), the amount of etching by the plasma and the boron carbide according to the present invention were similar, but during the etching process, grains were eliminated and particles were generated by the sintering aid, so uniform etching was not performed I can confirm.

In addition, in the case of CVD silicon carbide (SiC), it can be confirmed that a partial etching phenomenon occurred due to large grains.

Therefore, it can be seen that the boron carbide according to the present invention has excellent plasma resistance compared to commercial materials such as silicon, sintered boron carbide, and silicon carbide formed by the CVD method, and can be used as a plasma material even in a harsher etching environment. You can see that you can.

<Experimental Example 6> Measurement of grain size of boron carbide

XRD (X-RAY DIFFRACTION) analysis of the boron carbide prepared in the Example was performed under the conditions of a measurement range of 10 to 80°, power 40kV, 40mA, scan speed 10, and scan step 0.05.

Subsequently, in XRD analysis, the grain size of the boron carbide prepared in Example was measured using the following Scherrer equation based on the half width of the preferential growth peak.

Scherrer equation, grian size[nm] = 0.9 x (λ/ (B x cosθ))

Here, λ is the XRD measurement wavelength (1.54 using Cu target), B is the half width (rad) of the priority growth peak 021, and θ is the angle value (rad) of the priority growth peak.

11 is an XRD graph of boron carbide according to an embodiment of the present invention.

Referring to FIG. 11, it can be seen that the preferential growth peak is the (021) plane in the X-ray diffraction analysis of boron carbide according to an embodiment of the present invention.

12 is a graph showing a change in grain size according to a change in half width (deg) of a preferred growth peak in the XRD analysis of boron carbide according to an embodiment of the present invention.

In FIG. 12, T1 to T5 refer to different temperature conditions, and T1 is the lowest temperature and T5 is the highest temperature in the order of T1 <T2 <T3 <T4 <T5.

Referring to FIG. 12, when the half-value width (deg) increases, the size of the crystal grains decreases.In the boron carbide according to the present invention, when the half-value width (deg) is 0.2 or more, the size of the crystal grains is 50 nm or less.

When the size of the crystal grains is less than 55 nm, the same uniform etching as that of silicon is exhibited, so it can be seen that the half-value width (deg) should be 0.2 or more and preferably in the range of 0.25 to 0.4.

<Experimental Example 7> Characteristics change according to B/C composition change

While changing the B/C composition, changes in cross-sectional microstructure, plasma resistance and hardness were observed.

Table 4 shows the carbon content (at%) of the boron carbide used.

Carbon content B #1 17 at% N #1 (B ₄ C) 20 at% C#1 33 at% C#2 35 at% C#3 37 at% C#4 49 at% C#5 63 at%

13 is a graph showing a change in cross-sectional microstructure of boron carbide according to a change in B/C composition.

13, Boron-rich boron carbide and normal boron carbide (B ₄ C) have a similar cross-sectional structure, and in carbon-rich boron carbide, when the carbon content is 33 at% or less, the same small crystal grains show a uniform structure. Can be confirmed. However, when the carbon content is more than 34 at%, the carbon-rich area begins to appear, and the bright area is enlarged. Finally, when the carbon content is more than 60 at%, it is not possible to form a dense structure of bulk but is formed into a dendritic form. It can be seen that thin film or bulk production becomes impossible.

14 is a graph showing changes in plasma resistance characteristics of boron carbide according to a change in B/C composition.

Referring to FIG. 14, in the range in which the carbon content increases from 20 to 50 at%, the etching improvement roll was increased by 1% compared to the silicon etch amount compared to the conventional normal boron carbide (B ₄ C). The etch improvement rate decreased by more than 5% compared to the etch amount standard. However, when the carbon content was 20-50 at%, as the carbon content increased, partial etchings appeared on the etched surface, forming an uneven surface.

In addition, it can be seen that boron-rich boron carbide decreases the etching improvement rate by 2% compared to normal boron carbide (B ₄ C) based on the amount of silicon etching.

As a result, in carbon-rich boron carbide with an increased carbon content, a slight improvement in plasma resistance is achieved until the carbon content is 20 to 50 at%, but partial etching occurs on the surface as the carbon content increases. It can be seen that an increase in the above carbon content or boron content appears as a factor that lowers the plasma resistance of boron carbide.

15 is a graph showing a change in hardness of boron carbide according to a change in B/C composition.

Referring to FIG. 15, in the case of hardness, it can be seen that there is almost no change according to the change of carbon content, and then the hardness decreases rapidly at 60 at% or more.

In addition, boron-rich boron carbide showed the largest hardness value, and it can be seen that the hardness gradually decreases within the carbon content within 50 at% of normal boron carbide (B ₄ C).

This is a phenomenon caused by the carbon-rich structure on the microstructure, and it can be seen that the characteristic opposite to the plasma resistance within 50 at% is exhibited.

As described above, although the embodiments have been described by the limited drawings, a person of ordinary skill in the art can apply various technical modifications and variations based on the above. For example, the described techniques are performed in a different order from the described method, and/or components such as a system, structure, device, circuit, etc. described are combined or combined in a form different from the described method, or other components Alternatively, even if substituted or substituted by an equivalent, an appropriate result can be achieved.

Therefore, other implementations, other embodiments and claims and equivalents fall within the scope of the following claims.

Claims (16)

Including boron carbide formed by chemical vapor deposition (CVD) method,
In X-ray diffraction analysis, the preferential growth peak is the (021) plane,
The boron carbide has a crystal grain size of 1 nm to 55 nm,
Components for semiconductor manufacturing comprising a boron carbide-resistant plasma member.
delete The method of claim 1,
The size of the crystal grains,
It was measured using the Scherrer equation based on the half width (FWHM) of the preferential growth peak in X-ray diffraction analysis,
The half value width (deg) of the preferential growth peak is 0.2 or more,
Components for semiconductor manufacturing comprising a boron carbide-resistant plasma member.
The method of claim 1,
The crystal grains,
The atomic ratio of boron and carbon is 4:1,
Components for semiconductor manufacturing comprising a boron carbide-resistant plasma member.
The method of claim 1,
The boron carbide is formed at a temperature of 1,000 ℃ to 1,700 ℃,
Components for semiconductor manufacturing comprising a boron carbide-resistant plasma member.
The method of claim 1,
The boron carbide includes any one or more selected from the group consisting of B ₄ C, B ₂ C, B ₃ C, B ₅ C, B ₁₃ C ₂ , B ₁₃ C ₃ and B ₅₀ C ₂ ,
Components for semiconductor manufacturing comprising a boron carbide-resistant plasma member.
The method of claim 1,
The boron carbide has a purity of 99% or more,
Components for semiconductor manufacturing comprising a boron carbide-resistant plasma member.
The method of claim 1,
The boron carbide, the content of impurities is 0.1 ppm to 30 ppm,
Components for semiconductor manufacturing comprising a boron carbide-resistant plasma member.
The method of claim 8,
The impurities include any one or more selected from the group consisting of Al, Ca, Cr, Co, Cu, Fe, Li, Mg, Mn, Mo, Ni, K, Na, Ti, Zn and Si,
Components for semiconductor manufacturing comprising a boron carbide-resistant plasma member.
The method of claim 1,
The boron carbide has a pore-free crystal structure,
Components for semiconductor manufacturing comprising a boron carbide-resistant plasma member.
The method of claim 1,
The boron carbide has a relative density of 99% or more,
Components for semiconductor manufacturing comprising a boron carbide-resistant plasma member.
The method of claim 1,
The boron carbide,
In plasma etching conditions in which 10 sccm to 50 sccm of CF ₄ gas and 1 sccm to 30 sccm of Ar gas were supplied, the vacuum pressure was maintained at 1 mtorr to 20 mtorr, and the RF power was applied at 300 W to 1,000 W,
It represents a plasma etching amount of 20% to 40% compared to the silicon etching amount,
Components for semiconductor manufacturing comprising a boron carbide-resistant plasma member.
The method of claim 1,
The boron carbide,
In plasma etching conditions in which 10 sccm to 50 sccm of CF ₄ gas and 1 sccm to 30 sccm of Ar gas were supplied, the vacuum pressure was maintained at 1 mtorr to 20 mtorr, and the RF power was applied at 300 W to 1,000 W,
It represents the plasma etching amount of 60% to 70% compared to the silicon carbide (SiC) etching amount formed by chemical vapor deposition (CVD) method,
Components for semiconductor manufacturing comprising a boron carbide-resistant plasma member.
The method of claim 1,
The part, which includes any one of an edge ring, a susceptor and a showerhead,
Components for semiconductor manufacturing comprising a boron carbide-resistant plasma member.
Preparing a base material; And
Including; forming a boron carbide layer on the base material by a chemical vapor deposition (CVD) method; and
The boron carbide has a crystal grain size of 1 nm to 55 nm,
A method of manufacturing a component for semiconductor manufacturing comprising a boron carbide-resistant plasma member.
The method of claim 15,
The step of forming the boron carbide layer is performed at a temperature of 1,000 °C to 1,700 °C,
A method of manufacturing a component for semiconductor manufacturing comprising a boron carbide-resistant plasma member.

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