WO2024143947A1 - Tantalum carbide-coated material - Google Patents

Abstract

The present disclosure relates to a tantalum carbide-coated material, which may comprise a buffer layer formed on a substrate, and a tantalum carbide film.

Description

Tantalum carbide composite

The present disclosure relates to a tantalum carbide coated-material according to embodiments.

Susceptor parts used in semiconductor manufacturing equipment have the problem that the carbon material is etched by corrosive gas when the carbon material used in the existing semiconductor process is used as is, so silicon carbide (silicon carbide) is added to the surface of the carbon material structure. Parts coated with SiC) or tantalum carbide (TaC) are used.

A tantalum carbide composite material coated with tantalum carbide (TaC) on the surface of a carbon material generates stress due to the difference in thermal expansion coefficient between the carbon material and the tantalum carbide film, causing cracks and warping, which can cause damage and affect the lifespan of the parts to which it is applied. is giving

Parts coated with tantalum carbide (TaC) use a tantalum carbide composite material coated with tantalum carbide (TaC) on the surface of the carbon material. To reduce the stress between the carbon substrate and tantalum carbide (TaC) and prevent peeling of the coating layer, tantalum carbide (TaC) and tantalum carbide (TaC) are used. Carbon base materials with similar thermal expansion coefficients have been used. However, the types of carbon substrates with a coefficient of thermal expansion similar to tantalum carbide are limited, so there are problems in applying them to tantalum carbide coating materials. In addition, even if a carbon substrate having a coefficient of thermal expansion similar to that of tantalum carbide is applied, problems such as stress generation, bending, cracking, and peeling may occur.

Accordingly, in order to solve the above-mentioned problem, according to one embodiment, the present disclosure introduces a buffer layer for stress relief between the substrate and the tantalum carbide film to reduce stress, bending, cracking, peeling, etc. of the tantalum carbide coating layer and the carbon substrate. A relaxed tantalum carbide composite can be provided. According to one embodiment, the present disclosure can provide a semiconductor manufacturing component that includes a tantalum carbide composite incorporating a buffer layer for stress relief and can improve life stability and the stability and process efficiency of the semiconductor manufacturing process.

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

According to one embodiment, the tantalum carbide composite includes a substrate; and a tantalum carbide film formed on at least one surface of the substrate. It includes a buffer layer between the substrate and the tantalum carbide film; It includes, and the buffer layer may include a material of van der Waals bond.

According to one embodiment, the van der Waals bond material is at least one selected from the group consisting of pyrolytic carbon, BN (Boron Nitride), MoS ₂ , WSe ₂ , ReS ₂ , MoTe ₂ , and combinations thereof. It may include.

According to one embodiment, the thickness of the buffer layer may be 1 ㎛ to 50 ㎛.

According to one embodiment, the atomic ratio of Ta to C in the tantalum carbide film may be 0.9 to 1.34.

According to one embodiment, the tantalum carbide film may be formed by CVD.

According to one embodiment, the thickness of the tantalum carbide film may be 10 ㎛ to 100 ㎛.

According to one embodiment, the substrate may include at least one selected from the group consisting of graphene, graphite, and fullerene.

According to one embodiment, the warpage of the tantalum carbide composite may be 10 ㎛ to 50 ㎛. According to one embodiment, as a method of measuring warpage of the tantalum carbide composite, (a)

Manufacturing a tantalum carbide coated product measuring 200 mm x 3 mm; (b) measuring the height of the product based on the upper half of a CMM measuring machine ( Coordinate Measuring Machine, 3D shape measuring machine); and (c) measuring 10 points at equal intervals of 0°, 60°, and 120°; It is a measurement method that includes a total of 30 points, which may include expressing the deviation of the measured value as bending.

According to one embodiment, the tantalum carbide film may be crack-free or may include cracks with a width of 0.3 ㎛ to 0.6 ㎛.

According to one embodiment, the coefficient of thermal expansion (CTE) of the tantalum carbide film may be greater than 6 x 10 ^-6 /K, and the coefficient of thermal expansion (CTE) of the substrate may be 6 x 10 ^-6 /K or less.

According to one embodiment, the tantalum carbide composite may reduce the width size of cracks in the tantalum carbide film and reduce the occurrence of warpage by introducing a buffer layer for stress relief between the substrate (e.g., carbon substrate) and the tantalum carbide film.

According to one embodiment, components for semiconductor manufacturing have improved lifetime stability by applying a tantalum carbide composite material that introduces a buffer layer for stress relief between a substrate (e.g., carbon substrate) and a tantalum carbide film, and process stability in the semiconductor manufacturing process. And process efficiency can be improved.

Figure 1 exemplarily shows the configuration of a tantalum carbide composite material in which a tantalum carbide film is formed on one surface of a substrate, according to one embodiment.

Figure 2 exemplarily shows the configuration of a tantalum carbide composite material in which a tantalum carbide film is formed on the entire surface of the substrate, according to one embodiment.

Figure 3 shows a cross-sectional SEM image of a tantalum carbide composite, according to one embodiment.

FIGS. 4A, 4B, and 4C are SEM images of the surface of the tantalum carbide layer in a tantalum carbide composite, according to an embodiment. FIG. 4A is an SEM image of Comparative Example 1, and FIG. 4B is a SEM image of Example 4. This is an SEM image, and Figure 4c is an SEM image of Example 1.

Figure 5 shows the width size of fine cracks in a tantalum carbide composite material, according to one embodiment.

Figure 6 shows the warpage size of micro cracks in a tantalum carbide composite material, according to one embodiment.

Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings. In describing the present invention, if a detailed description of a related known function or configuration is judged to unnecessarily obscure the gist of the present invention, the detailed description will be omitted. Additionally, the terms used in this specification are terms used to appropriately express preferred embodiments of the present invention, and may vary depending on the intention of the user, operator, or customs in the field to which the present invention belongs. Therefore, definitions of these terms should be made based on the content throughout this specification. The same reference numerals in each drawing indicate the same members.

Throughout the specification, when a member is said to be located “on” another member, this includes not only cases where a member is in contact with another member, but also cases where another member exists between the two members.

Throughout the specification, when a part “includes” a certain component, this does not mean excluding other components, but rather means that it can further include other components.

Hereinafter, the tantalum carbide composite material of the present invention will be described in detail with reference to examples and drawings. However, the present invention is not limited to these examples and drawings.

According to one embodiment, Figure 1 shows a tantalum carbide composite. In Figure 1, the tantalum carbide composite includes a substrate 100; and a tantalum carbide film 300 formed on at least one surface of the substrate 100; It includes a buffer layer 200 between the substrate 100 and the tantalum carbide film 300; may include. As an example, referring to FIG. 1, the tantalum carbide film 300 may be formed on the top surface, the bottom surface, or both of the substrate 100. As an example, referring to FIG. 2, the tantalum carbide film 300 may be formed on the entire surface of the substrate 100.

According to one embodiment, the substrate 100 may be appropriately selected depending on the purpose of the tantalum carbide composite material, and for example, may be a carbon substrate in consideration of the tantalum carbide film 300 and the thermal expansion coefficient. In some examples, the substrate 100 may include at least one selected from the group consisting of graphene, graphite, and fullerene.

According to one embodiment, the thickness of the substrate 100 may be 1 mm (millimeter) to 10 mm. in some examples 1 mm to 10 mm; 1 mm to 8 mm; 1 mm to 6 mm; 1 mm to 4 mm; Or it may be 1 mm to 2 mm. In some examples, if the thickness of the substrate 100 is within the mentioned range, deformation of the substrate 100 after deposition of the tantalum carbide film 300 is minimized, and the lifespan of the component using the tantalum carbide composite incorporating the buffer layer 200 is increased. And process stability can be improved.

According to one embodiment, the buffer layer 200 may include one or two or more types of van der Waals bond materials. In some examples, the buffer layer 200 using a material of Van der Waals bond can alleviate the difference in physical properties (e.g., stress due to difference in thermal expansion coefficient) between the substrate 100 and the tantalum carbide film 300. . For example, the occurrence of cracks (eg, bending) and peeling can be reduced by relieving stress caused by a difference in thermal expansion coefficient between the substrate 100 and the tantalum carbide film 300.

According to one embodiment, the material of Van der Waals bond is Pyrolytic Carbon, BN (e.g., hexagonal boron nitride (h-BN)), MoS ₂ , WSe ₂ , It may include at least one selected from the group consisting of ReS ₂ , MoTe ₂ and combinations thereof. In some examples, pyrolytic carbon may be formed by pyrolyzing a carbon-based material containing at least one selected from hydrocarbons (C _x H _y ) (where x and y are natural numbers and x is 1<x<6). For example, the hydrocarbon may be selected from propane (C ₃ H ₈ ), butane (C ₄ H ₁₀ ), propylene (C ₃ H ₆ ), acetylene (C ₂ H ₂ ), and combinations thereof. For example, pyrolytic carbon may be a carbon-based material produced by pyrolyzing hydrocarbon gas at a temperature of 1100°C to 1800°C (e.g., deposition temperature, CVD deposition temperature, or heat treatment temperature).

According to one embodiment, the thickness of the buffer layer 200 may be 1 ㎛ to 50 ㎛. In some examples the thickness of the buffer layer is 1 μm to 5 μm; 1 μm to 10 μm; 1 μm to 15 μm; 1 μm to 20 μm; 1 μm to 25 μm; 1 μm to 30 μm; 1 μm to 35 μm; 1 μm to 40 μm; 1 μm to 45 μm; Or it may be 1 μm to 50 μm. In some examples the thickness of the buffer layer is 2 μm to 5 μm; 2 μm to 10 μm; 2 μm to 13 μm; 2 μm to 17 μm; 2 μm to 25 μm; 2 μm to 32 μm; 2 μm to 41 μm; or 2 μm to 48 μm. in some examples 5 μm to 12 μm; 5 μm to 23 μm; 5 μm to 34 μm; Or it may be 5 μm to 43 μm. In some examples, the thickness of the buffer layer is within the above range to reduce the stress caused by the difference in thermal expansion interface between the substrate 100 and the tantalum carbide film 300 to prevent the occurrence of cracks, pinholes, etc. in the tantalum carbide film 300, The lifespan and process stability of parts using tantalum carbide composites can be improved.

According to one embodiment, the thickness ratio of the buffer layer 200 to the tantalum carbide film 300 may be 0.1:1 to 0.01:1. In some examples, the thickness ratio of the buffer layer 200 to the tantalum carbide film 300 may preferably be 0.08:1 to 0.05:1. If it is within the thickness ratio range mentioned in some examples, the stress caused by the difference in thermal expansion interface between the substrate 100 and the tantalum carbide film 300 is reduced to prevent the occurrence of cracks, pinholes, etc. in the tantalum carbide film 300, and carbonization is prevented. The lifespan and process stability of parts using tantalum composites can be improved.

As an example, the atomic ratio of Ta to C in the tantalum carbide film 300 may be 0.9 to 1.34:1, and by adjusting the atomic ratio, the surface energy of the tantalum carbide film is lowered to prevent contaminants from attaching to the process. It is possible to prevent damage to the substrate 100 due to plasma and corrosive gases in the environment (e.g., semiconductor manufacturing process) and improve the lifespan and process stability of parts using tantalum carbide composites.

As an example, the tantalum carbide film 300 may be heat treated after synthesis and/or deposition (e.g., CVD deposition), for example, at a temperature of 2000 °C to 2500 °C, in an inert gas (e.g., Ar gas) atmosphere. and heat treatment for 1 hour to 20 hours.

As an example, the tantalum carbide film 300 may have a thickness of 10 ㎛ to 100 ㎛. in some examples 10 μm to 100 μm; 10 μm to 80 μm; 10 μm to 60 μm; 10 μm to 40 μm; Or it may be 10 μm to 20 μm.

For example, the tantalum carbide film 300 may include cracks in at least one of the surface, interior, or contact surface with the buffer layer. In some examples, the surface of the tantalum carbide film 300 may include cracks. In some examples, the tantalum carbide film 300 may include microcracks with a width of 0.3 ㎛ to 0.6 ㎛. For example, 0.3 μm to 0.55 μm; 0.3 μm to 0.5 μm; 0.3 μm to 0.4 μm; Alternatively, it may include fine cracks having a width of 0.3 ㎛ to 0.35 ㎛. In some examples, the crack width refers to measuring the width of a fine crack occurring in a carbon material containing a tantalum carbide coating layer, and images of the crack area are obtained using SEM analysis equipment (e.g. SEM model name: JEOL, JSM-6390). It is observed at 2000x magnification and represents the average of the values measured at 10 points in the vertical direction of the gap between cracks. In some examples, the tantalum carbide film 300 may be crack-free in at least one of the surface, interior, or contact surface with the buffer layer.

According to one embodiment, the warpage of the tantalum carbide composite may be 10 ㎛ to 50 ㎛. in some examples 10 μm to 50 μm; 10 μm to 40 μm; 10 μm to 30 μm; Or it may be 10 μm to 20 μm. The method for measuring warpage of the tantalum carbide composite according to a preferred embodiment of the present invention is (a)

Manufacturing a tantalum carbide coated product with a size of 200 A measurement method including the step of measuring 10 points at equal intervals may include expressing the deviation of the measured value of a total of 30 points as bending.

According to one embodiment, the coefficient of thermal expansion (CTE) of the tantalum carbide film 300 exceeds 6 x 10 ^-6 /K; 7 x 10 ^-6 /K; Or it may be more than 8 x 10 ^-6 /K. In some examples, the coefficient of thermal expansion (CTE) of the tantalum carbide film 300 is greater than 6 x 10 ^-6 /K to 7 x 10 ^-6 /K; 6.1 x 10 ^-6 /K to 7 x 10 ^-6 /K; Or it may be 6.3 x 10 ^-6 /K to 7 x 10 ^-6 /K.

According to one embodiment, the coefficient of thermal expansion (CTE) of the substrate 100 is 6 x 10 ^-6 /K or less; 5 x 10 ^-6 /K or less; Or it may be 4 x 10 ^-6 /K or less. In some examples, the coefficient of thermal expansion (CTE) of the substrate 100 may be 4 x 10 ^-6 /K to 6 x 10 ^-6 /K.

According to one embodiment, the difference in coefficient of thermal expansion (CTE) between the substrate 100 and the tantalum carbide film 300 is adjusted to control the size of parts (e.g., semiconductor manufacturing parts) (e.g., plasma process parts) to which the tantalum carbide composite is applied. It can protect substrates in extreme environments such as high temperatures, plasma, and corrosive gases, and improve component lifespan and process stability. In some examples, there is a difference in thermal expansion coefficient between the substrate 100 and the tantalum carbide film 300, but the introduction of the buffer layer 200 induces stress relief to prevent cracking and peeling of the tantalum carbide film 300, It can protect the substrate of the applied parts (e.g. semiconductor manufacturing parts) (e.g. plasma process parts) in a process environment containing high temperature, plasma, corrosive gas, etc. and improve the lifespan and process stability of the parts.

According to one embodiment, a part containing the tantalum carbide composite material of the present disclosure may be provided. As an example, the tantalum carbide composite may include the content mentioned in the description of the tantalum carbide composite mentioned above. As an example, the component may be a component used in a semiconductor process. For example, the component may be a component of single crystal SiC/AlN Epitaxy and SiC/AlN Growth process equipment.

The numerical range described in this document may be expressed or interpreted as less than, more than, less than, and/or more than a specific value within the range, as long as it does not deviate from the purpose and scope of the present invention. As used herein, “at least one or more” may mean one or a mixture of two or more.

Hereinafter, the present invention will be described in more detail through examples and comparative examples. However, the following examples are only for illustrating the present invention, and the content of the present invention is not limited to the following examples.

Example 1

The thermal expansion coefficient of the graphite substrate is 4.5x10 ^-6 /K, and a pyrolytic carbon layer was deposited on the substrate to a thickness of 5 ㎛ by CVD deposition, and then a TaC layer was formed on the pyrolytic carbon layer by CVD deposition.

Example 2

The thermal expansion coefficient of the graphite substrate is 4.5x10 ^-6 /K, and a 15㎛ thick pyrolytic carbon layer was deposited on the substrate by CVD deposition, and then a TaC layer was formed on the pyrolytic carbon layer by CVD deposition.

Example 3

The thermal expansion coefficient of the graphite substrate is 4.5x10 ^-6 /K, and a pyrolytic carbon layer was deposited on the substrate to a thickness of 25㎛ by CVD deposition, and then a TaC layer was formed on the pyrolytic carbon layer by CVD deposition.

Example 4

The thermal expansion coefficient of the graphite substrate is 5.5x10 ^-6 /K, and a pyrolytic carbon layer was deposited on the substrate to a thickness of 5 ㎛ by CVD deposition, and then a TaC layer was formed on the pyrolytic carbon layer by CVD deposition.

Comparative Example 1

A TaC composite was prepared in the same manner as in Example 1 except that the buffer layer was not formed.

Comparative Example 2

A TaC composite was prepared in the same manner as in Example 4 except that the buffer layer was not formed.

The cross-section of the TaC composite prepared in Example 1 was observed by measuring SEM ( Scanning Electron Microscope) images. The results are shown in Figure 3. In Figure 3, it can be seen that a pyrolytic carbon layer/TaC layer was formed on the graphite substrate.

Surface microstructure analysis

The surface microstructure of TaC prepared in Examples and Comparative Examples was observed using SEM, and the crack width results are shown in Figures 4a, 4b, 4c, and Table 1.

division	Comparative Example 1	Comparative Example 2	Example 1	Example 2	Example 3	Example 4
Substrate thermal expansion coefficient	4.5x10 -6 /K	5.5x10 -6 /K	4.5x10 -6 /K	4.5x10 -6 /K	4.5x10 -6 /K	5.5x10 -6 /K
buffer layer	doesn't exist	doesn't exist	has exist	has exist	has exist	has exist
Buffer layer thickness	-	-	5㎛	10㎛	25㎛	5㎛
Average width of cracks occurring on the TaC grain boundary surface (㎛)	3.3	1.1	0.36	0.51	0.55	Crack Free

Deflection measurement

The warpage of the composite materials of Examples and Comparative Examples was measured. The results are shown in Table 2.

How to measure warpage

A tantalum carbide coated product measuring 200 That is, the height of the product was measured at 10 points at equal intervals of 0°, 60°, and 120°. The deviation of the 30 point measured value was expressed as warpage.

division		Comparative Example 1	Example 1	Example 2	Example 3
Substrate thermal expansion coefficient		4.5x10 -6 /K	4.5x10 -6 /K	4.5x10 -6 /K	4.5x10 -6 /K
buffer layer		doesn't exist	has exist	has exist	has exist
Buffer layer thickness		-	5㎛	15㎛	25㎛
warp	Warpage (㎛)	198	14	27	40

Figures 4a, 4b, and 4c are SEM images of the surface of the TaC layer in the TaC composite. Figure 4a is the SEM image of Comparative Example 1, Figure 4b is the SEM image of Example 4, and Figure 4c is the example. This is the SEM image of 1.

Cracks on the surface were observed through SEM images of the composite materials of Examples and Comparative Examples in FIGS. 4A, 4B, and 4C. In Comparative Example 1, the crack width of the TaC surface was large and the gap between cracks was large. ), when measured in the vertical direction, corresponds to a maximum level of 3.0 ㎛ to 3.6 ㎛. This is due to the occurrence of internal stress between the graphite substrate and TaC. In Examples 1 and 3, in which a buffer layer was introduced, when the gap between cracks was measured in the vertical direction, fine cracks with a maximum width of 0.2 ㎛ to 0.4 ㎛ (Example 1) occurred or no cracks were observed (Example 4). That is, although there is a difference in thermal expansion coefficient between the graphite substrate and TaC, the introduction of a buffer layer can relieve the stress between them and reduce the crack width on the surface of the TaC layer or reduce the occurrence of cracks and warping, thereby reducing the possibility of delamination.

In Figure 5, when the buffer layer is applied, the width of micro cracks on the surface of the TaC layer can be reduced by up to 2.8 times (e.g., comparison of Example 1 and Comparative Example 1). In addition, it can be seen that the width size of the micro crack changes depending on the thickness of the buffer layer. When applying the buffer layer in FIG. 6, warpage on the surface of the TaC layer can be reduced by up to 14 times (e.g., comparison of Example 1 and Comparative Example 1). Additionally, it can be seen that warpage changes depending on the thickness of the buffer layer. Table 3 shows the results of measuring stress changes according to the thickness of the pyrolytic carbon layer and TaC layer.

Graphite (㎛)	Pyrolytic Carbon (㎛)	TaC (㎛)	Von mises stress (Mpa)	Crack Free (665Mpa)
3000	5	10	665.3763	O
		20	665.3780	O
		30	665.3812	O
		40	665.3952	O
		50	665.4037	O
	15	10	665.3799	O
		20	665.3800	O
		30	665.3813	O
		40	665.3983	O
		50	665.4058	O
	20	10	791.1817	X
		20	791.1818	X
		30	791.1819	X
		40	791.1820	X
		50	791.1822	X

(In Table 3, “O” means crack-free, and “x” means micro-crack occurrence.)

In Table 3, the lower the thickness of the pyrolytic carbon layer (buffer layer), the greater the stress alleviation effect between the graphite substrate and the TaC layer, which can lower the occurrence of cracks or reduce the width size of micro cracks.

As described above, although the embodiments have been described with limited examples and drawings, various modifications and variations can be made by those skilled in the art from the above description. For example, even if the described techniques are performed in a different order than the described method, and/or the described components are combined or combined in a different form than the described method, or are replaced or substituted by other components or equivalents. Adequate results can be achieved. Therefore, other implementations, other embodiments, and equivalents of the claims also fall within the scope of the claims described below.

Claims (9)

1. write; and

   A tantalum carbide film formed on at least one surface of the substrate; Including,

   a buffer layer between the substrate and the tantalum carbide film;

   Including,

   The buffer layer is,

   Containing a material of van der Waals bond,

   Tantalum carbide composite.
2. According to paragraph 1,

   The van der Waals material includes at least one selected from the group consisting of pyrolytic carbon, BN, MoS ₂ , WSe ₂ , ReS ₂ , MoTe ₂ , and combinations thereof,

   Tantalum carbide composite.
3. According to paragraph 1,

   The thickness of the buffer layer is 1 ㎛ to 50 ㎛,

   Tantalum carbide composite.
4. According to paragraph 1,

   The atomic ratio of Ta to C in the tantalum carbide film is 0.9 to 1.34,

   Tantalum carbide composite.
5. According to paragraph 1,

   The thickness of the tantalum carbide film is 10 ㎛ to 100 ㎛,

   Tantalum carbide composite.
6. According to paragraph 1,

   The above description,

   Containing at least one selected from the group consisting of graphene, graphite, fullerene, and combinations thereof,

   Tantalum carbide composite.
7. According to paragraph 1,

   A tantalum carbide composite, wherein the deflection of the tantalum carbide composite is 10 ㎛ to 50 ㎛.
8. According to paragraph 1,

   The tantalum carbide film is crack-free or contains cracks with a width of 0.3 ㎛ to 0.6 ㎛,

   Tantalum carbide composite.
9. According to paragraph 1,

   The coefficient of thermal expansion (CTE) of the tantalum carbide film is greater than 6 x10 ^-6 /K,

   The coefficient of thermal expansion (CTE) of the substrate is 6 x 10 ^-6 /K or less,

   Tantalum carbide composite.

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