Tantalum carbide composite material and preparation method thereof

Abstract

The invention relates to a tantalum carbide composite material and a preparation method thereof. The tantalum carbide composite material comprises a base material; a buffer layer deposited on all surfaces of the substrate; and a tantalum carbide layer deposited over the buffer layer.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a tantalum carbide composite material according to an embodiment and a method of manufacturing the same. BACKGROUND

[0002] A susceptor used in a semiconductor manufacturing apparatus has a problem in that a carbon material is etched by a corrosive gas if the carbon material is directly used in a conventional semiconductor process, and thus a member in which a carbon material is coated with silicon carbide (SiC) or tantalum carbide (TaC) is used.

[0003] However, a tantalum carbide composite material in which a carbon material is coated with tantalum carbide (TaC) has a problem in that stress is generated due to a difference in a thermal expansion coefficient between the carbon material and a tantalum carbide film, and thus cracks and warping are caused, resulting in damage to a member in which the tantalum carbide composite material is used and deterioration in a service life. SUMMARY

[0004] Problems to be Solved by the Invention

[0005] A member coated with tantalum carbide (TaC) uses a tantalum carbide composite material in which a carbon material is coated with tantalum carbide (TaC), but has a problem in that warping, cracks, peeling, and the like are easily caused due to thermal stress caused by a difference in a thermal expansion coefficient between a carbon substrate and the tantalum carbide (TaC). For this reason, there is a need to develop a buffer layer to relieve thermal stress between the carbon substrate and the tantalum carbide film.

[0006] To solve the above-described problems, according to an embodiment, the present disclosure provides a tantalum carbide composite material and a method of manufacturing the same, the tantalum carbide composite material introducing a stress-relieving buffer layer for relieving stress between a substrate and a tantalum carbide film (a tantalum carbide coating layer).

[0007] According to an embodiment, the present disclosure provides a tantalum carbide composite material introducing a stress-relieving buffer layer for relieving stress between a substrate and a tantalum carbide film, and preventing warping, cracks, peeling, and the like.

[0008] According to an embodiment, the present disclosure provides a method of using a tantalum carbide composite material introducing a stress-relieving buffer layer for relieving stress. According to an embodiment, the present disclosure can provide a member for semiconductor manufacturing including a tantalum carbide composite material introducing a stress-relieving buffer layer for relieving stress, and can improve life stability, stability of a semiconductor manufacturing process, and process efficiency.

[0009] However, the problems to be solved by the present invention are not limited to the above-described content, and those skilled in the art will clearly understand other problems not mentioned through the following description.

[0010] Technical Means for Solving the Problems

[0011] According to an embodiment of the present disclosure, a tantalum carbide composite material includes: a substrate; a buffer layer deposited on the substrate; and a tantalum carbide layer deposited on the buffer layer.

[0012] According to an embodiment, the buffer layer includes a substance bonded by Van-der-Waals force.

[0013] According to an embodiment, the substance bonded by Van-der-Waals force includes at least one selected from the group consisting of pyrolytic carbon, BN, MoS2, WSe2, ReS2, and MoTe2, or a combination thereof.

[0014] According to an embodiment, the buffer layer has a different coefficient of thermal expansion in a horizontal direction of a formation surface from a coefficient of thermal expansion in a vertical direction of the formation surface.

[0015] According to an embodiment, the coefficient of thermal expansion in the vertical direction of the formation surface of the buffer layer is greater than the coefficient of thermal expansion in the horizontal direction of the formation surface.

[0016] According to an embodiment, the coefficient of thermal expansion in the vertical direction of the formation surface of the buffer layer is about 6.0 x 10 -6 / K to about 7.0 x 10 -6 / K, and the coefficient of thermal expansion in the horizontal direction of the formation surface of the buffer layer is about 0.2 x 10 -6 / K to about 0.7 x 10 -6 / K.

[0017] According to an embodiment, the coefficient of thermal expansion in the vertical direction of the formation surface of the buffer layer satisfies at least one or all of the following conditions:

[0018] i) is lower than a coefficient of thermal expansion of the tantalum carbide layer;

[0019] ii) is higher than a coefficient of thermal expansion of the substrate;

[0020] iii) is higher than an intermediate value of the coefficients of thermal expansion of the substrate and the tantalum carbide layer.

[0021] According to an embodiment, the buffer layer has a thickness of about 1 μm to about 100 μm.

[0022] According to an embodiment, the tantalum carbide layer has a thickness of about 10 μm to about 100 μm.

[0023] According to an embodiment, the buffer layer is formed as a layered structure with respect to the substrate.

[0024] According to an embodiment, the tantalum carbide layer is crack-free. According to an embodiment, the substrate includes at least one of graphene, graphite, or fullerene, or a combination thereof.

[0025] According to one embodiment, the warpage of the tantalum carbide composite material is from about 10 μm to about 50 μm.

[0026] According to one embodiment, the tantalum carbide layer includes cracks with a width of about 0.3 μm to about 0.6 μm.

[0027] According to embodiments of this disclosure, a method for preparing tantalum carbide composite material includes the following steps: preparing a substrate; forming a buffer layer on the substrate; and forming a tantalum carbide layer on the buffer layer, the buffer layer comprising a substance bonded by van der Waals forces, the buffer layer being formed on at least one or all of the surfaces of the substrate.

[0028] According to one embodiment, the step of forming the tantalum carbide layer is to form a film on the buffer layer.

[0029] According to one embodiment, the step of forming the buffer layer is to deposit the buffer layer at a temperature of about 1500°C to about 1900°C and a pressure of about 500 to about 900 tor.

[0030] According to one embodiment, the step of forming the tantalum carbide layer is to deposit a tantalum carbide film at a temperature of about 1900°C to about 2300°C and a pressure of about 200 to about 400 tor.

[0031] According to one embodiment, the steps of forming the buffer layer and forming the tantalum carbide layer are performed using a CVD process.

[0032] According to one embodiment, the step of forming the buffer layer is to form a buffer layer comprising a material bonded by van der Waals forces, the material being bonded by van der Waals forces comprising at least one or a combination thereof selected from pyrolytic carbon, BN, MoS2, WSe2, ReS2 and MoTe2.

[0033] According to one embodiment, the preparation method is to prepare a tantalum carbide composite material according to the embodiments of this disclosure.

[0034] Invention Effects

[0035] This disclosure provides a tantalum carbide composite material and a method for preparing the same. The tantalum carbide composite material incorporates a stress-relieving buffer layer to alleviate stress between the substrate and the tantalum carbide film (tantalum carbide coating), preventing problems such as warping, cracking, and peeling. This disclosure also provides a component (e.g., a component for plasma processing) comprising the tantalum carbide composite material according to embodiments of this disclosure. Attached Figure Description

[0036] Figure 1a This is a structural example diagram of a tantalum carbide composite material having a tantalum carbide film formed on one side of a substrate, according to one embodiment.

[0037] Figure 1b is a structural example of a carbon-tantalum composite material in which a carbon-tantalum film is deposited on a substrate according to an embodiment.

[0038] Figure 2 is a structural example of a carbon-tantalum composite material according to an embodiment. Figure 1b is a structural example of a carbon-tantalum composite material according to an embodiment.

[0039] Figure 3 is a cross-sectional SEM image of a carbon-tantalum composite material according to an embodiment.

[0040] Figure 4a is a SEM image of a carbon-tantalum layer surface measured in a carbon-tantalum composite material according to an embodiment, which is a SEM image of Comparative Example 1.

[0041] Figure 4b is a SEM image of a carbon-tantalum layer surface measured in a carbon-tantalum composite material according to an embodiment, which is a SEM image of Example 4.

[0042] Figure 4c is a SEM image of a carbon-tantalum layer surface measured in a carbon-tantalum composite material according to an embodiment, which is a SEM image of Example 1.

[0043] Figure 5 is a width of a micro crack of a carbon-tantalum composite material according to an embodiment.

[0044] Figure 6 is a warpage size of a carbon-tantalum composite material according to an embodiment.

[0045] Figure 7a is a schematic diagram of a stress mitigation mechanism using a carbon-tantalum composite material according to an embodiment.

[0046] Figure 7b is a schematic diagram of a stress mitigation mechanism using a carbon-tantalum composite material according to an embodiment. DETAILED DESCRIPTION

[0047] Hereinafter, embodiments of the present application will be described in detail with reference to accompanying drawings. In describing the embodiments of the present application, when it is considered that detailed description of related known functions or constructions will unnecessarily obscure the gist of the present application, detailed description thereof will be omitted. Also, the terms used in the present specification are used to merely describe embodiments of the present application and the meanings of the terms can vary according to the intention of the user, operator, or the custom in the related art. Therefore, the definition of the terms should be made based on the overall content of the present specification.

[0048] Throughout the instruction manual, when it is stated that a component is "on" another component, this includes not only cases where one component is in contact with another component, but also cases where another component exists between the two components.

[0049] Throughout the specification, when it is stated that a part "includes" a certain element, other elements may also be included rather than excluding the possibility of the existence of other elements.

[0050] The tantalum carbide composite material and its preparation method of the present invention will be described below with reference to embodiments and accompanying drawings. However, the present invention is not limited to these embodiments and drawings.

[0051] According to one embodiment, Figure 1a and Figure 1b An example structure of a tantalum carbide composite material is shown. Figure 1a In the present invention, the tantalum carbide composite material includes a substrate 100 and a tantalum carbide layer 300, wherein a buffer layer 200 is included between the substrate 100 and the tantalum carbide layer 300.

[0052] According to one embodiment, the substrate 100 may be appropriately selected based on the intended use of the tantalum carbide composite material. For example, considering the tantalum carbide layer 300 and its coefficient of thermal expansion, the substrate 100 may be a carbon substrate. In some examples, the substrate 100 may comprise graphene, graphite, fullerene, or a combination thereof. In some examples, the substrate 100 may be graphene or graphite.

[0053] According to one embodiment, the thickness of the substrate 100 can be from about 1 mm to about 10 mm. In some examples, it can be from about 1 mm to about 10 mm; from about 1 mm to about 8 mm; from about 1 mm to about 6 mm; from about 1 mm to about 4 mm; or from about 1 mm to about 3 mm. In some examples, when the thickness of the substrate 100 is within the above range, deformation of the substrate 100 can be minimized after the deposition of the tantalum carbide layer 300, which can extend the life and improve the process stability for components made of tantalum carbide composite materials with buffer layer 200.

[0054] According to one embodiment, a buffer layer 200 is formed on a substrate 100. For example, the buffer layer 200 may be formed (deposited) on at least a portion or all of at least one or all of the surfaces of the substrate 100. In some examples, reference is made to... Figure 1a The buffer layer 200 may be formed on a portion or all of one side (e.g., the top or bottom) of the substrate 100. In some examples, refer to... Figure 1b The buffer layer 200 may be formed on at least a portion of all surfaces of the substrate 100, or formed on all surfaces (e.g., top, bottom and sides) to cover the substrate 100.

[0055] According to an embodiment, the buffer layer 200 can include one or more than two substances that are bonded by Van der Waals force. In some examples, the buffer layer 200 using substances bonded by Van der Waals force can reduce the difference in physical properties (e.g., stress based on the difference in coefficient of thermal expansion) between the substrate 100 and the tantalum carbide film 300. For example, cracks (e.g., warpage) and peeling can be reduced by mitigating stress caused by the difference in coefficient of thermal expansion between the substrate 100 and the tantalum carbide layer 300.

[0056] According to an embodiment, the substance bonded by Van der Waals force is at least one of the group consisting of pyrolytic carbon, BN (e.g., hexagonal boron nitride (h-BN)), MoS2, WSe2, ReS2, MoTe2, and combinations thereof. In some examples, the buffer layer 200 has a layered structure by applying a substance bonded by Van der Waals force, which has a large number of layers bonded by Van der Waals force (e.g., bonding in the vertical direction of the formation surface) with reference to the formation surface (or deposition surface) of the buffer layer 200. Thus, TaC expands in the horizontal direction of the formation surface along with thermal expansion during deposition, at which time the horizontal bonding of the formation surface does not break but the vertical bonding of the formation surface breaks, and internal peeling and interlayer sliding occur. That is, even if multiple internal peeling occurs within the layered structure, based on the Van der Waals bonding characteristics, interlayer sliding can effectively expand in matching with the expansion of TaC, thereby accommodating the expansion of TaC Figure 7a and 7b ).

[0057] According to an embodiment, a raw material for forming (e.g., depositing) a substance bonded by Van der Waals force can be appropriately selected according to the formation process (e.g., deposition process). The raw material of different phases (gases, solids (powders), etc.) can be appropriately selected depending on the process. In some examples of the raw material, pyrolytic carbon can be formed by 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 can be selected from propane (C3H8), butane (C4H 10), propylene (C3H6), or acetylene (C2H2), and combinations thereof. In some examples, examples of the starting materials are BN starting materials (e.g., B2H6and / or NH3), MoS2starting materials (e.g., S powder and MoO2powder), WSe2starting materials (e.g., WO3powder and Se gas), ReS2starting materials (e.g., NH4ReO4(ammonium perrhenate) (precursor (solid)) and S gas), or MoTe2starting materials (e.g., Te powder + MoCl5and MoO3powder), etc., but are not limited thereto. For example, pyrolytic carbon can be a carbon-based material produced by thermal decomposition of a hydrocarbon gas at a temperature (e.g., a deposition temperature, a CVD deposition temperature, or a heat treatment temperature) of about 1100 °C to about 2000 °C; about 1300 °C to about 2000 °C; about 1400 °C to about 2000 °C; about 1500 °C to about 1900 °C; about 1600 °C to about 1900 °C; or about 1700 °C to about 1800 °C. The buffer layer formation process of the present disclosure can refer to the preparation method process described below.

[0058] According to an embodiment, the thickness of the buffer layer 200 can be about 1 μm to about 50 μm. In some examples, the thickness of the buffer layer can be about 1 μm to about 5 μm; about 1 μm to about 10 μm; about 1 μm to about 15 μm; about 1 μm to about 20 μm; about 1 μm to about 25 μm; about 1 μm to about 30 μm; about 1 μm to about 35 μm; about 1 μm to about 40 μm; about 1 μm to about 45 μm; or about 1 μm to about 50 μm. In some examples, the thickness of the buffer layer can be about 2 μm to about 5 μm; about 2 μm to about 10 μm; about 2 μm to about 13 μm; about 2 μm to about 17 μm; about 2 μm to about 25 μm; about 2 μm to about 32 μm; about 2 μm to about 41 μm; or about 2 μm to about 48 μm. In some examples, it can be about 5 μm to about 12 μm; about 5 μm to about 20 μm; about 5 μm to about 23 μm; about 5 μm to about 34 μm; or about 5 μm to about 43 μm. In some examples, when the thickness of the buffer layer is within the above ranges, stress caused by the difference in thermal expansion interface between the substrate 100 and the tantalum carbide layer 300 can be reduced, thereby preventing cracks, pinholes, etc. in the tantalum carbide film 300, and improving the life and process stability of components using tantalum carbide composites.

[0059] According to an embodiment, the tantalum carbide layer 300 can be formed on at least a portion or the entire buffer layer 200, and can be formed as a single film. The single film can be a single layer or multiple layers.

[0060] According to an embodiment, the atomic ratio of Ta to C in the tantalum carbide layer 300 can be about 0.9 to about 1.34 : about 1; about 0.1 to about 1.34 : about 1; about 1.0 to about 1.34 : about 1; about 1.1 to about 1.34 : about 1; about 1.2 to about 1.34 : about 1; or about 1.3 to about 1.34 : about 1. By adjusting the atomic ratio, the surface energy of the tantalum carbide film can be reduced, preventing contaminants from adhering, and preventing plasma or corrosive gases in a process environment (e.g., a semiconductor manufacturing process) from damaging the substrate 100, improving the lifetime and process stability of components using the tantalum carbide composite.

[0061] According to an embodiment, the tantalum carbide film 300 can be heat treated after synthesis and / or deposition (e.g., CVD deposition) is completed, for example, at a temperature of 2000 °C to 2500 °C for about 1 hour to about 20 hours; about 2 hours to about 20 hours; about 4 hours to about 20 hours; about 6 hours to about 20 hours; about 8 hours to about 18 hours; or about 8 hours to about 15 hours in an inert gas (e.g., Ar) atmosphere.

[0062] According to an embodiment, the tantalum carbide film 300 can have a thickness of about 10 μm (micrometers) to about 100 μm (micrometers). In some examples, the thickness can be about 10 μm to about 100 μm; about 10 μm to about 80 μm; about 10 μm to about 60 μm; about 10 μm to about 40 μm; or about 10 μm to about 20 μm.

[0063] According to an embodiment, the thickness ratio of the buffer layer 200 to the tantalum carbide layer 300 can be about 0.1 : about 1 to about 0.01 : about 1. In some examples, the thickness ratio of the buffer layer 200 to the tantalum carbide layer 300 can preferably be about 0.08 : about 1 to about 0.05 : about 1. When the thickness ratio is within the range mentioned in the above examples, stress caused by the difference in the coefficient of thermal expansion between the substrate 100 and the tantalum carbide layer 300 can be reduced, preventing cracks, pinholes, etc. from occurring in the tantalum carbide layer 300, improving the lifetime and process stability of components using the tantalum carbide layer 300 composite.

[0064] According to one embodiment, the tantalum carbide film 300 may be crack-free, or it may contain cracks in at least one of its surface, interior, or contact surface with the buffer layer 200. In some examples, the surface of the tantalum carbide film 300 may have cracks. In some examples, the tantalum carbide film 300 may include microcracks with a width of about 0.3 μm to about 0.6 μm. For example, the crack width may be about 0.3 μm to about 0.55 μm; about 0.3 μm to about 0.5 μm; about 0.3 μm to about 0.4 μm; or about 0.3 μm to about 0.35 μm. In some examples, the crack width refers to the width of microcracks in the carbon material containing the tantalum carbide coating, which is the average value obtained by observing the crack location at 2000x magnification using a SEM analysis device (e.g., SEM model name: JEOL, JSM-6390) and measuring 10 points in the vertical direction of the crack gap (Gap). In some cases, at least one of the surfaces, interiors, or contact surfaces of the tantalum carbide film 300 may be free of cracks.

[0065] According to one embodiment, the coefficient of thermal expansion (CTE) of the substrate 100 can be approximately 6 x 10⁻⁶. -6 Below / K; approximately 5x10 -6 / K or less; or about 4x10 -6 / K or below. In some cases, the coefficient of thermal expansion (CTE) of substrate 100 can be approximately 4 x 10⁻⁶. -6 / K to approximately 6x10 -6 / K.

[0066] According to one embodiment, the coefficient of thermal expansion (CTE) of the buffer layer 200 (e.g., the average coefficient of thermal expansion) is... Figure 1a and Figure 1b The coefficient of thermal expansion in the horizontal direction of the surface on which the buffer layer 200 is formed is approximately 0.3 x 10⁻⁶. -6 / K or higher and approximately 0.5x10 -6 / K or less; Figure 1a and Figure 1b The coefficient of thermal expansion in the direction perpendicular to the surface where the buffer layer 200 is formed is approximately 6.0 x 10⁻⁶. -6 / K or higher and within 7.0x10 -6 / K or below. According to one embodiment, the buffer layer 200 has a van der Waals bond such that the vertical bonding force of the forming surface is less than the horizontal bonding force of the forming surface (e.g., covalent bonds). Even though the horizontal thermal expansion coefficient of the forming surface of the buffer layer is very low, when the forming surface expands horizontally with the thermal expansion of TaC (e.g., high-temperature expansion), the horizontal bonding of the forming surface will not break, but the vertical bonding of the forming surface will break and cause internal peeling (e.g., multiple peeling), resulting in interlayer slip in the van der Waals bond layer. Figure 7a and Figure 7b In other words, when the buffer layer 200 has a layered structure bound by van der Waals forces, it can be effectively expanded to match the expansion of TaC through internal interlayer sliding within the layered structure.

[0067] According to one embodiment, the coefficient of thermal expansion in the vertical direction of the forming surface of the buffer layer 200 can satisfy at least one of the following conditions i), ii), and iii):

[0068] i) The coefficient of thermal expansion is 300 lower than that of tantalum carbide layers;

[0069] ii) Higher than the substrate (e.g., Figure 1a and Figure 1b The coefficient of thermal expansion of the substrate (100) in the middle;

[0070] iii) Higher than the substrate (e.g., Figure 1a and Figure 1b The intermediate value of the coefficient of thermal expansion of the substrate 100 and the tantalum carbide layer 300.

[0071] According to one embodiment, the ratio of the coefficient of thermal expansion in the vertical direction of the forming surface of the buffer layer 200 to the coefficient of thermal expansion in the horizontal direction of the forming surface is about 1: about 1 (greater than) to about 14; about 1: about 1 (greater than) to about 14; about 1: about 1 (greater than) to about 12; about 1: about 1 (greater than) to about 10; about 1: about 1 (greater than) to about 8; about 1: about 1 (greater than) to about 5; about 1: about 1.1 to about 3; about 1: about 1.1 to about 2.5; about 1: about 1.1 to about 2.2; about 1: about 1.1 to about 2; about 1: about 1.1 to about 1.8; about 1: about 1.1 to about 1.6; about 1: about 1.1 to about 1.4; or about 1: about 1.1 to about 1.2.

[0072] According to one embodiment, the buffer layer 200 forms surfaces perpendicular to the direction (e.g., Figure 1a and Figure 1bThe ratio of the coefficient of thermal expansion (b or d) to the median of the coefficients of thermal expansion of the substrate 100 and the tantalum carbide layer 300 is approximately 1.1 to approximately 1.9: approximately 1; approximately 1.1 to approximately 1.8: approximately 1; approximately 1.1 to approximately 1.7: approximately 1; approximately 1.1 to approximately 1.5: approximately 1; approximately 1.1 to approximately 1.4: approximately 1; approximately 1.1 to approximately 1.3: approximately 1; approximately 1.1 to approximately 1.2: approximately 1; or approximately 1: approximately 1.2.

[0073] In this paper, the direction perpendicular to the formation surface of the buffer layer 200 corresponds to the growth direction (or deposition direction) of the buffer layer on the substrate 100. (Reference) Figure 1a and Figure 1b In this paper, the direction perpendicular to the formation surface of the buffer layer is Figure 1a In the Z-axis direction, when... Figure 1b When the deposited layer is formed on all surfaces to surround the substrate 100, it refers to the vertical direction based on the formation surfaces 110, 120, 130, and 140 of the buffer layer 200 of the substrate 100.

[0074] In this article, Figure 1a The formation surface of the buffer layer can be horizontal, either along the X-axis or the Y-axis. When, for example... Figure 1b When the deposited layer is formed on all surfaces to surround the substrate 100, the horizontal direction of the buffer layer forming surface refers to all directions parallel to the forming surfaces 110, 120, 130, and 140 of the buffer layer 200 of the substrate 100.

[0075] According to one embodiment, the coefficient of thermal expansion (e.g., average coefficient of thermal expansion) of the tantalum carbide film 300 is approximately greater than 6 x 10⁻⁶. -6 / K; approximately 7x10 -6 / K or more; or approximately 8x10 -6 / K or higher. In some cases, the coefficient of thermal expansion (CTE) of tantalum carbide film 300 is approximately greater than 6 x 10⁻⁶. -6 / K and in approximately 7x10 -6 Within / K; approximately 6.1x10 -6 / K to approximately 7x10 -6 / K; or approximately 6.3 x 10 -6 / K to approximately 7x10 -6 / K.

[0076] According to one embodiment, the coefficient of thermal expansion can be measured using a thermal expansion coefficient meter (DIL 402C) from room temperature to 1000°C. In this document, the coefficient of thermal expansion may refer to a maximum value, a minimum value, or an average value.

[0077] According to an embodiment, the warp of the tantalum carbide composite material can be about 10 μm to about 50 μm. In some examples, it can be about 10 μm to about 50 μm; about 10 μm to about 40 μm; about 10 μm to about 30 μm; or about 10 μm to about 20 μm. The method for measuring the warp of the tantalum carbide composite material according to the preferred embodiment of the present disclosure includes the following steps: step (a), preparing a tantalum carbide coated product with a size of 200 mm x 3 mm; step (b), measuring the height of the product based on the upper half of the coordinate measuring machine (3D shape); step (c), measuring 10 points at the same interval of 0°, 60°, 120°, and the warp can be expressed as the deviation of the measurement values of a total of 30 points.

[0078] According to an embodiment, adjusting the difference in the coefficient of thermal expansion (CTE) between the base material 100 and the tantalum carbide layer 300 can protect the base material in extreme environments such as high temperature, plasma, corrosive gas, etc. for the components (e.g., semiconductor manufacturing components) to which the tantalum carbide composite material is applied, extend the service life of the components, and improve process stability. In some examples, there is a difference in the coefficient of thermal expansion between the base material 100 and the tantalum carbide layer 300, but the buffer layer 200 can alleviate stress to prevent cracks and peeling of the tantalum carbide layer 300, etc. for the components (e.g., semiconductor manufacturing components) to which it is applied, can protect the base material in extreme environments such as high temperature, plasma, corrosive gas, etc., extend the service life of the components, and improve process stability.

[0079] According to an embodiment, a component including the tantalum carbide composite material of the present disclosure can be provided. For example, the tantalum carbide composite material can include the contents mentioned in the above-described tantalum carbide composite material. For example, the component can be a component used in a semiconductor process. For example, the component can be a component of a single crystal SiC / AlN Epitaxy and SiC / AlN Growth process apparatus.

[0080] According to an embodiment, Figure 2 A flowchart of a method for manufacturing a tantalum carbide composite material according to an embodiment of the present disclosure is shown in FIG. 4, and the method for manufacturing a tantalum carbide composite material includes the steps of preparing a base material 410, forming a buffer layer 420, and forming a tantalum carbide layer 430. Figure 2

[0081] According to an embodiment, the step of preparing a base material 410 can be the step of preparing a base material mentioned in the tantalum carbide composite material of the present disclosure (e.g., the base material 100 of the tantalum carbide composite material of Figure 1a and Figure 1b ). Figure 1a Figure 1b

[0082] ​​​According to an embodiment, the substrate prepared in the step 410 of preparing a substrate (e.g., the substrate 100 of Figure 1a and Figure 1b ) can be loaded into a deposition chamber and evacuated to a vacuum state.

[0083] According to an embodiment, the step 420 of forming a buffer layer can be a step of forming a buffer layer (e.g., the buffer layer 200 of Figure 1a and Figure 1b ) on the substrate (e.g., the substrate 100 of Figure 1a and Figure 1b ). According to an embodiment, the buffer layer (e.g., the buffer layer 200 of Figure 1a and Figure 1b ) can be formed on at least a portion of at least one side or all sides of the substrate (e.g., the substrate 100 of Figure 1a and Figure 1b ). According to an embodiment, the buffer layer (e.g., the buffer layer 200 of Figure 1a and Figure 1b ) can be formed on at least a portion of all sides or all of all sides of the substrate (e.g., the substrate 100 of Figure 1a and Figure 1b ). Preferably, the buffer layer (e.g., the buffer layer 200 of Figure 1a and Figure 1b ) can be a single film formed on all sides of the substrate (e.g., the substrate 100 of Figure 1a and Figure 1b ). In some examples, the buffer layer (e.g., the buffer layer 200 of Figure 1a and Figure 1b ) can be a single layer or multiple layers.

[0084] According to an embodiment, the step of forming a buffer layer can be depositing the buffer layer at a temperature (e.g., a deposition temperature, a CVD deposition temperature, or a heat treatment temperature) of about 1100 °C to about 2000 °C; about 1300 °C to about 2000 °C; about 1400 °C to about 2000 °C; about 1500 °C to about 1900 °C; about 1600 °C to about 1900 °C; or about 1700 °C to about 1900 °C, at a pressure of about 400 torr (Torr) to about 1000 Torr; about 500 Torr to about 1000 Torr; or about 500 Torr to about 900 Torr.

[0085] According to one embodiment, step 420 of forming the buffer layer can be achieved by depositing the buffer layer by supplying raw materials for depositing the buffer layer at the aforementioned temperature and pressure. In some examples, a raw material gas and a carrier gas can be supplied. In some examples, a suitable raw material gas for deposition (e.g., CVD) can be selected based on the composition of the buffer layer. For example, when the buffer layer is pyrolytic carbon, propane (C3H8) or butane (C4H8) can be supplied. 10 The process involves pyrolyte (C3H6), propylene (C2H2), acetylene (C2H2), or a combination thereof, and the hydrocarbon gas is pyrolyzed under the aforementioned process conditions. A buffer layer is obtained by depositing the resulting carbon-based material. In some examples, the carrier gas may be selected from hydrogen (H2), argon, or nitrogen.

[0086] According to one embodiment, step 420 of forming the buffer layer involves forming a buffer layer comprising a material bonded by van der Waals forces (e.g., Figure 1a or Figure 1b In the step of forming the buffer layer 200, the van der Waals bonded material includes at least one or a combination thereof selected from pyrolytic carbon, BN, MoS2, WSe2, ReS2, and MoTe2. According to one embodiment, step 420 of forming the buffer layer uses a raw material for forming (e.g., depositing) the van der Waals bonded material, and the raw material can be appropriately selected based on the forming process (e.g., deposition process). According to one embodiment, the phase of the raw material, such as gas or solid (powder), can be appropriately selected according to the process. In the example of the raw material described above, pyrolytic carbon can be formed from a pyrolytic carbon-based material containing hydrocarbons (C... x H y (where x and y are natural numbers and x is 1 < x < 6) at least one of the following. For example, the hydrocarbon may be selected from propane (C3H8), butane (C4H8), etc. 10 ), propylene (C3H6), acetylene (C2H2), and combinations thereof. In some examples, non-limiting examples of the raw materials include BN raw materials (e.g., B2H6 and / or NH3), MoS2 raw materials (e.g., S powder and MoO2 powder), WSe2 raw materials (e.g., WO3 powder and Se gas), ReS2 raw materials (e.g., NH4ReO4 (ammonium perrhenate) (precursor (solid)) and S gas) or MoTe2 raw materials (e.g., Te powder + MoCl5 and MoO3 powder).

[0087] According to one embodiment, step 420 of forming the tantalum carbide layer is performed in a buffer layer (e.g., Figure 1a and Figure 1b A tantalum carbide film can be formed on the buffer layer 200 in the buffer layer (e.g., Figure 3 andFigure 3 synthesizing or depositing (e.g., CVD deposition) a tantalum carbide film (e.g., TaC) on at least a portion or all of the buffer layer 200 in the substrate 100. Figure 1a and Figure 4a the tantalum carbide film 300).

[0088] According to an embodiment, the forming a tantalum carbide layer step 420 is depositing a tantalum carbide film (e.g., TaC) at a temperature of about 1800 °C to about 2300 °C; about 1900 °C to about 2300 °C; or about 2000 °C to about 2300 °C and a pressure of about 200 torr to about 400 torr. Figure 4b and Figure 4c the tantalum carbide film 300). According to an embodiment, the forming a tantalum carbide layer step 420 can be depositing a tantalum carbide film by supplying a raw material gas required for depositing the tantalum carbide layer under the above-mentioned temperature and pressure conditions. In some examples, a raw material gas and a carrier gas can be supplied. In some examples, the raw material gas can be a raw material gas suitable for a deposition process (e.g., CVD). In some examples, the raw material gas can employ any raw material known in the art for supplying Ta and C (carbon), the specific description of which is omitted herein. In some examples, the atomic ratio of Ta to C in the raw material gas is about 0.9 to about 1.34 : about 1; about 0.1 to about 1.34 : about 1; about 1 to about 1.34 : about 1; about 1.1 to about 1.34 : about 1. In some examples, the carrier gas can be selected from inert gases.

[0089] According to an embodiment, after the forming a tantalum carbide layer step 430, a cooling or heat treatment to a room temperature (rt) or a temperature close to the room temperature can be performed. For example, after the forming a tantalum carbide layer step 430, a heat treatment can be performed at a temperature of about 2000 °C to about 2500 °C under an inert gas (e.g., Ar gas) atmosphere for about 1 hour to about 20 hours; about 2 hours to about 20 hours; about 4 hours to about 20 hours; about 6 hours to about 20 hours; about 8 hours to about 18 hours; or about 8 hours to about 15 hours. After the heat treatment, a cooling to a room temperature (rt) or a temperature close to the room temperature can be performed.

[0090] According to an embodiment, various deposition processes can be used to implement the forming a buffer layer step 420 and the forming a tantalum carbide layer step 430, for example, a chemical vapor deposition (CVD), a physical vapor deposition (PVD), a plasma chemical vapor deposition, a sputtering process, etc., and preferably a CVD process is used to form a stress-reducing material layer.

[0091] The numerical ranges recited herein are inclusive of the endpoints and also include any number subsumed therein. "At least one" as used herein means one or more than one.

[0092] The present application will be explained in more detail by examples and comparative examples below. However, the examples below are only for illustrating the present application, and the scope of the present application is not limited to the examples below.

[0093] Example 1

[0094] The coefficient of thermal expansion of the graphite substrate was 4.5 x 10 -6 / K, a pyrolytic carbon (PyC) layer having a thickness of 5 μm was deposited on the substrate by a CVD deposition method, and then a TaC layer was formed on the pyrolytic carbon (PyC) layer by a CVD deposition method.

[0095] Example 2

[0096] The coefficient of thermal expansion of the graphite substrate was 4.5 x 10 -6 / K, a pyrolytic carbon (PyC) layer having a thickness of 15 μm was deposited on the substrate by a CVD deposition method, and then a TaC layer was formed on the pyrolytic carbon (PyC) layer by a CVD deposition method.

[0097] Example 3

[0098] The coefficient of thermal expansion of the graphite substrate was 4.5 x 10 -6 / K, a pyrolytic carbon (PyC) layer having a thickness of 25 μm was deposited on the substrate by a CVD deposition method, and then a TaC layer was formed on the pyrolytic carbon (PyC) layer by a CVD deposition method.

[0099] Example 4

[0100] The coefficient of thermal expansion of the graphite substrate was 5.5 x 10 -6 / K, a pyrolytic carbon (PyC) layer having a thickness of 5 μm was deposited on the substrate by a CVD deposition method, and then a TaC layer was formed on the pyrolytic carbon (PyC) layer by a CVD deposition method.

[0101] Comparative Example 1

[0102] A TaC composite was prepared in the same manner as in Example 1 except that no buffer layer was formed.

[0103] Comparative Example 2

[0104] A TaC composite was prepared in the same manner as in Example 4 except that no buffer layer was formed.

[0105] A cross section of the TaC composite prepared in Example 1 was measured and observed using a SEM (Scanning Electron Microscope) image. The results are shown in FIG. 1. Figure 4a As shown in FIG. 1, the TaC layer was formed on the pyrolytic carbon (PyC) layer, and the interface between the TaC layer and the pyrolytic carbon (PyC) layer was clear. Figure 4bAs can be seen, a pyrolytic carbon (PyC) layer / TaC layer is formed on the graphite substrate. In addition, as shown in FIG. 1, the TaC composite material prepared in this embodiment is formed with a deposition layer on the entire surface of the substrate and the buffer layer. Figure 4c

[0106] Deposition process of the embodiment

[0107] The graphite substrate was loaded into the deposition chamber, and after evacuation to a vacuum for 1 to 20 hours, pyrolytic carbon was deposited. That is, pyrolytic carbon was deposited by supplying a raw material C3H8to a first carrier gas H2at a high temperature of 1700°C and a process pressure of 400 torr, and in an N2gas atmosphere. Then, TaC was deposited by supplying a raw material Ta to a second carrier gas Ar and CH4at a high temperature of 2100°C and a process pressure of 400 torr. After the deposition process was completed, cooling to room temperature was performed.

[0108] Deposition process of the comparative example

[0109] The graphite substrate was loaded into the deposition chamber, and after evacuation to a vacuum for 1 to 20 hours, TaC was deposited by supplying a raw material Ta to a second carrier gas Ar and CH4at a high temperature of 2100°C and a process pressure of 400 torr. After the deposition process was completed, cooling to room temperature was performed.

[0110] Surface microstructure analysis

[0111] The surface microstructure of the TaC prepared in the embodiment and the comparative example was observed using an SEM, and the crack width was measured as shown in FIGS. 1, 2, 3, and 4, and Table 1. Figure 4a Figure 4b Figure 4c

[0112] [Table 1]

[0113]

[0114] * The average width corresponds to the average value of the cracks measured at 20 points.

[0115] Warpage measurement

[0116] The warpage of the embodiment and the comparative example was measured. The results are shown in Table 2.

[0117] Warpage measurement method

[0118] A TaC-coated product having a size of 200 x 3 mm was prepared, and the height of the product was measured with the upper half of the coordinate measuring instrument as a reference. That is, 10 points were measured at the same intervals of 0°, 60°, and 120°. The deviation of the measured values of 30 points was expressed as warpage.

[0119] [Table 2] ​​​​

[0120]

[0121] Figure 5 、 Figure 6 、 Figure 7a SEM images of the surface of the TaC layer in the TaC composite material, wherein (a) is Comparative Example 1, (b) is Example 4, and (c) is Example 1. Figure 7b 、 Figure 7a 、 Figure 7b In the SEM images of the composite material of the Examples and Comparative Examples, surface cracks were observed. In Comparative Example 1, the crack width of the TaC surface was large, and when the crack gap was measured in the perpendicular direction, the maximum was 3.0 to 3.6 pm. This is because internal stress was generated between the graphite substrate and the TaC. In Examples 1 and 3 in which the buffer layer was introduced, when the crack gap was measured in the perpendicular direction, a slight crack having a maximum width of 0.2 to 0.4 pm (Example 1) appeared, or no crack was observed (Example 4). That is, although there is a difference in the coefficient of thermal expansion between the graphite substrate and the TaC, the buffer layer can relieve the stress between the two and reduce the crack width of the TaC layer surface or prevent the occurrence of cracks, warpage, and peeling.

[0122] In Figure 7a , when the buffer layer was applied, the width (pm) of the slight crack on the surface of the TaC layer could be reduced by a maximum of 2.8 times (e.g., Example 1 and Comparative Example 1). In addition, the width of the slight crack could vary depending on the thickness of the buffer layer. When the buffer layer in Figure 7b was applied, the warpage of the TaC layer surface was reduced by up to 14 times (e.g., comparison of Example 1 and Comparative Example 1). In addition, it can be seen that the warpage varies depending on the thickness of the buffer layer. Table 3 shows the stress variation depending on the thickness of the pyrolytic carbon layer and the TaC layer.

[0123] [Table 3]

[0124]

[0125] (Table 3, "O" indicates that peeling occurs, and "x" indicates that peeling does not occur.)

[0126] In Table 3, the smaller the thickness of the pyrolytic carbon layer (buffer layer), the better the stress relief effect between the graphite substrate and the TaC layer, and the occurrence of peeling can be prevented or reduced, or the crack width can be reduced.

[0127] In addition, when the thickness of the buffer layer is higher than a certain degree, due to the coefficient of thermal expansion in the vertical direction (e.g., the thickness direction) of the formation surface in the buffer layer, it can expand more in the vertical direction (e.g., the thickness direction) of the formation surface than in the horizontal direction of the formation surface, eventually leading to warping and cracking.

[0128] In addition, when the buffer layer is formed by CVD, if the thickness of the buffer layer is less than 1 μm or lower, it can not be possible to deposit the TaC layer well.

[0129] The coefficient of thermal expansion in each of the X, Y, and Z axis directions of the buffer layer formed on the substrate prepared in Examples 1 to 4 was measured, respectively. For each direction, the coefficient of thermal expansion was measured at 30 points at the same interval, and the average value thereof was calculated.

[0130] The coefficient of thermal expansion from room temperature to 1000°C was measured using a dilatometer (DIL 402C).

[0131] According to an embodiment, the tantalum carbide composite material can reduce the width of cracks in the tantalum carbide film and reduce the occurrence of warping by a buffer layer for relieving stress between the substrate (e.g., carbon substrate) and the tantalum carbide film.

[0132] According to an embodiment, the semiconductor manufacturing component employs a tantalum carbide composite material that incorporates a buffer layer for relieving stress between the substrate (e.g., carbon substrate) and the tantalum carbide film, thereby improving the stability of the lifetime, the stability of the semiconductor manufacturing process, and the process efficiency.

[0133] According to an embodiment, due to the difference in physical properties between the graphite substrate and the TaC coating, there is no stress in the high-temperature CVD process, but during the cooling process, due to the difference in physical properties between the two materials, particularly, a large stress can occur due to the coefficient of thermal expansion. As a result, the stress generated is mainly manifested as deformation or cracking, and the degree of damage increases with the number of times the part is used (the degree of damage increases as the temperature increases). Therefore, according to an embodiment, the tantalum carbide composite material can relieve stress by forming a buffer layer (e.g., pyrolytic carbon) having intermediate physical properties between graphite and TaC. It utilizes the difference in the coefficient of expansion between the horizontal (X axis, Y axis) and vertical (Z axis) directions of the formation surface of the buffer layer (e.g., pyrolytic carbon) and the graphite substrate and the TaC coating to relieve stress.

[0134] According to an embodiment, considering the last deposition CTE high Tac, when using existing buffer layer materials, the buffer layer cannot withstand the expansion of TaC. However, according to an embodiment of the present disclosure, the composite material is a buffer layer formed on a substrate by van der Waals force bonding, the buffer layer has a formation surface horizontal direction CTE lower than a formation surface vertical direction CTE, and is formed in a layered structure (for example, using CVD), thereby using the van der Waals force bonding characteristics to withstand the expansion of TaC by internal interlayer sliding (Slide). Referring to Figure 7b and Figure 7a , Figure 7b and ​ are schematic diagrams of a stress relief mechanism using a tantalum carbide composite material according to an embodiment, wherein ​ and ​ The van der Waals force bonding characteristics possessed by the buffer layer of ​ When TaC expands in the horizontal direction of the formation surface as it thermally expands, the horizontal direction bonding of the formation surface does not break, but the bonding in the vertical direction of the formation surface breaks and internal peeling occurs, thereby causing interlayer sliding (cutting line at right side 200 in ​ and ​ The upper part and the line in the left side 200 in

[0135] According to an embodiment, compared to simply applying a buffer layer having a material (for example, SiC or TaC) with a CTE different from the substrate and / or coating, the present disclosure utilizes a buffer layer having a layered structure bonded by van der Waals force, which can withstand the expansion of TaC by internal interlayer sliding based on the van der Waals force bonding characteristics.

[0136] In summary, the embodiments have been described through limited drawings, and those of ordinary skill in the art can make various changes and modifications based on the description. For example, the described technology is executed in a different sequence from the described method, and / or the described constituent elements are combined or combined in a different form from the described method, or replaced or replaced by other constituent elements or equivalents, and appropriate results can be obtained.

Claims

1. A tantalum carbide composite material, characterized by, comprising: a substrate; a buffer layer deposited on the substrate; and a tantalum carbide layer deposited on the buffer layer.

2. The tantalum carbide composite material according to claim 1, wherein the buffer layer comprises a substance bound by van der Waals force.

3. The tantalum carbide composite material according to claim 2, wherein the substance bound by van der Waals force comprises at least one selected from the group consisting of pyrolytic carbon, BN, MoS2, WSe2, ReS2, and MoTe2, or a combination thereof.

4. The tantalum carbide composite material according to claim 1, wherein a coefficient of thermal expansion in a horizontal direction of a formation surface of the buffer layer and a coefficient of thermal expansion in a vertical direction of the formation surface are different.

5. The tantalum carbide composite material according to claim 4, wherein the coefficient of thermal expansion in the vertical direction of the formation surface of the buffer layer is greater than the coefficient of thermal expansion in the horizontal direction of the formation surface.

6. The tantalum carbide composite material according to claim 5, wherein 7. The tantalum carbide composite material according to claim 4, wherein The coefficient of thermal expansion in the vertical direction of the formation surface of the buffer layer is 6.0 x 10 -6 / K to 7.0 x 10 -6 / K. The coefficient of thermal expansion in the horizontal direction of the formation surface of the buffer layer is 0.2 x 10 -6 / K to 0.7 x 10 -6 / K. the coefficient of thermal expansion in the vertical direction of the formation surface of the buffer layer satisfies at least one of i), ii), and iii): i) is lower than a coefficient of thermal expansion of the tantalum carbide layer; ii) is higher than a coefficient of thermal expansion of the substrate; iii) is higher than an intermediate value of the coefficients of thermal expansion of the substrate and the tantalum carbide layer.

8. The tantalum carbide composite material according to claim 1, wherein a thickness of the buffer layer is 1 μm to 100 μm.

9. The tantalum carbide composite material according to claim 1, wherein a thickness of the tantalum carbide layer is 1 μm to 100 μm.

10. The tantalum carbide composite material according to claim 1, wherein the buffer layer is formed as a layered structure with reference to an upper surface of the substrate.

11. The tantalum carbide composite material according to claim 1, wherein the tantalum carbide layer is free of cracks.

12. The tantalum carbide composite material according to claim 1, wherein a warpage of the tantalum carbide composite material is 10 μm to 50 μm.

13. The tantalum carbide composite material according to claim 1, wherein the tantalum carbide layer includes cracks having a width of 0.3 μm to 0.6 μm. comprising the steps of:

14. A method of producing a tantalum carbide composite material, characterized by, preparing a substrate; forming a buffer layer on the substrate; and forming a tantalum carbide layer on the buffer layer, the buffer layer comprises a substance bound by van der Waals force, the buffer layer is formed on at least one surface or all surfaces of the substrate.

15. The method for producing a tantalum carbide composite material according to claim 14, wherein the step of forming the tantalum carbide layer is forming a film on the buffer layer.

16. The method for producing a tantalum carbide composite material according to claim 14, wherein the step of forming the buffer layer is depositing the buffer layer at a temperature of 1500°C to 1900°C and a pressure of 500 torr to 900 torr.

17. The method for producing a tantalum carbide composite material according to claim 14, wherein the step of forming the tantalum carbide layer is depositing a tantalum carbide film at a temperature of 1900°C to 2300°C and a pressure of 200 torr to 400 torr. ​ 18. The method of producing a tantalum carbide composite material according to claim 14, wherein the step of forming the buffer layer and the step of forming the tantalum carbide layer are performed by a CVD process.

19. The method of producing a tantalum carbide composite material according to claim 14, wherein the step of forming the buffer layer is a step of forming a buffer layer including a substance that is bonded by van der Waals force, the substance that is bonded by van der Waals force includes at least one selected from the group consisting of pyrolytic carbon, BN, MoS2, WSe2, ReS2, and MoTe2, or a combination thereof.

20. The method of producing a tantalum carbide composite material according to claim 14, wherein the method of producing is a method of producing the tantalum carbide composite material according to claim 1.

Images