KR20240106956A - Manufacturing method of low-resistance thermal spray coating layer having antistatic function and thermal spray coating layer thereof - Google Patents

Abstract

The present disclosure relates to a method of manufacturing a low-resistance thermal spray coating layer with an antistatic function and the resulting thermal spray coating layer. The present disclosure includes the steps of transferring a coating powder containing a mixed composition of Al ₂ O ₃ and Y ₂ O ₃ as a matrix and TiO ₂ as a filler; and causing the transferred coating powder to pass through high-temperature plasma so that the partially or completely melted particles collide with the substrate in the air at a speed of 100 m/s to 700 m/s to form a coating layer on the substrate. It provides a thermal spray coating method and a thermal spray coating layer according thereto, including the step of, wherein the volume resistance of the coating layer is 10 ⁸ Ω·cm to 10 ¹⁴ Ω·cm.

Description

Manufacturing method of low-resistance thermal spray coating layer having antistatic function and thermal spray coating layer thereof}

This disclosure relates to a method of manufacturing a low-resistance thermal spray coating layer with an antistatic function and the resulting thermal spray coating layer.

Thermal spray coating technology is an advanced technology that melts or semi-melts powder with specific properties required for the surface using a heat source such as plasma in an air or vacuum atmosphere and then sprays it on the substrate at high speed to provide an overlay coating layer. It is one of the most common surface modification methods. In terms of the lack of material limitations, the provision of a coating layer using thermal spray coating technology allows the use of various materials ranging from metal materials, ceramics, and polymer materials alone or in combination, providing a more improved type of coating layer through research on materials. can do. In addition, in view of the existence of various process variables, the functionality of the material can be maximized by changing the microstructure by changing the process variables and studying the coating properties according to the microstructure to develop process variable control technology to achieve optimal microstructure. Therefore, basic research on this must take precedence, and based on this, direct improvement in characteristics becomes possible through continuous applied research.

The above-described information disclosed in the background technology of this invention is only for improving understanding of the background of the present disclosure, and therefore may include information that does not constitute prior art.

The problem to be solved according to the present disclosure is a method of manufacturing a low-resistance thermal spray coating layer having an antistatic function that not only has high density and low resistance mechanical/electrical properties, but also excellent uniformity and stable composition and electrical property distribution, and the same. The purpose is to provide a thermal spray coating layer according to the present invention.

An exemplary method of manufacturing a low-resistance thermal spray coating layer according to the present disclosure includes transferring a coating powder containing a mixed composition of Al ₂ O ₃ and Y ₂ O ₃ as a matrix and TiO ₂ as a filler; and causing the transferred coating powder to pass through high-temperature plasma so that the partially or completely melted particles collide with the substrate in the air at a speed of 100 m/s to 700 m/s to form a coating layer on the substrate. It includes the step of, and the volume resistance of the coating layer may be 10 ⁸ Ω·cm to 10 ¹⁴ Ω·cm.

In some examples, the weight ratio of the Al ₂ O ₃ and Y ₂ O ₃ mixed composition constituting the matrix may be 1:9 to 9:1.

In some examples, when the weight ratio of the coating powder is 100 wt%, the weight ratio of TiO ₂ filled in the matrix of the mixed composition may be 5 wt% to 30 wt%.

In some examples, the coating powder may be a spherical coating powder prepared using a spray drying method.

In some examples, the average particle size of the coating powder may be 1 μm to 25 μm.

In some examples, the thickness of the coating layer may be 100 ㎛ to 1000 ㎛.

An exemplary low-resistance thermal spray coating layer according to the present disclosure transfers a coating powder containing a mixed composition of Al ₂ O ₃ and Y ₂ O ₃ as a matrix and TiO ₂ as a filler, and the transferred coating powder is subjected to high-temperature plasma. A coating layer is formed on the substrate by allowing partially or completely melted particles to collide with the substrate in the air at a speed of 100 m/s to 700 m/s, and the volume resistance of the coating layer is 10 ⁸ . It may be Ω·cm to 10 ¹⁴ Ω·cm.

In some examples, the weight ratio of the Al ₂ O ₃ and Y ₂ O ₃ mixed composition constituting the matrix may be 1:9 to 9:1.

In some examples, when the weight ratio of the coating powder is 100 wt%, the weight ratio of TiO ₂ filled in the matrix of the mixed composition may be 5 wt% to 30 wt%.

In some examples, the coating powder may be a spherical coating powder prepared using a spray drying method.

In some examples, the average particle size of the coating powder may be 1 μm to 25 μm.

In some examples, the thickness of the coating layer may be 100 ㎛ to 1000 ㎛.

The present disclosure provides a method for manufacturing a low-resistance thermal spray coating layer that not only has high density and low resistance mechanical/electrical properties, but also has excellent uniformity and a stable composition and electrical property distribution and has an antistatic function, and a thermal spray coating layer resulting therefrom. .

1 is a schematic diagram illustrating an exemplary thermal spray coating device according to the present disclosure.
2 is a schematic diagram illustrating an exemplary thermal spray coating method according to the present disclosure.
3 is a cross-sectional view of a coating layer according to an exemplary thermal spray coating method according to the present disclosure.
Figure 4a is a SEM (Scanning Electron Microscope) cross-sectional photograph of a thermal spray coating layer according to an example of the present disclosure, and Figure 4b is a SEM cross-sectional photograph of a thermal spray coating layer according to a comparative example of the present disclosure.
FIG. 5A is a planar photograph according to the weight ratio (wt%) of titanium dioxide (TiO ₂ ) in an exemplary thermal spray coating layer according to the present disclosure, and FIG. 5B is a weight ratio of titanium dioxide (TiO ₂ ) in an exemplary thermal spray coating layer according to the present disclosure. This is a graph showing volume resistance (Ω·cm) according to (wt%).
Figure 6 is a schematic diagram showing a simple mixing state of a conventional commercial powder and a complex granular powder according to the present disclosure.
Figure 7 is a schematic diagram showing the required resistivity area of a low-resistance dielectric layer for an easy dechucking electrostatic chuck.
FIGS. 8A and 8B are graphs showing the chucking force (kgf) and dechucking time (sec) of a high-resistance electrostatic chuck and a low-resistance electrostatic chuck.
9A to 9F are cross-sectional views showing an exemplary electrostatic chuck according to the present disclosure.

Hereinafter, preferred embodiments of the present disclosure will be described in detail with reference to the attached drawings.

This disclosure is provided to more completely explain the present disclosure to those skilled in the art, and the following examples may be modified in various other forms, and the scope of the present disclosure is limited to the following examples. It doesn't work. Rather, these embodiments are provided to make the disclosure more faithful and complete, and to fully convey the spirit of the disclosure to those skilled in the art.

In addition, in the drawings below, the thickness and average particle size of each layer are exaggerated for convenience and clarity of explanation, and the same symbols refer to the same elements in the drawings. As used herein, the term “and/or” includes any one and all combinations of one or more of the listed items. In addition, the meaning of "connected" in this specification refers not only to the case where member A and member B are directly connected, but also to the case where member C is interposed between member A and member B to indirectly connect member A and member B. do.

Terms used herein are used to describe specific embodiments and are not intended to limit the disclosure. As used herein, the singular forms include the plural forms unless the context clearly indicates otherwise. Additionally, when used herein, “comprise, include,” and/or “comprising, including” refer to mentioned features, numbers, steps, operations, members, elements, and/or groups thereof. It specifies presence and does not exclude the presence or addition of one or more other shapes, numbers, movements, members, elements and/or groups.

Although the terms first, second, etc. are used herein to describe various members, parts, regions, layers and/or parts, these members, parts, regions, layers and/or parts are limited by these terms. It is obvious that this cannot be done. These terms are used only to distinguish one member, component, region, layer or section from another region, layer or section. Accordingly, a first member, component, region, layer or portion described below may refer to a second member, component, region, layer or portion without departing from the teachings of the present disclosure.

Space-related terms such as “beneath,” “below,” “lower,” “above,” and “upper” are used to refer to an element or feature shown in a drawing. It can be used to facilitate understanding of other elements or features. Terms related to this space are for easy understanding of the present disclosure according to various process states or usage states of the present disclosure, and are not intended to limit the present disclosure. For example, if an element or feature in a drawing is turned over, an element or feature described as “bottom” or “below” becomes “top” or “above.” Therefore, “lower” is a concept encompassing “upper” or “lower.”

1 is a schematic diagram illustrating an exemplary thermal spray coating device 100 according to the present disclosure.

As shown in FIG. 1, an exemplary thermal spray coating device 100 according to the present disclosure includes a plasma spray gun 110, a quantitative powder supply unit 120, a quantitative powder supply pipe 130, a non-quantitative powder supply unit 140, It may include a non-quantified powder supply pipe 150, a transfer gas supply unit 160, and transfer gas supply pipes 171 and 172.

The plasma spray gun 110 includes a first electrode 111 installed at the center to have a length in a horizontal direction, a second electrode 112 spaced around the first electrode 111 and formed to have a length in an approximately horizontal direction, and , a plasma gas supply pipe 113 formed to be spaced apart around the circumference of the first and second electrodes 111 and 112 to have a length in a substantially horizontal direction, and coolant formed to be spaced apart around the plasma gas supply pipe 113 and the second electrode 112. It may include a supply pipe (114). Here, a power supply unit 115 that supplies high voltage may be connected between the first electrode 111 and the second electrode 112. Additionally, an insulating member 116 may be further interposed between the plasma gas supply pipe 113 and the cooling water supply pipe 114. In addition, a nozzle 117 through which plasma gas is sprayed outward may be formed at the end of the second electrode 112.

In this way, when the high voltage by the power supply unit 115 is applied between the first electrode 111 and the second electrode 112 and the plasma gas flows through the gap between the first and second electrodes 111 and 112, approximately A plasma gas flame of 5,000°C or higher may be sprayed through the nozzle 117.

The quantitative powder supply unit 120 may be attached to one side of the plasma spray gun 110. For example, the fixed-quantity powder supply unit 120 may be directly attached to the upper side of the cooling water supply pipe 114 using an adhesive. In some examples, the fixed-quantity powder supply unit 120 may store a fixed amount of ceramic powder.

In some examples, the powder is alumina (Al ₂ O ₃ ), yttria (Y ₂ O ₃ ), YF ₃ , YOF, Y ₄ O ₅ F ₇ , YAM(Y ₄ Al ₂ O ₉ ), YAP(YAlO ₃ ). , YAG (Y ₃ Al ₅ O ₁₂ ), titanium dioxide (TiO ₂ ), and/or rare earth series (series of elements with atomic numbers 57 to 71, including Y and Sc) oxides.

In some examples, the powders include calcium phosphate, bioglass, silicon (SiO ₂ ), hydroxyapatite, Pb(Zr,Ti)O ₃ (PZT), zirconia (ZrO ₂ ), yttria-zirconia (YSZ, Yttria). stabilized Zirconia), dysprosia (Dy ₂ O ₃ ), gadolinia (Gd ₂ O ₃ ), ceria (CeO ₂ ), Gadolinia-ceria (GDC, Gadolinia doped Ceria), magnesia (MgO), barium titanate (BaTiO ₃ ), nickel manganate (NiMn ₂ O ₄ ), potassium sodium niobate (KNaNbO ₃ ), bismuth potassium titanate (BiKTiO ₃ ), bismuth sodium titanate (BiNaTiO ₃ ), CoFe ₂ O ₄ , NiFe ₂ O ₄ , BaFe ₂ O ₄ , NiZnFe ₂ O ₄ , ZnFe ₂ O ₄ , MnxCo _3-x O ₄ (where x is a positive real number of 3 or less), bismuth ferrite (BiFeO ₃ ), bismuth zinc niobate (Bi _1.5 Zn ₁ Nb _1.5O7 ), lithium aluminum titanium phosphate glass ceramic, Li-La-Zr-O based garnet oxide, Li-La-Ti-O based Perovskite oxide, La-Ni-O based oxide, lithium iron phosphate, lithium- Cobalt oxide, Li-Mn-O spinel oxide (lithium manganese oxide), lithium aluminum gallium phosphate, tungsten oxide, tin oxide, lanthanum nickel oxide, lanthanum-strontium-manganese oxide, lanthanum-strontium-iron-cobalt oxide, silicate. Phosphors based on SiAlON, aluminum nitride, silicon nitride, titanium nitride, AlON, silicon carbide, titanium carbide, tungsten carbide, magnesium boride, titanium boride, mixtures of metal oxides and metal nitrides, mixtures of metal oxides and metal carbides, ceramics and polymers. It may be a mixture, or a mixture of one or two types selected from the group consisting of a mixture of ceramics and metals.

Meanwhile, the average particle size of such powder may be approximately 1 ㎛ to approximately 25 ㎛. If the average particle size of the powder is greater than approximately 25 ㎛, the porosity may be greater than approximately 4% and the film quality may be poor. Powders with an average particle size of approximately 1 ㎛ are expensive and practically difficult to obtain. When the average particle size of the powder is approximately 1 ㎛ to approximately 25 ㎛, the coating layer 181 can be formed on the substrate 180 with excellent film quality and a porosity of approximately 1% to approximately 3%.

The quantitative powder supply pipe 130 may connect the quantitative powder supply unit 120 and the nozzle 117 of the plasma spray gun 110. In some examples, the fixed-quantity powder supply pipe 130 may be bent approximately in an “L” shape, and the end may be positioned spaced apart from the tip of the nozzle 117. Here, the length of the fixed-quantity powder supply pipe 130 may be approximately 1 cm to approximately 200 cm. Accordingly, the ceramic powder 191 provided by the quantitative powder supply unit 120 may not be provided with time or area for agglomeration while flowing along the quantitative powder supply pipe 130. That is, because the length of the quantitative powder supply pipe 130 is relatively short, the powders 191 may not aggregate with each other or deposit on the inner wall of the quantitative powder supply pipe 130. Here, it is difficult to implement that the length of the quantitative powder supply pipe 130 is less than approximately 1 cm, and if the length of the quantitative powder supply pipe 130 is greater than approximately 200 cm, the powder may agglomerate inside the supply pipe 130 or powder may form on the inner wall. This can be calming. In some examples, the quantitative powder supply pipe 130 may be fixed to the plasma spray gun 110 through a bracket.

The non-quantitative powder supply unit 140 may be installed at a location spaced apart from the plasma spray gun 110 to supply powder to the quantitative powder supply unit 120 discontinuously or continuously. In some examples, the capacity of the non-quantified powder supply unit 140 may be relatively larger than the capacity of the quantitative powder supply unit 120.

The non-quantitative powder supply pipe 150 may connect the non-quantitative powder supply unit 140 and the fixed-quantity powder supply unit 120 to each other. The length of the non-quantified powder supply pipe 150 varies depending on the length or operating radius of the robot equipped with the plasma spray gun 110, but may be approximately 5 m to approximately 10 m. A powder flow meter 151 capable of controlling the transfer flow rate of powder may be installed in the non-quantitative powder supply pipe 150.

The transport gas supply unit 160 may be connected to the quantitative powder supply unit 120 and/or the non-quantitative powder supply unit 140 to supply transport gas. In some examples, the transport gas may include air, argon, helium, or carbon dioxide.

The transport gas supply pipes 171 and 172 may connect the transport gas supply unit 160 to the quantitative powder supply unit 120 and/or the non-quantitative powder supply unit 140. In some examples, a fixed-quantity powder transfer gas supply pipe 171 and a flow meter 173 may be installed between the transfer gas supply unit 160 and the fixed-quantity powder supply unit 120. In some examples, a non-quantified powder transfer gas supply pipe 172 and a flow meter 174 may be installed between the transfer gas supply unit 160 and the non-quantified powder supply unit 140.

2 is a schematic diagram illustrating an exemplary thermal spray coating method according to the present disclosure.

As shown in FIG. 2, the operation sequence of the thermal spray coating device 100 according to an embodiment of the present disclosure includes an operation step (S1) of the non-quantitative powder supply unit 140 and an operation step (S2) of the quantitative powder supply unit 120. ), a thermal spray coating step (S3), a determination step (S4) of insufficient quantitative powder of the quantitative powder supply unit 120, a thermal spray coating stop step (S5), and an operation step (S6) of the non-quantitative powder supply unit 140. there is.

In the operation step S1 of the non-quantitative powder supply unit 140, powder may be supplied to the fixed-quantity powder supply unit 120 through the non-quantitative powder supply unit 140 and the non-quantitative powder supply pipe 150. To this end, the flow meter 151 of the non-quantified powder supply pipe 150 may be opened, and the flow meter 174 installed in the transfer gas supply pipe 172 connected to the transfer gas supply unit 160 may be opened. In addition, the flow meter 173 installed in the transfer gas supply pipe 171 connected to the transfer gas supply unit 160 may be closed.

In some examples, since the capacity of the non-quantified powder supply unit 140 is smaller than the capacity of the fixed-quantity powder supply unit 120, a relatively small capacity of powder may be supplied to the fixed-quantity powder supply unit 120.

In the operation step (S2) of the fixed-quantity powder supply unit 120, the transfer gas is supplied to the fixed-quantity powder supply unit 120 through the transfer gas supply unit 160 and the fixed-quantity powder transfer gas supply pipe 171, thereby Powder may be supplied to the nozzle 117 of the plasma spray gun 110 through the quantitative powder supply pipe 130 connected to. Here, the flow meter 173 installed in the transfer gas supply pipe 171 connected to the transfer gas supply unit 160 may be opened. Additionally, the flow meter 151 of the non-quantified powder supply pipe 150 may be closed, and the flow meter 174 installed in the transfer gas supply pipe 172 connected to the transfer gas supply unit 160 may be closed.

In the thermal spray coating step (S3), a high voltage is applied between the first and second electrodes 111 and 112 of the plasma spray gun 110, and plasma gas is supplied between the first and second electrodes 111 and 112, thereby forming the nozzle 117. A plasma flame of approximately 5,000°C to 30,000°C, preferably approximately 10,000°C to approximately 15,000°C, is provided, and powder is supplied to this plasma flame through the above-described quantitative powder supply pipe 130, thereby generating a spray stream. And, the coating layer 181 may be formed to a predetermined thickness on the substrate 180 by this spray stream.

In some examples, the spray stream comprising partially or fully molten particles that have passed through the high-temperature plasma flame travels in air at a speed of approximately 100 m/s to approximately 700 m/s, preferably approximately 200 m/s to approximately 600 m/s. The thermal spray coating layer 181 may be formed by colliding on the substrate 180 at a speed of s, more preferably approximately 300 m/s to approximately 500 m/s.

In the determination step (S4) of the quantitative powder shortage of the quantitative powder supply unit 120, it is determined whether the powder in the quantitative powder supply unit 120 is less than the reference value. In some examples, a powder sensor (not shown) installed inside the quantitative powder supply unit 120 may be further included for this determination. The powder sensor may include a laser sensor that senses the powder density within the quantitative powder supply unit 120 or a mass sensor that senses the mass of the quantitative powder supply unit 120. In this determination step, if it is determined that the powder in the fixed-quantity powder supply unit 120 is less than a predetermined reference value, the next step (S5) may be performed.

In the thermal spray coating stop step (S5), the formation of the coating layer 181 by the plasma spray gun 110 may be stopped.

In the operation step S6 of the non-quantitative powder supply unit 140, powder may be supplied to the fixed-quantity powder supply unit 120 through the non-quantitative powder supply unit 140 and the non-quantitative powder supply pipe 150. In some examples, transport gas is supplied to the non-quantitated powder supply unit 140 through the transfer gas supply unit 160 and the non-quantitated transfer gas supply pipe 172, so that the powder of the non-quantitated powder supply unit 140 is transferred to the quantitative powder supply unit 120. ) can be supplied.

To this end, the flow meter 151 of the non-quantified powder supply pipe 150 may be opened, and the flow meter 174 installed in the transfer gas supply pipe 172 connected to the transfer gas supply unit 160 may be opened. In addition, the flow meter 173 installed in the transfer gas supply pipe 171 connected to the transfer gas supply unit 160 may be closed.

In some examples, non-metered powder supply 140 may also be performed during thermal spray coating. That is, during the formation of the coating layer 181 by the plasma spray gun 110, the transfer gas is supplied to the non-quantified powder supply unit 140 through the transfer gas supply unit 160 and the transfer gas supply pipe 172, thereby Powder 140 may be supplied to the quantitative powder supply unit 120. To this end, while the flow meter 173 installed in the transport gas supply pipe 171 of the transport gas supply unit 160 is open, the flow meter 151 of the non-quantitative powder supply pipe 150 is opened, and the transport gas supply unit 160 ) The flow meter 174 installed in the transfer gas supply pipe 172 connected to ) may be opened.

In this way, the embodiment of the present disclosure is an atmospheric pressure plasma spray or thermal spray coating that can supply powder having an average particle size of approximately 1 ㎛ to approximately 25 ㎛, can prevent agglomeration of the powder, and can form a dense coating layer. A device 100 may be provided.

3 is a cross-sectional view of a coating layer according to an exemplary thermal spray coating method according to the present disclosure.

As shown in FIG. 3, the coating powder having an average particle size of approximately 1 ㎛ to approximately 25 ㎛ is transferred and partially or completely melted particles that have passed through the high-temperature plasma are moved at approximately 300 m/s to approximately 500 m/s in the air. A thermal spray coating layer 181 of a certain thickness may be formed by colliding with the substrate 180 at a speed of s.

In some examples, the thickness of the coating layer 181 may be approximately 100 μm to approximately 1000 μm, preferably approximately 200 μm to approximately 800 μm, and more preferably approximately 300 μm to approximately 600 μm.

In some examples, the grain size within coating layer 181 may be approximately 0.1 μm to approximately 25 μm, preferably approximately 0.2 μm to approximately 20 μm, and more preferably approximately 0.3 μm to approximately 10 μm.

Meanwhile, the coating layer 181 includes a plurality of grains and grain boundaries in an approximately two-dimensional plane, and has a ratio (a/b) of the average horizontal length (a) of the grains and the average vertical height (b) of the grains, that is, the aspect ratio. (a/b) may be less than approximately 6.5, preferably less than approximately 5.8, and more preferably less than approximately 5.5.

Additionally, the ratio ((a/b)/m) of the aspect ratio (a/b) and the average particle size (m) of the coating powder may be greater than approximately 0.3, preferably greater than approximately 0.6, and more preferably greater than approximately 1.1. In this way, the coating layer 181 according to the present disclosure has flatter grains (i.e., spreads wider and longer in the horizontal direction), and thus has a very dense membrane structure with a porosity of approximately 1% to approximately 3%.

Figure 4a is a SEM (Scanning Electron Microscope) cross-sectional photograph of a thermal spray coating layer according to an example of the present disclosure, and Figure 4b is a SEM cross-sectional photograph of a thermal spray coating layer according to a comparative example of the present disclosure. In some examples, the present disclosure transfers a coating powder comprising a mixed composition of Al ₂ O ₃ and Y ₂ O ₃ as a matrix and TiO ₂ as a filler, and passes the transferred coating powder through a high temperature plasma to partially Alternatively, the completely molten particles may be allowed to collide with the substrate in the air at a speed of 100 m/s to 700 m/s to form a coating layer on the substrate.

In some examples, the weight ratio of the Al ₂ O ₃ and Y ₂ O ₃ mixed composition that makes up the matrix may be approximately 1:9 to approximately 9:1. In some examples, when the weight ratio of the coating powder is 100 wt%, the weight ratio of TiO ₂ filled in the matrix of the mixed composition may be approximately 5 wt% to approximately 30 wt%.

In some examples, the coating powder may be a spherical coating powder prepared using a spray drying method. In general, methods for manufacturing coating powder include many drying methods such as natural drying, artificial drying, spray drying, film drying, foam drying, and freeze drying, but the drying method according to the present disclosure may include a spray drying method. In some examples, the spray drying method is a drying method in which powder is sprayed into hot air to increase the unit surface area and evaporate the moisture in the powder with hot air, using a spray nozzle, a cylinder that can be connected to the hot air, and a collector that separates the powder and hot air. It can be included. In this way the powder can eventually be provided in spherical, complexed and granulated form.

In some examples, the average particle size of the coating powder may be approximately 1 μm to approximately 40 μm. In some examples, the thickness of the coating layer may be approximately 100 μm to approximately 1000 μm.

In this way, the present disclosure transfers a coating powder containing a mixed composition of Al ₂ O ₃ and Y ₂ O ₃ as a matrix and TiO ₂ as a filler to form a thermal spray coating layer by the above-described method, as shown in Figure 4a. As described above, a coating layer with no layer separation and high density can be obtained.

On the other hand, when a coating powder containing TiO ₂ as a filler is transferred to a matrix of Al ₂ O ₃ to form a thermal spray coating layer by the above-described method, as shown in FIG. 4b, layer separation occurs and a coating layer with low density appears. can be obtained.

Figure 5a is a photograph according to the weight ratio (wt%) of TiO ₂ in an exemplary thermal spray coating layer according to the present disclosure, and Figure 5b is a photograph according to the weight ratio (wt%) of TiO ₂ in an exemplary thermal spray coating layer according to the present disclosure ( This is a graph showing Ω·cm). In Figure 5b, the X-axis is the weight ratio of TiO ₂ (wt%), and the Y-axis is the volume resistance of TiO ₂ (Ω·cm). _As shown in FIGS. 5A and 5B _, the thermal spray coating layer according to the present disclosure has a volume resistance of ^5.86 X 10 ¹³ Ω· ^cm _, and when the weight ratio of TiO ₂ is 20wt%, _the volume resistance is ^1.28 As the weight ratio increases, the volume resistance decreases, and accordingly, the thermal spray coating layer according to the present disclosure can be used as a low-resistance thermal spray coating layer with an antistatic function.

In _addition , the thermal spray coating layer ^according to _the present disclosure has a ^leakage current of _1.66 When the weight ratio _was ^20wt %, the leakage current _was ^7.35

In _addition , the thermal spray coating layer ^according to the present disclosure has _an insulation resistance _of ^6.04 _At 20wt ^% , _the insulation resistance was ^1.28

In addition, the thermal spray coating layer according to the present disclosure has an electrostatic capacity of 101 pF when the weight ratio of TiO ₂ is 5wt%, an electrostatic resistance of 111 pF when the weight ratio of TiO ₂ is 10wt%, and an electrostatic capacity when the weight ratio of TiO ₂ is 20wt%. It is 116 pF, and when the weight ratio of TiO ₂ is 30wt%, the electrostatic capacitance is 122 pF, and as the weight ratio of TiO ₂ increases, the electrostatic capacitance increases.

In addition, the thermal spray coating layer according to the present disclosure has a relative dielectric constant of 11.7 εr when the weight ratio of TiO ₂ is 5wt%, a relative dielectric constant of 13.2 εr when the weight ratio of TiO ₂ is 10wt%, and a relative dielectric constant when the weight ratio of TiO ₂ is 20wt%. When the weight ratio of TiO 2 was 13.9 εr and the weight ratio of TiO ₂ was 30 wt%, the relative dielectric constant was 14.4 pF, and as the weight ratio of TiO ₂ increased, the relative dielectric constant increased.

Table 1 below summarizes the weight ratio of TiO2, coating thickness, leakage current, insulation resistance, volume resistance, capacitance, and relative dielectric constant as described above.

[Table 1]

Figure 6 is a schematic diagram showing a simple mixed state of a conventional commercial powder and a complexed granular powder state according to the present disclosure. As shown in the left drawing of FIG. 6, in the conventional simple mixed powder, a concentration gradient occurs between the compositions within the coating layer due to cohesion between constituent materials, etc., which may cause layer separation within the coating layer. However, as shown in the right drawing of FIG. 6, in the case of the composite granular powder according to the present disclosure, it is possible to form a coating layer with a uniform composition during coating, and accordingly, layer separation does not occur within the coating layer.

Figure 7 is a schematic diagram showing the required resistivity area of a low-resistance dielectric layer for an easy dechucking electrostatic chuck.

Electrostatic chucks for manufacturing semiconductors and/or displays may also be provided with a coating layer (also referred to as a dielectric layer). Electrostatic chucks churn or de-chuck semiconductor wafers, display substrates, etc., and even when the applied voltage is turned off, the electric charge on the surface of the dielectric layer is not discharged but remains on the surface, and the attractive force with the wafer or substrate is not immediately relieved. Chucking problems may occur. From the perspective of the upper dielectric layer of the electrostatic chuck, the above specific resistance is in the resistance range of Johnson-Rabeck (10 ⁹ Ω·cm to 10 ¹³ Ω·cm), so it has the effect of improving the chucking force compared to the Coulomb type electrostatic chuck when voltage is applied, and the applied voltage is turned off. Dechucking performance can be improved by developing an anti-static function.

Figure 8a is a graph showing the chucking force (kgf) and dechucking time (sec) of a high-resistance electrostatic chuck and a low-resistance electrostatic chuck. In Figure 8a, the X-axis is the applied voltage (kV) and the Y-axis is the chucking force (kgf). In addition, in Figure 8a, the high-resistance electrostatic chuck is a case where the dielectric layer is provided only by Al ₂ O ₃ powder as in the prior art, and the low-resistance electrostatic chuck has a mixed composition of Al ₂ O ₃ and Y ₂ O ₃ as the matrix as described in the present disclosure. It is a dielectric layer provided by a coating powder containing TiO ₂ as a filler. As shown in FIG. 8A, the high-resistance electrostatic chuck exhibited a chucking force of 0.2 kgf to 1.8 kgf at an applied voltage of 1 kV to 3 kV. Additionally, as shown in FIG. 8A, the low-resistance electrostatic chuck exhibited a chucking force of 1.3 kgf to 2.3 kgf at an applied voltage of 1 kV to 3 kV. Therefore, it can be seen that the chucking force of the low-resistance electrostatic chuck according to the present disclosure is higher than the chucking force of the conventional high-resistance electrostatic chuck.

Figure 8b is a graph showing the dechucking time (sec) of a high-resistance electrostatic chuck and a low-resistance electrostatic chuck. In Figure 8b, the X-axis is the applied voltage (kV) and the Y-axis is the dechucking time (sec). In addition, in Figure 8b, the high-resistance electrostatic chuck is a case in which the dielectric layer is provided only by Al ₂ O ₃ powder as in the prior art, and the low-resistance electrostatic chuck has a mixed composition of Al ₂ O ₃ and Y ₂ O ₃ as the matrix of the present disclosure. It is a dielectric layer provided by a coating powder containing TiO ₂ as a filler. As shown in FIG. 8B, the high-resistance electrostatic chuck exhibited a dechucking time of 0 sec to 24 sec after an applied voltage of 1 kV to 3 kV. Additionally, as shown in FIG. 8A, the low-resistance electrostatic chuck exhibited a dechucking time of 5 sec to 8 sec after an applied voltage of 1 kV to 3 kV. Therefore, it can be seen that the dechucking time of the low-resistance electrostatic chuck according to the present disclosure is faster than the dechucking time of the conventional high-resistance electrostatic chuck.

9A to 9F are cross-sectional views showing exemplary electrostatic chucks according to the present disclosure.

As shown in FIG. 9A, an exemplary electrostatic chuck according to the present disclosure includes a low-resistance insulating layer 1811, an electrostatic chuck electrode 1812, and a low-resistance dielectric layer 1813 sequentially provided on a metal base member 180M. It can be. In some examples, low-resistance insulating layer 1811 may be referred to as a lower dielectric layer and low-resistance dielectric layer 1813 may be referred to as an upper dielectric layer. In some examples, metal base member 180M may generally include aluminum or titanium.

Similarly as described above, the low-resistance insulating layer 1811 transfers coating powder containing a mixed composition of Al ₂ O ₃ and Y ₂ O ₃ as a matrix and TiO ₂ as a filler, and the transferred coating powder is exposed to high temperature plasma. The partially or completely melted particles are allowed to pass through and collide with the metal base member 180M at a speed of 100 m/s to 700 m/s in the air, so that the low-resistance insulating layer 1811 is formed on the metal base member 180M. ), and the volume resistance of the low-resistance insulating layer 1811 is 10 ⁹ Ω·cm to 10 ¹³ Ω·cm. The electrostatic chuck electrode 1812 may be a monopolar type or a bipolar type, and may be provided on the low-resistance insulating layer 1811.

Similar to the above-mentioned, the low-resistance dielectric layer 1813 transfers coating powder containing a mixed composition of Al ₂ O ₃ and Y ₂ O ₃ as a matrix and TiO ₂ as a filler, and the transferred coating powder is exposed to high-temperature plasma. The partially or completely melted particles are allowed to pass through and collide on the low-resistance insulating layer 1811 and the electrostatic chuck electrode 1812 at a speed of 100 m/s to 700 m/s in the air to form the low-resistance dielectric layer 1813. ) is formed on the low-resistance insulating layer 1811 and the electrostatic chuck electrode 1812, and the volume resistance of the low-resistance dielectric layer 1813 is 10 ⁹ Ω·cm to 10 ¹³ Ω·cm.

As shown in FIG. 9B, an exemplary electrostatic chuck according to the present disclosure includes a high-resistance insulating layer 1811H, an electrostatic chuck electrode 1812, and a low-resistance dielectric layer 1813 sequentially provided on a metal base member 180M. It can be. In some examples, high-resistance insulating layer 1811H may be referred to as a lower dielectric layer and low-resistance dielectric layer 1813 may be referred to as an upper dielectric layer.

Similar to what was described above, the high-resistance insulating layer 1811H transfers coating powder containing Al ₂ O ₃ and/or Y ₂ O ₃ , and allows the transferred coating powder to pass through high-temperature plasma to partially or completely melt. The particles collide with the metal base member 180M in the air at a speed of 100 m/s to 700 m/s so that a high-resistance insulating layer 1811H is formed on the metal base member 180M. The electrostatic chuck electrode 1812 may be a monopolar type or a bipolar type, and may be provided on the high-resistance insulating layer 1811H.

Similar to the above-mentioned, the low-resistance dielectric layer 1813 transfers coating powder containing a mixed composition of Al ₂ O ₃ and Y ₂ O ₃ as a matrix and TiO ₂ as a filler, and the transferred coating powder is exposed to high-temperature plasma. The partially or completely melted particles are allowed to pass through and collide with the high-resistance insulating layer 1811H and the electrostatic chuck electrode 1812 at a speed of 100 m/s to 700 m/s in the air, thereby colliding with the low-resistance dielectric layer 1813. ) is formed on the high-resistance insulating layer 1811H and the electrostatic chuck electrode 1812, and the volume resistance of the low-resistance dielectric layer 1813 is 10 ⁹ Ω·cm to 10 ¹³ Ω·cm.

As shown in FIG. 9C, the exemplary electrostatic chuck according to the present disclosure may further include a high-resistance buffer layer 1811B between the high-resistance insulating layer 1811H and the low-resistance dielectric layer 1813.

Similar to the above-mentioned, the high-resistance buffer layer (1811B) transfers coating powder containing Al ₂ O ₃ and/or Y ₂ O ₃ and allows the transferred coating powder to pass through high temperature plasma to be partially or completely melted. Particles are allowed to collide on the high-resistance insulating layer 1811H and the electrostatic chuck electrode 1812 in the air at a speed of 100 m/s to 700 m/s so that the high-resistance buffer layer 1811B is formed on the high-resistance insulating layer 1811H. and formed on the electrostatic chuck electrode 1812.

Similar to the above-mentioned, the low-resistance dielectric layer 1813 transfers coating powder containing a mixed composition of Al ₂ O ₃ and Y ₂ O ₃ as a matrix and TiO ₂ as a filler, and the transferred coating powder is exposed to high-temperature plasma. The partially or completely melted particles are allowed to pass through and collide with the high-resistance buffer layer 1811B at a speed of 100 m/s to 700 m/s in the air, so that the low-resistance dielectric layer 1813 is formed on the high-resistance buffer layer 1811B. However, the volume resistance of the low-resistance dielectric layer 1813 is 10 ⁹ Ω·cm to 10 ¹³ Ω·cm.

As shown in FIG. 9D, an exemplary electrostatic chuck according to the present disclosure may sequentially provide an electrostatic chuck electrode 1812 and a low-resistance dielectric layer 1813 on a ceramic base member 180C. In some examples, low-resistance dielectric layer 1813 may be referred to as a top dielectric layer. In some examples, ceramic base member 180C may include alumina (Al ₂ O ₃ ), aluminum nitride (AlN), or SiC.

The electrostatic chuck electrode 1812 may be provided directly on the ceramic base member 180C. Since the ceramic base member 180C has electrically insulating properties, the plurality of electrostatic chuck electrodes 1812 do not electrically short-circuit each other.

Similar to the above-mentioned, the low-resistance dielectric layer 1813 transfers coating powder containing a mixed composition of Al ₂ O ₃ and Y ₂ O ₃ as a matrix and TiO ₂ as a filler, and the transferred coating powder is exposed to high-temperature plasma. The low-resistance dielectric layer 1813 is caused to pass through the partially or fully melted particles to impact the ceramic base member 180C and the electrostatic chuck electrode 1812 at a speed of 100 m/s to 700 m/s in the air. It is formed on the ceramic base member 180C and the electrostatic chuck electrode 1812, and the low-resistance dielectric layer 1813 has a volume resistance of 10 ⁹ Ω·cm to 10 ¹³ Ω·cm.

As shown in FIG. 9E, the exemplary electrostatic chuck according to the present disclosure may be provided with a high-resistance buffer layer 1811B between the ceramic base member 180C and the low-resistance dielectric layer 1813.

Similar to the above-mentioned, the high-resistance buffer layer (1811B) transfers coating powder containing Al ₂ O ₃ and/or Y ₂ O ₃ and allows the transferred coating powder to pass through high temperature plasma to be partially or completely melted. Particles are allowed to collide on the ceramic base member 180C and the electrostatic chuck electrode 1812 in the air at a speed of 100 m/s to 700 m/s so that the high-resistance buffer layer 1811B is electrostatically deposited on the ceramic base member 180C. It is formed on the chuck electrode 1812.

Similar to the above-mentioned, the low-resistance dielectric layer 1813 transfers coating powder containing a mixed composition of Al ₂ O ₃ and Y ₂ O ₃ as a matrix and TiO ₂ as a filler, and the transferred coating powder is exposed to high-temperature plasma. The partially or completely melted particles are allowed to pass through and collide with the high-resistance buffer layer 1811B at a speed of 100 m/s to 700 m/s in the air, so that the low-resistance dielectric layer 1813 is formed on the high-resistance buffer layer 1811B. However, the volume resistance of the low-resistance dielectric layer 1813 is 10 ⁹ Ω·cm to 10 ¹³ Ω·cm.

As shown in FIG. 9F, the exemplary electrostatic chuck according to the present disclosure may be provided with a (high-resistance) buffer layer between the ceramic base member 180C, the electrostatic chuck electrode 1812, and the low-resistance dielectric layer 1813.

Similar to the above-mentioned, the high-resistance buffer layer (1811B) transfers coating powder containing Al ₂ O ₃ and/or Y ₂ O ₃ and allows the transferred coating powder to pass through high temperature plasma to be partially or completely melted. Particles are allowed to collide on the ceramic base member 180C in the air at a speed of 100 m/s to 700 m/s so that a high-resistance buffer layer 1811B is formed on the ceramic base member 180C. Additionally, an electrostatic chuck electrode 1812 is provided on the high-resistance buffer layer 1811B.

Similar to the above-mentioned, the low-resistance dielectric layer 1813 transfers coating powder containing a mixed composition of Al ₂ O ₃ and Y ₂ O ₃ as a matrix and TiO ₂ as a filler, and the transferred coating powder is exposed to high-temperature plasma. The partially or completely melted particles are allowed to pass through and collide with the high-resistance buffer layer 1811B at a speed of 100 m/s to 700 m/s in the air, so that the low-resistance dielectric layer 1813 is formed on the high-resistance buffer layer 1811B. and the electrostatic chuck electrode 1812, and the low-resistance dielectric layer 1813 has a volume resistance of 10 ⁹ Ω·cm to 10 ¹³ Ω·cm. Here, the high-resistance buffer layer 1811B compensates for the adhesion force of the low-resistance dielectric layer 1813, thereby preventing the low-resistance dielectric layer 1813 from peeling.

In this way, electrostatic chucks according to the present disclosure commonly include a low-resistance dielectric layer or upper dielectric layer 1813 having a volume resistance of 10 ⁹ Ω·cm to 10 ¹³ Ω·cm. Accordingly, electrostatic chucks not only have excellent anti-static function as described above, but also include the technical advantages of excellent electrostatic power and dechucking time.

What has been described above is only an example of a method for manufacturing a low-resistance thermal spray coating layer with an exemplary antistatic function according to the present disclosure and an example for carrying out the thermal spray coating layer according to the same, and the present disclosure is not limited to the above-described embodiments. , as claimed in the following patent claims, it is said that the technical spirit of the present disclosure exists to the extent that various modifications can be made by anyone skilled in the field without departing from the gist of the present disclosure. .

Claims (12)

Transferring a coating powder containing a mixed composition of Al ₂ O ₃ and Y ₂ O ₃ as a matrix and TiO ₂ as a filler; and
Allowing the transferred coating powder to pass through high-temperature plasma so that the partially or completely melted particles collide with the substrate in the air at a speed of 100 m/s to 700 m/s to form a coating layer on the substrate. Includes steps,
The volume resistance of the coating layer is 10 ⁸ Ω·cm to 10 ¹⁴ Ω·cm. The thermal spray coating method. According to paragraph 1,
The weight ratio of the Al ₂ O ₃ and Y ₂ O ₃ mixed composition constituting the matrix is 1:9 to 9:1. According to paragraph 1,
When the weight ratio of the coating powder is 100wt%, the weight ratio of the TiO ₂ filled in the matrix of the mixed composition is 5wt% to 30wt%. According to paragraph 1,
The thermal spray coating method, wherein the coating powder is a spherical coating powder manufactured using a spray drying method. According to paragraph 1,
The thermal spray coating method wherein the average particle size of the coating powder is 1 ㎛ to 25 ㎛. According to paragraph 1,
A thermal spray coating method wherein the thickness of the coating layer is 100 ㎛ to 1000 ㎛. A coating powder containing a mixed composition of Al ₂ O ₃ and Y ₂ O ₃ as a matrix and TiO ₂ as a filler is transferred, and the transferred coating powder is passed through high temperature plasma to form partially or completely melted particles. A coating layer is formed on the substrate by colliding with the substrate at a speed of 100 m/s to 700 m/s in the air, and the volume resistance of the coating layer is 10 ⁸ Ω·cm to 10 ¹⁴ Ω·cm. Coating layer. In clause 7,
The weight ratio of the Al ₂ O ₃ and Y ₂ O ₃ mixed composition constituting the matrix is 1:9 to 9:1, thermal spray coating layer. In clause 7,
When the weight ratio of the coating powder is 100 wt%, the weight ratio of the TiO ₂ filled in the matrix of the mixed composition is 5 wt% to 30 wt%. In clause 7,
The coating powder is a thermal spray coating layer that is a spherical coating powder manufactured using a spray drying method. In clause 7,
The thermal spray coating layer wherein the average particle size of the coating powder is 1 ㎛ to 25 ㎛. In clause 7,
The thermal spray coating layer has a thickness of 100 ㎛ to 1000 ㎛.