Spray coating method of fine powder, spray coating layer thereby, and fine powder supply device therefor

Abstract

The present disclosure relates to a spray coating method of fine powder, a spray coating layer thereby, and a fine powder supply device therefor. The present disclosure provides a spray coating method, a spray coating layer thereby, and a powder supply device, the method comprising the steps of: transferring a dry powder having an average particle size of 1㎛ to 25㎛; and allowing the transferred dry powder to pass through high-temperature plasma so that partially or completely melted particles collide with an electrostatic chuck in the atmosphere at a speed of 100m / s to 700m / s, and thus, a coating layer having grains and grain boundaries is formed on the electrostatic chuck, wherein the aspect ratio (a / b) of the average horizontal length (a) of the grains to the average vertical height (b) of the grains is less than 6.5, and the ratio ((a / b) / m) of the aspect ratio (a / b) to the average particle size (m) of the dry powder is greater than 0.3 or, a volume resistance of the coating layer in a temperature range of 100℃ to 400℃ is 1012 Ω·cm to 1014 Ω·cm, or the volume resistance of the coating layer in a voltage range of less than 3 KV is 1013 Ω·cm to 1014 Ω·cm.

Description

A method for spray coating fine powder, a spray coating layer according to the method, and a fine powder supply device therefor

[0001] The present disclosure relates to a method for spray coating a fine powder, a spray coating layer according to the method, and a fine powder supply device therefor.

[0002] Thermal spray coating technology is an advanced surface modification method that uses a heat source such as plasma in an air or vacuum environment to melt or semi-melt powder with specific surface properties, and then sprays it at high speed onto a substrate to provide an overlay coating layer. Because thermal spray coating technology is not limited to a wide range of materials, it can be used singly or in combination with a wide range of materials, from metals to ceramics and polymers. Therefore, research into these materials can yield improved coating layers. Furthermore, given the diverse process variables involved, it is crucial to study these variables to alter the microstructure and the coating characteristics based on the microstructure. This can lead to the development of process variable control techniques that achieve optimal microstructures, thereby maximizing material functionality. Therefore, fundamental research in this area is essential. This, in turn, can lead to direct property enhancement through ongoing application research.

[0003] The average particle size of the powder used in this thermal spray coating is larger than approximately 30 ㎛, and the porosity of the coating layer is higher than approximately 4%, so it is difficult to say that the film quality is excellent. That is, when the average particle size of the powder is approximately 25 ㎛, the porosity of the coating layer is known to be approximately 1% to approximately 3%, and the film quality is excellent. However, it is difficult for the current thermal spray coating method to supply powder having an average particle size of less than approximately 30 ㎛. That is, the distance from the powder supply unit to the thermal spray coating device (e.g., plasma spray gun) is relatively far, so that the powder is deposited in the transport pipe or agglomerated during transport. In particular, when the average particle size of the powder is smaller than approximately 10 ㎛, the agglomeration phenomenon during transport is very severe, making powder supply almost impossible.

[0004] Meanwhile, fine powders, smaller than tens of micrometers in size, adhere to each other due to electrostatic attraction, forming larger aggregates. These aggregates are comprised of numerous weakly bound primary particles. As the aggregates grow in size, their fluidity deteriorates significantly, making it extremely difficult to continuously and consistently transport the powder using conventional methods.

[0005] In particular, continuous transport and supply of powder is very important in cases where fine powder must be used, such as in plasma spray, flame spray, arc spray, high velocity oxy-fuel spray, cold spray, and aerosol deposition coating, and depending on the transport condition of the powder, not only the consumption of powder but also the speed and uniformity of the coating change.

[0006] For example, conventionally, the methods used to supply powder to a vacuum device used in coating using aerosol deposition included a screw method and a vibration method. Here, the screw method is a method of transporting powder through a screw. In this method, when the powder is smaller than a few micrometers in size, the powder clumps and the clumped powder becomes compacted inside the screw and tube, which makes it difficult to practically apply when transporting fine powder. In addition, the vibration method is a method of applying vibration to a powder container to suspend powder and using a transport gas to supply the suspended powder to a vacuum device. When vibration and transport gas are used in this way, the supply of powder becomes discontinuous due to the vibration and the powder becomes compacted against the container wall, which makes it difficult to continuously provide fine powder and limits the amount of powder that can be used.

[0007] The above-described information disclosed in the background technology of this invention is only intended to improve understanding of the background of the present disclosure and may therefore include information that does not constitute prior art.

[0008] The problem to be solved by the present disclosure is to provide a method for spray coating fine powder, which enables stable supply of fine powder without blocking the powder transport pipe by preventing agglomeration of fine powder during the transport process of fine powder, and a spray coating layer according to the method.

[0009] Another problem to be solved according to the present disclosure is to provide a method for spray coating using fine powder and a spray coating layer using the same, which can be applied to a dielectric of a high-temperature electrostatic chuck for manufacturing a display or semiconductor by reducing grain size and porosity or pores in a coating layer using fine powder and thereby improving insulating properties at high temperatures.

[0010] Another problem to be solved according to the present disclosure is to provide a method for spray coating of fine powder and a spray coating layer thereof that can be applied as a dielectric of a high-insulation electrostatic chuck for manufacturing a display or semiconductor by reducing the grain size and porosity or pores in the coating layer using fine powder and thereby improving electrical characteristics at high voltage.

[0011] Another problem to be solved according to the present disclosure is to provide a method for spray coating of fine powder applicable as a dielectric in a process chamber for manufacturing a display or semiconductor by reducing grain size and porosity or pores in a coating layer using fine powder, thereby improving plasma resistance in a plasma environment and reducing particle generation, and a spray coating layer according to the method.

[0012] Another problem to be solved according to the present disclosure is to provide a fine powder supply device that can stably supply fine powder without clogging the powder transport pipe by preventing agglomeration of fine powder during the process of transporting the fine powder.

[0013] An exemplary method for thermal spray coating of fine powder according to the present disclosure comprises the steps of: transporting dry powder having an average particle size of 1 μm to 25 μm; and allowing the transported dry powder to pass through a high-temperature plasma so that partially or completely melted particles collide with a substrate in the air at a speed of 100 m / s to 700 m / s, thereby forming a coating layer having grains and grain boundaries on the substrate, wherein an aspect ratio (a / b) of an average horizontal length (a) of the grains to an average vertical height (b) of the grains is less than 6.5, and a ratio ((a / b) / m) of the aspect ratio (a / b) to an average particle size (m) of the dry powder is greater than 0.3, or a volume resistivity of the coating layer in a temperature range of 100°C to 400°C is less than 10. 12 Ω·cm to 10 14Ω·cm, or the volume resistivity of the coating layer is 10 in the voltage range less than 3 kV. 13 Ω·cm to 10 14 It can be Ω·cm.

[0014] In some examples, the dry powder is alumina (Al2O3), yttria (Y2O3), YF3, YOF, Y4O5F7, YAM (Y4Al2O9), YAP (YAlO3), YAG (Y3Al5O 12 ) or rare earth series (a series of elements with atomic numbers from 57 to 71, including Y and Sc) oxides.

[0015] In some examples, the aspect ratio (a / b) may be 5.5 to 6.5, and the ratio ((a / b) / m) may be 0.3 to 1.1.

[0016] In some examples, the thickness of the coating layer may be from 100 μm to approximately 1000 μm.

[0017] In some examples, the size of the grains may be from 0.1 μm to 25 μm.

[0018] An exemplary fine powder thermal spray coating layer according to the present disclosure is formed by transporting dry powder having an average particle size of 1 ㎛ to 25 ㎛, allowing the transported dry powder to pass through a high-temperature plasma so that partially or completely melted particles collide with an electrostatic chuck in the air at a speed of 100 m / s to 700 m / s, so that a coating layer having grains and grain boundaries is formed on the electrostatic chuck, wherein an aspect ratio (a / b) of an average horizontal length (a) of the grains and an average vertical height (b) of the grains is smaller than 6.5, and a ratio ((a / b) / m) of the aspect ratio (a / b) and the average particle size (m) of the dry powder is greater than 0.3, or a volume resistivity of the coating layer is 10 in a temperature range of 100°C to 400°C. 12 Ω·cm to 10 14 Ω·cm, or the volume resistivity of the coating layer is 10 in the voltage range less than 3 kV.13 Ω·cm to 10 14 It can be Ω·cm.

[0019] In some examples, the dry powder is alumina (Al2O3), yttria (Y2O3), YF3, YOF, Y4O5F7, YAM (Y4Al2O9), YAP (YAlO3), YAG (Y3Al5O 12 ) or rare earth series (a series of elements with atomic numbers from 57 to 71, including Y and Sc) oxides.

[0020] In some examples, the aspect ratio (a / b) may be 5.5 to 6.5, and the ratio ((a / b) / m) may be 0.3 to 1.1.

[0021] In some examples, the thickness of the coating layer may be from 100 μm to approximately 1000 μm.

[0022] In some examples, the size of the grains may be from 0.1 μm to 25 μm.

[0023] An exemplary powder supply device according to the present disclosure may include a powder storage unit that compresses and stores dry powder having an average particle size of 5 μm to 100 μm, a housing unit having a first side opening formed inwardly from a side of the powder storage unit, and a vertical opening formed perpendicular to the first side opening for vertically dropping the powder; a circular head unit having a disc that rotates at 1 RPM to 5,000 RPM and is coupled to the first side opening, and a powder storage hole provided along the circumference of the disc at a position corresponding to the vertical opening in the disc; and a gas powder supply unit having a support body, a second side opening formed on the side of the support body so that the disc is coupled, a gas supply hole to which a gas supply pipe is coupled to an upper portion of the second side opening, and a gas powder injection hole to which a gas powder injection pipe is coupled to a lower portion of the second side opening.

[0024] In some examples, the powder storage hole formed in the disc may include an inclined inner wall whose diameter gradually decreases from top to bottom with respect to a vertical central axis.

[0025] In some examples, the powder storage hole formed in the disc may include an inner wall having the same diameter from top to bottom with respect to a vertical central axis.

[0026] In some examples, the disc includes a flat upper surface and a flat lower surface opposite the upper surface, the powder storage hole penetrates the upper surface and the lower surface, and an angle (θ) between the inner wall of the powder storage hole and the lower surface may be 30° to 90°.

[0027] In some examples, the disc may include a flat upper surface and a flat lower surface opposite the upper surface, and the powder storage hole may include a first inner wall having a diameter that gradually decreases from the upper surface toward the lower surface, a second inner wall having a diameter that increases horizontally from the first inner wall, and a third inner wall having the same diameter from the second inner wall to the lower surface.

[0028] In some examples, the gas supply hole of the gas powder supply unit may include a first supply hole having the same diameter from top to bottom, and a second supply hole having a diameter that gradually decreases from the first supply hole to bottom.

[0029] In some examples, the diameter of the gas powder injection hole may be larger than the diameter of the powder storage hole of the disc.

[0030] In some examples, the rotational center axis of the circular head portion may be coupled to the housing portion.

[0031] In some examples, the disc includes a flat upper surface and a flat lower surface opposite the upper surface, the powder storage hole penetrates the upper surface and the lower surface, and an angle (θ) between the inner wall of the powder storage hole and the lower surface may be 90° to 150°.

[0032] In some examples, the average particle size of the dry powder may be from 1 nm to 25 μm.

[0033] The present disclosure provides a method for spray coating fine powder, which enables stable supply of fine powder without clogging of a powder transport pipe and without agglomeration of fine powder during the transport process of the fine powder, and a spray coating layer according to the method.

[0034] The present disclosure provides a method for spray coating of fine powder and a spray coating layer thereof, which can be applied as a dielectric of a high-temperature electrostatic chuck for manufacturing a display or semiconductor by reducing grain size and porosity or pores in a coating layer using fine powder and thereby improving insulating properties at high temperatures.

[0035] The present disclosure provides a method for spray coating of fine powder and a spray coating layer thereof, which can be applied as a dielectric of a high-insulation electrostatic chuck for manufacturing a display or semiconductor by reducing grain size and porosity or pores in a coating layer using fine powder and improving electrical properties at high voltage.

[0036] The present disclosure provides a method for spray coating of fine powder applicable as a dielectric in a process chamber for manufacturing a display or semiconductor by reducing grain size and porosity or pores in a coating layer using fine powder, thereby improving plasma resistance in a plasma environment and reducing particle generation, and a spray coating layer resulting therefrom.

[0037] The present disclosure provides a fine powder supply device capable of stably supplying fine powder without clogging a powder transport pipe and preventing agglomeration of fine powder during the transport process of fine powder.

[0038] FIG. 1 is a schematic diagram illustrating an exemplary fine powder spray coating device according to the present disclosure.

[0039] FIG. 2 is a schematic diagram illustrating an exemplary fine powder spray coating method according to the present disclosure.

[0040] FIG. 3 is a cross-sectional view of a coating layer according to an exemplary fine powder spray coating method according to the present disclosure.

[0041] FIG. 4 is a graph showing the relationship between the average particle size of the powder and the aspect ratio (a / b) in the coating layer according to the exemplary fine powder spray coating method according to the present disclosure.

[0042] FIG. 5 is a cross-sectional view illustrating an example of a high-temperature and / or high-insulation electrostatic chuck having a coating layer applied thereto according to an exemplary fine powder spray coating method according to the present disclosure.

[0043] FIG. 6 is a graph showing the relationship between temperature and volume resistance in a coating layer according to an exemplary fine powder spray coating method according to the present disclosure.

[0044] FIG. 7 is a graph showing the relationship between the applied voltage and the leakage current in the coating layer according to the exemplary fine powder spray coating method according to the present disclosure.

[0045] FIG. 8 is a graph showing the relationship between applied voltage and insulation resistance in a coating layer according to an exemplary fine powder spray coating method according to the present disclosure.

[0046] FIG. 9 is a graph showing the relationship between the applied voltage and the volume resistance in a coating layer according to an exemplary fine powder spray coating method according to the present disclosure.

[0047] [Revised 21.08.2024 under Rule 91] Figure 10 is a cross-sectional view illustrating an exemplary fine powder supply device according to the present disclosure.

[0048] FIGS. 11 to 17 are cross-sectional views illustrating a powder storage hole and its surrounding structure among exemplary fine powder supply devices according to the present disclosure.

[0049] Fig. 18 is a surface and cross-sectional photograph of a spray coating film by an exemplary fine powder supply device according to the present disclosure.

[0050] FIG. 19a is a graph showing the powder discharge amount per minute according to the rotation speed of the circular head portion in an exemplary fine powder supply device according to the present disclosure.

[0051] FIG. 19b is a graph showing the powder discharge amount per minute versus the number of discharge amount evaluations in an exemplary fine powder supply device according to the present disclosure.

[0052] Hereinafter, preferred embodiments of the present disclosure will be described in detail with reference to the attached drawings.

[0053] The present disclosure is provided to more fully explain the present disclosure to those skilled in the art. The following examples may be modified in various ways, and the scope of the present disclosure is not limited to the following examples. Rather, these examples are provided to more faithfully and completely convey the spirit of the present disclosure to those skilled in the art.

[0054] In addition, in the drawings below, the thickness and average grain size of each layer are exaggerated for convenience and clarity of explanation, and the same reference numerals in the drawings indicate the same elements. 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 means not only when member A and member B are directly connected, but also when member C is interposed between member A and member B, so that member A and member B are indirectly connected.

[0055] The terminology used herein is for the purpose of describing particular embodiments and is not intended to be limiting of the present disclosure. As used herein, the singular forms "a," "an," and "the" may include plural forms unless the context clearly dictates otherwise. Furthermore, as used herein, the words "comprise" and "include" and / or "comprising" and "including" specify the presence of stated features, numbers, steps, operations, elements, components, and / or groups thereof, but do not preclude the presence or addition of one or more other features, numbers, operations, elements, components, and / or groups thereof.

[0056] Although terms such as first, second, etc. are used herein to describe various elements, components, regions, layers, and / or portions, it is to be understood that these elements, components, regions, layers, and / or portions are not limited by these terms. These terms are only used to distinguish one element, component, region, layer, or portion from another. Accordingly, a first element, component, region, layer, or portion described below may also refer to a second element, component, region, layer, or portion without departing from the teachings of the present disclosure.

[0057] Spatial terms such as "beneath," "below," "lower," "above," and "upper" may be used to facilitate understanding of one element or feature depicted in the drawings and other elements or features. These spatial terms are provided to facilitate understanding of the present disclosure in 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 the drawing is flipped, an element or feature described as "beneath" or "below" becomes "above" or "above." Therefore, "below" is a concept encompassing "upper" or "below."

[0058] FIG. 1 is a schematic diagram illustrating an exemplary fine powder spray coating device (100) according to the present disclosure.

[0059] As illustrated in FIG. 1, an exemplary spray coating device (100) according to the present disclosure may include a plasma spray gun (110), a quantitative powder supply unit (120), a quantitative powder supply pipe (130), a non-quantitative powder supply unit (140), a non-quantitative powder supply pipe (150), a transport gas supply unit (160), and a transport gas supply pipe (171, 172).

[0060] The plasma spray gun (110) may include a first electrode (111) installed at the center to have a length in a horizontal direction, a second electrode (112) formed to have a length in a substantially horizontal direction while spaced apart from the periphery of the first electrode (111), a plasma gas supply pipe (113) formed to have a length in a substantially horizontal direction while spaced apart from the periphery of the first and second electrodes (111, 112), and a cooling water supply pipe (114) formed to have a length in a substantially horizontal direction while spaced apart from the periphery of the plasma gas supply pipe (113) and the second electrode (112). Here, a power supply unit (115) for supplying a high voltage may be connected between the first electrode (111) and the second electrode (112). In addition, an insulating member (116) may be further interposed in the plasma gas supply pipe (113) and the cooling water supply pipe (114). Additionally, a nozzle (117) through which plasma gas is sprayed outward may be formed at the end of the second electrode (112).

[0061] In this way, when a 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, 112), a plasma gas flame of approximately 5,000°C or higher can be sprayed through the nozzle (117).

[0062] The quantitative powder supply unit (120) can be attached to one side of the plasma spray gun (110). For example, the quantitative powder supply unit (120) can be directly bonded to the upper side of the cooling water supply pipe (114) using an adhesive. In some examples, the quantitative powder supply unit (120) can quantitatively store ceramic powder.

[0063] In some examples, the powders are alumina (Al2O3), yttria (Y2O3), YF3, YOF, Y4O5F7, YAM (Y4Al2O9), YAP (YAlO3), YAG (Y3Al5O 12 ) and / or rare earth series (a series of elements with atomic numbers from 57 to 71, including Y and Sc) oxides.

[0064] In some examples, the powder may be calcium phosphate, bioglass, silicon (SiO2), hydroxyapatite, Pb(Zr,Ti)O3 (PZT), titanium dioxide (TiO2), zirconia (ZrO2), yttria-stabilized zirconia (YSZ), dysprosia (Dy2O3), gadolinia (Gd2O3), ceria (CeO2), gadolinia-ceria (GDC), magnesia (MgO), barium titanate (BaTiO3), nickel manganate (NiMn2O4), potassium sodium niobate (KNaNbO3), bismuth potassium titanate (BiKTiO3), bismuth sodium titanate (BiNaTiO3), CoFe2O4, NiFe2O4, BaFe2O4, NiZnFe2O4, ZnFe2O4,MnxCo 3-x O4 (where x is a positive real number less than or equal to 3), bismuth ferrite (BiFeO3), bismuth zinc niobate (Bi 1.5 Zn1Nb 1.5O7), lithium aluminum titanium phosphate glass ceramics, Li-La-Zr-O series Garnet oxide, Li-La-Ti-O series Perovskite oxide, La-Ni-O series oxide, lithium iron phosphate, lithium-cobalt oxide, Li-Mn-O series Spinel oxide (lithium manganese oxide), lithium aluminum gallium phosphate oxide, tungsten oxide, tin oxide, lanthanum nickelate, lanthanum-strontium-manganese oxide, lanthanum-strontium-iron-cobalt oxide, silicate phosphor, SiAlON series phosphor, 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, mixtures of ceramics and polymers, or mixtures of ceramics and metals. It can be a mixture of one or two selected types.

[0065] Meanwhile, the average particle size of the powder may be approximately 1 ㎛ to approximately 25 ㎛. When 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 having an average particle size of approximately 1 ㎛ or smaller are expensive and practically difficult to obtain. When the average particle size of the powder is approximately 1 ㎛ to approximately 25 ㎛, a coating layer (181) having excellent film quality and a porosity of approximately 1% to approximately 3% can be formed on the substrate (180).

[0066] The quantitative powder supply pipe (130) can be connected between the quantitative powder supply unit (120) and the nozzle (117) of the plasma spray gun (110). In some examples, the quantitative powder supply pipe (130) can be bent in an approximately “L” shape, and the end can be positioned spaced apart from the tip of the nozzle (117). Here, the length of the quantitative powder supply pipe (130) can be approximately 1 cm to approximately 200 cm. Accordingly, the ceramic powder (191) by the quantitative powder supply unit (120) can flow along the quantitative powder supply pipe (130) without providing time or area for agglomeration. That is, since the length of the quantitative powder supply pipe (130) is relatively short, the powder (191) can be prevented from agglomerating with each other or depositing on the inner wall of the quantitative powder supply pipe (130). Here, it is difficult to implement a length of the quantitative powder supply pipe (130) of less than approximately 1 cm, and if the length of the quantitative powder supply pipe (130) is greater than approximately 200 cm, powder may aggregate inside the supply pipe (130) or powder may be deposited on the inner wall. In some examples, the quantitative powder supply pipe (130) may be fixed to the plasma spray gun (110) via a bracket.

[0067] The non-quantitative powder supply unit (140) is installed at a location spaced apart from the plasma spray gun (110) and can supply powder discontinuously or continuously to the quantitative powder supply unit (120). In some examples, the capacity of the non-quantitative powder supply unit (140) may be relatively large compared to the capacity of the quantitative powder supply unit (120).

[0068] The non-quantitative powder supply pipe (150) can connect the non-quantitative powder supply unit (140) and the quantitative powder supply unit (120) to each other. The length of the non-quantitative powder supply pipe (150) varies depending on the length or operating radius of the robot equipped with the plasma spray gun (110), but can be approximately 5 m to approximately 10 m. A powder flow meter (151) capable of controlling the conveying flow rate of the powder can be installed in the non-quantitative powder supply pipe (150).

[0069] The transport gas supply unit (160) can be connected to the quantitative powder supply unit (120) and / or the non-quantitative powder supply unit (140) to supply the transport gas. In some examples, the transport gas can include air, argon, helium, or carbon dioxide.

[0070] The transfer gas supply pipe (171, 172) can connect the transfer gas supply unit (160) to the quantitative powder supply unit (120) and / or the non-quantitative powder supply unit (140). In some examples, a quantitative powder transfer gas supply pipe (171) and a flow meter (173) can be installed between the transfer gas supply unit (160) and the quantitative powder supply unit (120). In some examples, a non-quantitative powder transfer gas supply pipe (172) and a flow meter (174) can be installed between the transfer gas supply unit (160) and the non-quantitative powder supply unit (140).

[0071] FIG. 2 is a schematic diagram illustrating an exemplary fine powder spray coating method according to the present disclosure.

[0072] As illustrated in FIG. 2, the operation sequence of the spray coating device (100) according to the embodiment of the present disclosure may include an operation step (S1) of the non-quantitative powder supply unit (140), an operation step (S2) of the quantitative powder supply unit (120), a spray coating step (S3), a quantitative powder shortage determination step (S4) of the quantitative powder supply unit (120), a spray coating stop step (S5), and an operation step (S6) of the non-quantitative powder supply unit (140).

[0073] In the operation step (S1) of the non-quantitative powder supply unit (140), powder can be supplied to the quantitative 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-quantitative powder supply pipe (150) can be opened, and also, the flow meter (174) installed in the transport gas supply pipe (172) connected to the transport gas supply unit (160) can be opened. In addition, the flow meter (173) installed in the transport gas supply pipe (171) connected to the transport gas supply unit (160) can be closed.

[0074] In some examples, since the capacity of the non-quantitative powder supply unit (140) is smaller than the capacity of the quantitative powder supply unit (120), a relatively small capacity of powder can be supplied to the quantitative powder supply unit (120).

[0075] In the operation step (S2) of the quantitative powder supply unit (120), the transport gas is supplied to the quantitative powder supply unit (120) through the transport gas supply unit (160) and the quantitative powder transport gas supply pipe (171), so that the powder can be supplied to the nozzle (117) of the plasma spray gun (110) through the quantitative powder supply pipe (130) connected to the quantitative powder supply unit (120). Here, the flow meter (173) installed in the transport gas supply pipe (171) connected to the transport gas supply unit (160) can be opened. In addition, the flow meter (151) of the non-quantitative powder supply pipe (150) can be closed, and also the flow meter (174) installed in the transport gas supply pipe (172) connected to the transport gas supply unit (160) can be closed.

[0076] In the plasma spray coating step (S3), a high voltage is applied between the first and second electrodes (111, 112) of the plasma spray gun (110), and plasma gas is supplied between the first and second electrodes (111, 112), thereby providing a plasma flame of about 5,000°C to about 30,000°C, preferably about 10,000°C to about 15,000°C, through the nozzle (117), and furthermore, powder is supplied to the plasma flame through the quantitative powder supply pipe (130) described above, thereby generating a spray stream, and a coating layer (181) can be formed on a substrate (180) with a predetermined thickness by this spray stream.

[0077] In some examples, a spray stream comprising partially or fully molten particles that have passed through a high-temperature plasma flame may impinge on a substrate (180) at a velocity of about 100 m / s to about 700 m / s, preferably about 200 m / s to about 600 m / s, and more preferably about 300 m / s to about 500 m / s in air, thereby forming a spray coating layer (181).

[0078] In the quantitative powder shortage determination step (S4) of the quantitative powder supply unit (120), it is determined whether the powder in the quantitative powder supply unit (120) is less than a 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 in 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 quantitative powder supply unit (120) is less than a predetermined reference value, the next step (S5) may be performed.

[0079] In the warrior coating stop step (S5), the formation of the coating layer (181) by the plasma spray gun (110) can be stopped.

[0080] In the operation step (S6) of the non-quantitative powder supply unit (140), powder can be supplied to the quantitative powder supply unit (120) through the non-quantitative powder supply unit (140) and the non-quantitative powder supply pipe (150). In some examples, the powder of the non-quantitative powder supply unit (140) can be supplied to the quantitative powder supply unit (120) by supplying the transport gas to the non-quantitative powder supply unit (140) through the transport gas supply unit (160) and the non-quantitative transport gas supply pipe (172).

[0081] To this end, the flow meter (151) of the non-quantitative powder supply pipe (150) may be opened, and also the flow meter (174) installed in the transport gas supply pipe (172) connected to the transport gas supply unit (160) may be opened. In addition, the flow meter (173) installed in the transport gas supply pipe (171) connected to the transport gas supply unit (160) may be closed.

[0082] In some examples, the non-quantitative powder supply unit (140) can be performed even during the thermal spray coating. That is, during the formation of the coating layer (181) by the plasma spray gun (110), the powder of the non-quantitative powder supply unit (140) can be supplied to the quantitative powder supply unit (120) by supplying the transport gas through the transport gas supply unit (160) and the transport gas supply pipe (172). 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) can be opened, and also the flow meter (174) installed in the transport gas supply pipe (172) connected to the transport gas supply unit (160) can be opened.

[0083] In this way, the embodiment of the present disclosure can provide an atmospheric pressure plasma spray or thermal spray coating device (100) capable of supplying powder having an average particle size of about 1 ㎛ to about 25 ㎛, preventing agglomeration of the powder, and forming a dense coating layer.

[0084] FIG. 3 is a cross-sectional view of a coating layer according to an exemplary fine powder spray coating method according to the present disclosure.

[0085] As illustrated in FIG. 3, a dry powder having an average particle size of about 1 ㎛ to about 25 ㎛ is transferred and partially or completely melted particles that have passed through a high-temperature plasma collide on a substrate (180) at a speed of about 300 m / s to about 500 m / s in the air, thereby forming a spray coating layer (181) of a certain thickness.

[0086] In some examples, the thickness of the coating layer (181) may be from about 100 μm to about 1000 μm, preferably from about 200 μm to about 800 μm, and more preferably from about 300 μm to about 600 μm.

[0087] In some examples, the grain size within the coating layer (181) may be from about 0.1 μm to about 25 μm, preferably from about 0.2 μm to about 20 μm, and more preferably from about 0.3 μm to about 10 μm.

[0088] Meanwhile, the coating layer (181) includes a plurality of grains and grain boundaries in an approximately two-dimensional plane, and the ratio (a / b) of the average horizontal length (a) of the grains and the average vertical height (b) of the grains, i.e., 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.

[0089] Additionally, the ratio of the aspect ratio (a / b) to the average particle size (m) of the dry powder ((a / b) / m) 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 grains that are flatter (i.e., spread wider and longer in the horizontal direction), and thus has a very dense film structure with a porosity of approximately 1% to approximately 3%.

[0090] [Example 1]

[0091] A coating layer (film) was formed using the above-described method using dry powder having an average particle size of approximately 25 ㎛. At this time, the average horizontal length (a) of the coated particles or grains was approximately 28 ㎛, the average vertical height (b) was approximately 4.3 ㎛, and accordingly, the aspect ratio (a / b) was calculated to be approximately 6.5, and (a / b) / m was calculated to be approximately 0.3.

[0092] [Example 2]

[0093] A coating layer was formed by the above-described method using dry powder having an average particle size of approximately 10 μm. At this time, the average horizontal length (a) of the coated particles was approximately 22 μm, the average vertical height (b) was approximately 3.8 μm, and accordingly, the aspect ratio (a / b) was calculated to be approximately 5.8, and (a / b) / m was calculated to be approximately 0.6.

[0094] [Example 3]

[0095] A coating layer was formed using dry powder having an average particle size of approximately 5 μm. At this time, the average horizontal length (a) of the coated particles was approximately 16 μm, the average vertical height (b) was approximately 2.9 μm, and accordingly, the aspect ratio (a / b) was calculated to be approximately 5.5, and (a / b) / m was calculated to be approximately 1.1.

[0096] [Comparative Example 1]

[0097] A coating layer was formed by a conventional method using dry powder having an average particle size of approximately 35 μm. At this time, the average horizontal length (a) of the coated particles was approximately 33 μm, the average vertical height (b) was approximately 4.8 μm, and accordingly, the aspect ratio (a / b) was calculated to be approximately 6.9, and (a / b) / m was calculated to be approximately 0.2.

[0098] Table 1 below summarizes the average particle size (m) of the dry powder for use in the spraying according to Comparative Example 1 and Examples 1 to 3, the average horizontal length (a) of the coated particles, the average vertical height (b) of the coated particles, the aspect ratio (a / b), and the ratio ((a / b) / m).

[0099] Comparative Example 1 Example 1 Example 2 Example 3 Average particle size of powder (m, ㎛) 3525105 Average horizontal length of coated particles (a) 33282216 Average vertical length of coated particles (b) 4.84.33.82.9 Aspect ratio (a / b) 6.96.55.85.5 (a / b) / m 0.20.30.61.1

[0100] FIG. 4 is a graph showing the relationship between the average particle size (㎛) of the powder and the aspect ratio (a / b) in the coating layer according to the thermal spray coating method of an exemplary fine powder according to the present disclosure. In FIG. 4, the X-axis represents the average particle size (㎛) of the powder, and the Y-axis represents the ratio of the average horizontal length (a) to the average vertical height (b) of the grains in the thermal spray coating layer, i.e., the aspect ratio (a / b). As can be seen in FIG. 4, as the average particle size (㎛) of the powder decreases, the average aspect ratio (a / b) of the grains also decreases. Here, the slope between the average particle size (㎛) of the powder and the average aspect ratio (a / b) of the grains was calculated to be approximately 0.0467.

[0101] In this way, the coating layer according to the present disclosure includes a plurality of grains and grain boundaries in an approximately two-dimensional plane, and the ratio (a / b) of the average transverse length (a) of the grains and the average vertical height (b) of the grains, that is, the aspect ratio (a / b), is less than approximately 6.5, and the ratio ((a / b) / m) of the aspect ratio (a / b) and the average particle size (m) of the powder is greater than approximately 0.3, so that the transverse length of the grains becomes longer and flatter in the transverse direction compared to the average particle size of the powder, and accordingly, a coating layer having an excellent density and a porosity of approximately 1% to approximately 3% can be provided.

[0102] FIG. 5 is a cross-sectional view illustrating an example of a high-temperature and / or high-insulation electrostatic chuck (200) to which a coating layer is applied according to an exemplary fine powder spray coating method according to the present disclosure.

[0103] In the example illustrated in FIG. 5, a high temperature and / or high insulation electrostatic chuck (200) according to the exemplary fine powder spray coating method according to the present disclosure may include a base member (210) and a support member (220).

[0104] The base member (210) may include a lower region (212) having a relatively large width and an upper region (214) having a relatively small width on the lower region (212). In some examples, a plurality of cooling lines (211) may be provided in the lower region (212) with a predetermined pitch, and a heating line (213) may be provided in the upper region (214) with a predetermined pitch. A cooling medium may flow through the cooling lines (211) to cool the lower region (212) of the base member (210) to a predetermined temperature, and an electric current may flow through the heating lines (213) to heat the upper region (214) of the base member (210) to a predetermined temperature. In some examples, the heating line (213) may be formed of a nickel-chromium heating wire and an insulator surrounding the same. In some examples, the base member (210) may be provided as an aluminum alloy, pure titanium, or a titanium alloy.

[0105] The support member (220) may be provided directly on the base member (210). In some examples, the support member (220) may include a first dielectric layer (221), an electrode layer (223), and a second dielectric layer (222). The first dielectric layer (221) may be provided on the base member (210). The electrode layer (223) may be provided on the first dielectric layer (221). The second dielectric layer (222) may be provided on the first dielectric layer (221) and the electrode layer (223).

[0106] In some examples, the first dielectric layer (221) may be provided on the base member (210) by the spray coating method described above. In some examples, the second dielectric layer (222) may be provided on the electrode layer (223) and the first dielectric layer (221) by the spray coating method described above.

[0107] In some examples, at least one of the first and second dielectric layers (221, 122) is formed of alumina (Al2O3), yttria (Y2O3), YF3, YOF, Y4O5F7, YAM (Y4Al2O9), YAP (YAlO3), YAG (Y3Al5O 12 ) and / or rare earth series (a series of elements with atomic numbers from 57 to 71, including Y and Sc) oxides.

[0108] In some examples, the base member (210) and / or the support member (220) may be provided in an approximately circular shape when viewed from above when the base member (210) and / or the support member (220) are for semiconductor wafers, and may be provided in an approximately square shape when viewed from above when the base member (210) and / or the support member (220) are for display glass. In some examples, when the electrostatic chuck (200) is used for semiconductor manufacturing, the diameter of the support member (220) may be approximately 100 mm to approximately 400 mm. In some examples, when the electrostatic chuck is used for display manufacturing, the length of one side of the support member (220) may be approximately 400 mm to approximately 3500 mm.

[0109] In some examples, the electrostatic chuck (200) can be used in a temperature range of about 100° C. to about 800° C. In some examples, the standard deviation of the thermal expansion coefficient between the base member (210) and the support member (220) can be about 0.01% to about 15%. Therefore, in the range of about 100° C. to about 800° C., which is the operating temperature of the electrostatic chuck, the warping phenomenon due to the difference in the thermal expansion coefficient between the base member (210) and the support member (220) can be minimized, and thus the flatness of the electrostatic chuck can be maintained excellently in a high-temperature environment.

[0110] In some examples, when the base member (210) is provided with an aluminum alloy (CTE: 23) and the first and second dielectric layers (221, 122) constituting the support member (220) are provided with aluminum oxide (CTE: 7.3), the standard deviation of the CTE is approximately 11%. In some examples, when the base member (210) is provided with a titanium alloy (CTE: 9.4) and the first and second dielectric layers (221, 122) constituting the support member (220) are provided with yttrium oxide (CTE: 10), the standard deviation of the CTE may be approximately 1.9%. In some examples, when the base member (210) is provided with a titanium alloy (CTE: 9.4) and the first and second dielectric layers (221, 122) constituting the support member (220) are provided with aluminum oxide (CTE: 7.3), the standard deviation of the CTE may be approximately 1.5%. In some examples, when the base member (210) is provided with pure titanium (CTE: 8.6) and the first and second dielectric layers (221, 122) constituting the support member (220) are provided with aluminum oxide (CTE: 7.3), the standard deviation of the CTE may be approximately 0.9%. In this way, in some examples, even when the electrostatic chuck (200) is used in a high temperature environment of about 100°C to about 800°C, the standard deviation of the thermal expansion coefficient between the base member (210) and the support member (220) can be managed to be less than about 2%, so that warping hardly occurs and excellent flatness can be maintained.

[0111] In some examples, the first dielectric layer (121) and / or the second dielectric layer (122) described above may be provided by transporting dry alumina powder having an average particle size of about 1 μm to about 25 μm as a transport gas while allowing partially or fully molten particles that have passed through a high-temperature plasma to collide on the base member (210) in the air at a speed of about 100 m / s to about 700 m / s, preferably about 200 m / s to about 600 m / s, and more preferably about 300 m / s to about 500 m / s.

[0112] In some examples, the first dielectric layer (121) and / or the second dielectric layer (122) described above includes a plurality of grains and grain boundaries in an approximately two-dimensional plane, and the ratio (a / b) of the average transverse length (a) of the grains to the average vertical height (b) of the grains, i.e., the aspect ratio, may be less than about 6.5, preferably less than about 5.8, and more preferably less than about 5.5. In addition, the ratio ((a / b) / m) of the aspect ratio (a / b) to the average particle size (m) of the dry powder may be greater than about 0.3, preferably greater than about 0.6, and more preferably greater than about 1.1.

[0113] In some examples, the first dielectric layer (121) and / or the second dielectric layer (122) described above has a volume resistivity of about 10 in a high temperature environment of about 100°C to about 800°C. 12 Ω·cm to approximately 10 14 It may be Ω·cm. In the present disclosure, due to the reduction in grain size and curvature within the first dielectric layer (121) and / or the second dielectric layer (122), the electrical properties are improved at high temperatures, and thus, the electrostatic chuck can be used for the manufacture of semiconductors and / or displays.

[0114] [Example 4]

[0115] A dielectric layer (coating layer) was formed by the above-described coating method using alumina dry powder having an average particle size of approximately 10 ㎛. The dielectric layer had a thickness of 4.39 X 10 at 100°C. 14 It exhibited a volume resistivity of Ω·cm and 2.36 X 10 at 200℃. 14 It exhibited a volume resistivity of Ω·cm and 4.68 X 10 at 300℃. 13 It exhibited a volume resistivity of Ω·cm and 3.37 X 10 at 400℃. 12 It exhibited a volume resistivity of Ω·cm.

[0116] [Comparative Example 2]

[0117] A dielectric layer (coating layer) was formed by a conventional coating method using alumina dry powder having an average particle size of approximately 35 ㎛. The dielectric layer had a thickness of 9.03 X 10 at 100°C. 13 It exhibited a volume resistivity of Ω·cm and 2.77 X 10 at 200℃. 13 It exhibited a volume resistivity of Ω·cm and 1.36 X 10 at 300℃. 12 It exhibited a volume resistivity of Ω·cm and 5.13 X 10 at 400℃. 10 It exhibited a volume resistivity of Ω·cm.

[0118] Table 2 below shows the volume resistance (Ω·cm) by temperature (℃) according to Example 4 and Comparative Example 2.

[0119] Classification 100℃200℃300℃400℃Example 44.39 X 10 14 2.36 X 10 14 4.68 X 10 13 3.37 X 10 12 Comparative example 29.03 X 10 13 2.77 X 10 13 1.36 X 10 12 5.13 X 10 10

[0120] Fig. 6 is a graph showing the relationship between the temperature and the volume resistivity in the coating layer according to the spray coating method of an exemplary fine powder according to the present disclosure. In Fig. 6, the X-axis is temperature (℃), and the Y-axis is volume resistivity (Ω cm). As shown in Fig. 6, at 100℃ to 400℃, the dielectric layer according to Example 4 has a volume resistivity of approximately 4.39 X 10 14 Ω·cm or approximately 3.37 X 10 12 It has a volume resistivity of Ω·cm, but at 100℃ to 400℃, the dielectric layer according to Comparative Example 2 has a resistivity of approximately 9.03 X 10 13 Ω·cm or approximately 5.13 X 10 10 It has a volume resistivity of Ω·cm.

[0121] In this way, the coating layer or dielectric layer according to the present disclosure has a density of approximately 4.39 X 10 in a high temperature environment. 14 Ω·cm or approximately 3.37 X 10 12 Having a volume resistivity of Ω·cm, it can be used as a dielectric layer of an electrostatic chuck for semiconductor and / or display manufacturing.

[0122] Fig. 7 is a graph showing the relationship between the applied voltage and the leakage current in the coating layer according to the exemplary fine powder spray coating method according to the present disclosure. Here, the X-axis represents the applied voltage (V) and the Y-axis represents the leakage current (A).

[0123] As shown in Fig. 7, in Example 4, the dielectric layer has a leakage current of approximately 5.73 X 10 in a high voltage environment of approximately 1 kV to approximately 3 kV. -10 A to approximately 8.39 X 10 -9 A may be, but in Comparative Example 2, the dielectric layer has a leakage current of approximately 1.09 X 10 in a high voltage environment of approximately 1 kV to approximately 3 kV. -8 A to approximately 2.51 X 10 -7 It could be A.

[0124] Fig. 8 is a graph showing the relationship between applied voltage and insulation resistance in a coating layer according to an exemplary fine powder spray coating method according to the present disclosure. Here, the X-axis represents the applied voltage (V) and the Y-axis represents the insulation resistance (Ω).

[0125] As shown in Fig. 8, in Example 4, the dielectric layer has an insulation resistance of approximately 1.74 X 10 in a high voltage environment of approximately 1 kV to approximately 3 kV. 12 Ω or approximately 3.58 X 10 11 Ω, but in Comparative Example 2, the dielectric layer has an insulation resistance of approximately 9.18 X 10 in a high voltage environment of approximately 1 kV to approximately 3 kV. 10 Ω or approximately 1.19 X 10 10 It could be Ω.

[0126] FIG. 9 is a graph showing the relationship between the applied voltage and the volume resistance in a coating layer according to an exemplary fine powder spray coating method according to the present disclosure. Here, the X-axis represents the applied voltage (V) and the Y-axis represents the insulation resistance (Ω).

[0127] As shown in Fig. 9, in Example 4, the dielectric layer has a volume resistivity of approximately 1.59 X 10 in a high voltage environment of approximately 1 kV to approximately 3 kV. 14 Ω·cm or approximately 3.25 X 10 13 Ω·cm, but in Comparative Example 2, the dielectric layer has an insulation resistance of approximately 8.79 X 10 in a high voltage environment of approximately 1 kV to approximately 3 kV. 12 Ω·cm or approximately 1.14 X 10 12 It can be Ω·cm.

[0128] In this way, the dielectric layer according to the present disclosure has improved electrical properties in a high-voltage environment due to a reduction in grain size and a reduction in void ratio, and thus can be used in an electrostatic chuck for manufacturing semiconductors and / or displays.

[0129] Meanwhile, the present disclosure can form a plasma-resistant coating layer by transporting a dry powder containing yttrium having an average particle size of about 1 ㎛ to about 25 ㎛ and passing it through a high-temperature plasma so that partially or fully melted particles collide on a process component for manufacturing a semiconductor or display at a speed of about 300 m / s to about 500 m / s in the air. Similarly to the above, the coating layer includes a plurality of grains and grain boundaries in an approximately two-dimensional plane, and the ratio (a / b) of the average horizontal length (a) of the grains to the average vertical height (b) of the grains, i.e., the aspect ratio, may be less than about 6.5, preferably less than about 5.8, and more preferably less than about 5.5. In addition, the ratio ((a / b) / m) of the aspect ratio (a / b) and the average particle size (m) of the dry powder may be greater than about 0.3, preferably greater than about 0.6, and more preferably greater than about 1.1.

[0130] In some examples, the dry powder containing yttrium is selected from the group consisting of yttria (Y2O3), YF3, YOF, Y4O5F7, YAM (Y4Al2O9), YAP (YAlO3) and / or YAG (Y3Al5O 12 ) may be included.

[0131] [Comparative Example 3]

[0132] A plasma-resistant coating layer was manufactured by spraying yttrium dry powder having an average particle size of approximately 37 μm onto the surface of a process part using a conventional method.

[0133] [Example 5]

[0134] A plasma-resistant coating layer was produced by spraying yttrium dry powder having an average particle size of approximately 10 μm onto the surface of a process part using the coating method described above.

[0135] [Example 6]

[0136] A plasma-resistant coating layer was produced by spraying yttrium dry powder having an average particle size of approximately 3 μm onto the surface of a process part using the above-described coating method.

[0137] Table 3 below summarizes the average particle size (m) of the dry powder containing yttrium, the surface roughness of the plasma-resistant coating layer, and the electrical characteristics of the plasma-resistant coating layer.

[0138] Note: Size of powder (㎛, D) 50 )Surface roughness (㎛)Electrical propertiesVolume resistivity (Ω·cm)Insulation strength (V / ㎛)Comparative example 3379.076.34X10 14 9.21 Example 5102.611.32X10 15 35.89 Example 633.053.05X10 15 38.74

[0139] In the case of Comparative Example 3, the surface roughness of the plasma-resistant coating layer was approximately 9.07 ㎛, and the volume resistivity of the plasma-resistant coating layer was approximately 6.34X10 14 Ω·cm, the insulating strength of the plasma-resistant coating layer was approximately 9.21 V / m. In the case of Example 5, the surface roughness of the plasma-resistant coating layer was approximately 2.61 ㎛, and the volume resistivity of the plasma-resistant coating layer was approximately 1.32X10 15 Ω·cm, the insulation strength of the plasma coating layer was found to be approximately 35.89 V / m.

[0140] In the case of Example 6, the surface roughness of the plasma-resistant coating layer was approximately 2.23 ㎛, and the volume resistivity of the plasma-resistant coating layer was approximately 3.05X10 15 Ω·cm, the insulation strength of the plasma coating layer was found to be approximately 35.74 V / m.

[0141] As described above, compared to the coating layer of Comparative Example 3, the coating layers of Examples 5 and 6 have relatively small surface roughness and relatively large volume resistivity and dielectric strength. Therefore, the coating layer according to the present disclosure not only has a reduced grain size and porosity, but also has a reduced surface roughness, thereby significantly reducing the particle generation rate. Therefore, the coating layer according to the present disclosure has improved plasma resistance characteristics, and can be used in semiconductor or display process components requiring plasma resistance characteristics.

[0142] In some examples, the process components may include a heater, a focus ring, an edge ring, a covering, a ring shower, an insulator, an EPD window, an electrode, a view port, an inner shutter, an electro static chuck, a chamber liner, a shower head, a CVD boat, a wall liner, a shield, a cold pad, a source head, an outer liner, a deposition shield, an upper liner, an exhaust plate, or a mask frame.

[0143] [Revised 21.08.2024 under Rule 91] Fig. 10 is a cross-sectional view illustrating an exemplary fine powder supply device (300) according to the present disclosure. As illustrated in Fig. 10, the exemplary fine powder supply device (300) according to the present disclosure may include a powder storage housing portion (310), a circular head portion (320), and a gas powder supply portion (330).

[0144] The powder storage housing (310) may include a powder storage (311), a first side opening (312), and a first vertical opening (313). The powder storage (311) may compress and store dry powder having an average particle size of about 1 nm to about 100 μm. In some examples, the powder storage (311) may store dry powder and compressed gas together, so that the dry powder may remain suspended within the powder storage (311). The first side opening (312) may be provided by being recessed inward from the side of the powder storage housing (311) with a predetermined depth and width. A portion of the circular head (320) may be coupled to the first side opening (312). The first vertical opening (313) may be provided by being perforated with a predetermined diameter in a vertical direction to the first side opening (312). In some examples, the first vertical opening (313) may be provided on the upper wall of the first side opening (312), which may be aligned with the center of the powder storage hole (323) provided in the circular head portion (320). In some examples, the center of the first vertical opening (313) may be the same as the center of the powder storage hole (323).

[0145] In some examples, the powders are alumina (Al2O3), yttria (Y2O3), YF3, YOF, Y4O5F7, YAM (Y4Al2O9), YAP (YAlO3), YAG (Y3Al5O 12 ) and / or rare earth series (a series of elements with atomic numbers from 57 to 71, including Y and Sc) oxides.

[0146] In some examples, the powder may be calcium phosphate, bioglass, silicon (SiO2), hydroxyapatite, Pb(Zr,Ti)O3 (PZT), titanium dioxide (TiO2), zirconia (ZrO2), yttria-stabilized zirconia (YSZ), dysprosia (Dy2O3), gadolinia (Gd2O3), ceria (CeO2), gadolinia-ceria (GDC), magnesia (MgO), barium titanate (BaTiO3), nickel manganate (NiMn2O4), potassium sodium niobate (KNaNbO3), bismuth potassium titanate (BiKTiO3), bismuth sodium titanate (BiNaTiO3), CoFe2O4, NiFe2O4, BaFe2O4, NiZnFe2O4, ZnFe2O4,MnxCo 3-x O4 (where x is a positive real number less than or equal to 3), bismuth ferrite (BiFeO3), bismuth zinc niobate (Bi 1.5 Zn1Nb 1.5O7 ), lithium aluminum titanium phosphate glass ceramics, Li-La-Zr-O series Garnet oxide, Li-La-Ti-O series Perovskite oxide, La-Ni-O series oxide, lithium iron phosphate, lithium-cobalt oxide, Li-Mn-O series Spinel oxide (lithium manganese oxide), lithium aluminum gallium phosphate oxide, tungsten oxide, tin oxide, lanthanum nickelate, lanthanum-strontium-manganese oxide, lanthanum-strontium-iron-cobalt oxide, silicate phosphor, SiAlON series phosphor, 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, mixtures of ceramics and polymers, or mixtures of ceramics and metals. It can be a mixture of one or two selected types.

[0147] Meanwhile, the average particle size of the powder may be, as described above, from about 1 nm to about 100 μm, from about 100 nm to about 50 μm, or from about 1 μm to about 25 μm. When the average particle size of the powder is greater than about 25 μm, the porosity of the coating film may be greater than about 4% and the film quality may be poor. Powders having an average particle size of about 1 μm or smaller are expensive and practically difficult to obtain. When the average particle size of the powder is from about 1 μm to about 25 μm, a coating film having excellent film quality and a porosity of about 1% to about 3% or less can be formed.

[0148] The circular head portion (320) may include a circular plate (322) having a rotational center axis (321) and a plurality of powder storage holes (323). The circular plate (322) may rotate at about 1 RPM to about 5,000 RPM with the rotational center axis (321) as the reference / center, and most of the area may be coupled to the first side opening (312) of the powder storage housing portion (310). The plurality of powder storage holes (323) may be provided along the periphery of the circular plate (322) at positions corresponding to the first vertical openings (313) of the circular plate (322). In some examples, the powder storage holes (323) may be arranged in a circular ring shape along the periphery of the circular plate (322). In some examples, the rotational center axis (321) of the circular head portion (320) may be coupled to a rotational axis of an electric motor. Accordingly, the rotation speed of the circular head part (320) can be controlled by the electric motor. When the rotation speed of the circular head part (320) is low, the powder supply speed becomes low, and when the rotation speed of the circular head part (320) is high, the powder supply speed becomes high. The circular head part (320) can be made of metal, ceramic, plastic, etc., and the material thereof is not limited in the present invention. In some examples, the rotation center axis (321) of the circular head part (320) can be penetratedly coupled to the powder storage housing part (310). In addition, the upper region, the side region, and the lower region of the circular head part (320) are configured to be mostly surrounded by the powder storage housing part (310), so that the powder does not leak to an unwanted region when the circular head part (320) rotates at high speed. However, a part of the circular head part (320) can be coupled to the side of the gas powder supply part (330).

[0149] The gas powder supply unit (330) may include a support body (331), a second side opening (332), a gas supply hole (333), and a gas powder injection hole (334). The support body (331) may fix a gas supply pipe (335) and a gas powder injection pipe (336). The second side opening (332) may be formed with a certain depth and width on the side of the support body (331) so that a portion of the circular plate (322) may be coupled. The gas supply hole (333) may be provided at an upper portion of the second side opening (332) so that the gas supply pipe (335) may be coupled. The gas powder injection hole (334) may be provided at a lower portion of the second side opening (332) so that the gas powder injection pipe (336) may be coupled. In some examples, the gas supply pipe (335) may be connected to a gas supply unit, and the gas powder injection pipe (336) may be connected to a powder injection unit or powder nozzle.

[0150] In this way, the circular head part (320) is coupled to the powder storage housing part (310) and the gas powder supply part (330), and the powder supply speed can be controlled according to the rotation speed thereof. In addition, since powder storage holes (323) are provided at regular intervals along the circumference of the circular head part (320), the powder can be supplied in a pulse form. That is, the powder can be supplied substantially only when the powder storage holes (323) of the circular head part (320) are in a vertical straight line with the gas supply holes (333) and the gas powder injection holes (334) of the gas powder supply part (330), and in particular, the powder supply speed can be adjusted according to the rotation speed of the circular head part (320).

[0151] In some examples, the exemplary fine powder supply device (300) according to the present disclosure may be installed in the quantitative powder supply unit (120) and / or the non-quantitative powder supply unit (140) among the exemplary fine powder spray coating device (100) illustrated in FIG. 1. In some examples, the gas supply pipe (335) may be the transport gas supply pipe (171) illustrated in FIG. 1, and the gas powder injection pipe (336) may be the quantitative powder supply pipe (130) illustrated in FIG. 1.

[0152] Figures 11 to 17 are cross-sectional views illustrating a powder storage hole and its surrounding structure among exemplary fine powder supply devices (300) according to the present disclosure. Although Figures 11 to 17 are described separately herein, those skilled in the art will understand that the structures illustrated in Figures 11 to 17 can be selectively combined with each other.

[0153] As illustrated in Fig. 11, the circular plate (322) of the circular head portion (320) can be coupled to the first side opening (312) provided in the support body (331) of the gas powder supply portion (330). In addition, the circular plate (322) in the circular head portion (320) includes a flat upper surface (322a) and a flat lower surface (322b) opposite to the upper surface (322a), and the powder storage hole (323) can vertically penetrate the upper surface (322a) and the lower surface (322b).

[0154] As illustrated in Fig. 12, the powder storage hole (323) may include an inclined inner wall (323a) whose diameter gradually decreases from the top to the bottom with respect to a vertical central axis. In addition, the powder storage hole (323) may be aligned in a vertical straight line with the gas supply hole (333) and the gas powder injection hole (334) provided in the support body (331).

[0155] In some examples, the upper diameter of the powder storage hole (323) may be the same as the diameter of the gas supply hole (333). In some examples, the lower diameter of the powder storage hole (323) may be smaller than the diameter of the gas supply hole (333) or the gas powder injection hole (334). In some examples, the angle (θ) between the inner wall (323a) and the lower surface (322b) of the powder storage hole (323) may be about 30° to about 90°. When the angle of the inner wall (323a) of the powder storage hole (323) is less than about 90°, the phenomenon of powder flowing down can be prevented, thereby reducing the loss of powder while the circular head part (320) transports the powder from the powder storage housing part (310) to the gas powder supply part (330).

[0156] As illustrated in Fig. 13, the powder storage hole (323) formed in the plate (322) of the circular head portion (320) may include an inner wall (323a) having the same diameter from top to bottom based on the vertical central axis. Since the upper and lower portions of the circular head portion (320) are mostly sealed by the powder storage housing portion (310), the powder is not dispersed to the outside while the circular head portion (320) transports the powder from the powder storage portion (311) to the gas powder supply portion (330), and thus, as described above, the upper and lower diameters of the inner wall (323a) of the powder storage hole (323) may be the same.

[0157] As illustrated in Fig. 14, the powder storage hole (323) provided in the circular plate (322) of the circular head portion (320) may include a first inner wall (323a) whose diameter gradually decreases from the upper surface (322a) toward the lower surface (322b), a second inner wall (323b) whose diameter increases horizontally from the first inner wall (323a), and a third inner wall (323c) whose diameter is the same from the second inner wall (323b) to the lower surface (322b). In this way, the pressure of the powder filling the powder storage hole (323) is relieved due to the first inner wall (323a) and the third inner wall (323c) having different diameters, thereby improving the supply efficiency of the powder.

[0158] As illustrated in FIG. 15, the gas supply hole (333) of the gas powder supply unit (330) may include a first supply hole (333a) having the same diameter from top to bottom, and a second supply hole (333b) having a diameter that gradually decreases from the first supply hole (333a) toward the bottom. In some examples, the lower diameter of the second supply hole (333b) may be smaller than the diameter of the powder storage hole (323). In this way, the gas supply hole (333) has the same vertical center and the lower diameter is smaller than the upper diameter, so that gas can be supplied to the powder storage hole (323) at a high pressure.

[0159] As illustrated in FIG. 16, the powder storage hole (323) formed in the disk (322) of the circular head portion (320) may include an inclined inner wall (323a) whose diameter gradually increases from the top to the bottom with respect to the vertical center. In some examples, the angle (θ) between the inner wall (323a) and the lower surface (322b) of the powder storage hole (323) may be approximately 90° to approximately 150°. In some examples, in the case of ultrafine powder (e.g., when the average particle size is less than approximately 1 ㎛), the gas pressure of the gas powder supply portion (330) may cause strong agglomeration between powders, preventing powder spraying or discharging. In such a case, as described above, by gradually increasing the diameter of the inner wall (323a) of the powder storage hole (323) from the top to the bottom, powder spraying or discharging by the gas pressure may become more favorable.

[0160] As illustrated in Fig. 17, the diameter of the gas powder injection hole (334) may be larger than the diameter of the powder storage hole (323) of the disc (322). Therefore, the powder passing through the powder storage hole (323) of the disc (322) may be transferred to the powder injection unit without being deposited in the gas powder injection hole (334).

[0161] FIG. 18 is a photograph of the surface and cross section of a spray coating film formed by an exemplary fine powder supply device (300) according to the present disclosure. As shown in the left photograph of FIG. 18, for example, when spray coating was performed using particles or powder having an average particle size of 126 μm, the surface roughness was observed to be relatively high and the porosity was approximately 5%. However, as shown in the right photograph of FIG. 18, for example, when spray coating was performed using particles or powder having an average particle size of 14 μm, the surface roughness was observed to be relatively low and the porosity was observed to be approximately less than 1%.

[0162] FIG. 19A is a graph showing the powder output per minute according to the rotation speed of the circular head portion in an exemplary fine powder supply device according to the present disclosure. In FIG. 19A, the X-axis represents the rotation speed (RPM) of the circular head portion, and the Y-axis represents the powder output per minute (g / min). As shown in FIG. 19A and Table 4, it can be seen that as the rotation speed of the circular head portion increases, the powder output per minute increases. For example, when the rotation speed of the circular head portion is 500 RPM, the output per minute is 3.01 g / min, when the rotation speed of the circular head portion is 1000 RPM, the output per minute is 5.84 g / min, when the rotation speed of the circular head portion is 2000 RPM, the output per minute is 10.72 g / min, and when the rotation speed of the circular head portion is 3000 RPM, the output per minute is 16.38 g / min. Therefore, in the present invention, the amount of powder discharged can be precisely controlled by adjusting the rotation speed of the circular head portion.

[0163] Circular head rotation speed (RPM) 500 1000 2000 3000 Discharge per minute (g / min) 3.0 15.8 4 10.7 2 16.38

[0164] FIG. 19b is a graph illustrating the powder discharge amount per minute versus the number of discharge amount evaluations in an exemplary fine powder supply device according to the present disclosure. In FIG. 10b, the X-axis represents the rotation speed (RPM) of the circular head portion, and the Y-axis represents the powder discharge amount per minute (g / min). As shown in FIG. 19b and Table 5, when the circular head portion rotated at the same speed for 1 to 10 times at different times, the discharge amount per minute was consistently measured to be 16.08 g / min to 16.95 g / min. Therefore, it can be seen that the method of controlling the discharge amount per minute by the rotation speed of the circular head portion in the present invention is highly reliable.

[0165] Number of evaluations: 12345678910 Discharge per minute (g / min) 16.15 16.25 16.21 16.28 16.19 16.18 16.85 16.08 16.95 16.27

[0166] The above description is only one embodiment for implementing the exemplary fine powder spray coating method according to the present disclosure, the spray coating layer according to the same, and the fine powder supply device therefor, and the present disclosure is not limited to the above-described embodiment, and it will be understood that the technical spirit of the present disclosure exists to the extent that various modifications can be implemented by anyone having ordinary skill in the art to which the present invention pertains without departing from the gist of the present disclosure as claimed in the following claims.

Claims

A step of transporting dry powder having an average particle size of 1.1 ㎛ to 25 ㎛; and A step of allowing the above-described transported dry powder to pass through a high-temperature plasma so that partially or completely melted particles collide with a substrate in the air at a speed of 100 m / s to 700 m / s, thereby forming a coating layer having grains and grain boundaries on the substrate. The aspect ratio (a / b) of the average horizontal length (a) of the grain and the average vertical height (b) of the grain is less than 6.5, and the ratio of the aspect ratio (a / b) to the average particle size (m) of the dry powder ((a / b) / m) is greater than 0.3, or The volume resistivity of the coating layer is 10 in the temperature range of 100°C to 400°C. 12 Ω·cm to 10 14 Ω·cm, or In the voltage range less than 3 kV, the volume resistivity of the coating layer is 10 13 Ω·cm to 10 14 Ω·cm, spray coating method.

2. In paragraph 1, The above dry powders are alumina (Al2O3), yttria (Y2O3), YF3, YOF, Y4O5F7, YAM (Y4Al2O9), YAP (YAlO3), YAG (Y3Al5O 12 ) or a method for spray coating comprising oxides of rare earth series (elements of atomic numbers 57 to 71, including Y and Sc).

3. In paragraph 1, A spray coating method wherein the aspect ratio (a / b) is 5.5 to 6.5 and the ratio ((a / b) / m) is 0.3 to 1.

1.

4. In paragraph 1, A spray coating method, wherein the thickness of the coating layer is 100 ㎛ to approximately 1000 ㎛.

5. In paragraph 1, A method for spray coating, wherein the size of the above grains is 0.1 ㎛ to 25 ㎛. A dry powder having an average particle size of 6.1 ㎛ to 25 ㎛ is transferred, and the transferred dry powder is allowed to pass through a high-temperature plasma so that partially or completely melted particles collide with a substrate in the air at a speed of 100 m / s to 700 m / s, so that a coating layer having grains and grain boundaries is formed on the substrate. The aspect ratio (a / b) of the average horizontal length (a) of the grain and the average vertical height (b) of the grain is less than 6.5, and the ratio of the aspect ratio (a / b) to the average particle size (m) of the dry powder ((a / b) / m) is greater than 0.3, or The volume resistivity of the coating layer is 10 in the temperature range of 100°C to 400°C. 12 Ω·cm to 10 14 Ω·cm, or In the voltage range less than 3 kV, the volume resistivity of the coating layer is 10 13 Ω·cm to 10 14 Ω·cm, thermal spray coating layer.

7. In paragraph 6, The above dry powders are alumina (Al2O3), yttria (Y2O3), YF3, YOF, Y4O5F7, YAM (Y4Al2O9), YAP (YAlO3), YAG (Y3Al5O 12 ) or a rare earth series (a series of elements with atomic numbers from 57 to 71, including Y and Sc) oxide, a spray coating layer.

8. In paragraph 6, A spray coating layer having an aspect ratio (a / b) of 5.5 to 6.5 and a ratio ((a / b) / m) of 0.3 to 1.

1.

9. In paragraph 6, A spray coating layer having a thickness of 100 ㎛ to approximately 1000 ㎛.

10. In paragraph 6, A spray coating layer having a grain size of 0.1 ㎛ to 25 ㎛. A housing part having a powder storage part for compressing and storing dry powder having an average particle size of 11.5 ㎛ to 100 ㎛, a first side opening formed inwardly from a side of the powder storage part, and a vertical opening formed in a vertical direction to the first side opening for vertically dropping the powder; A circular head having a disc that rotates at 1 RPM to 5,000 RPM and is coupled to the first side opening, and a powder storage hole provided along the circumference of the disc at a position corresponding to the vertical opening of the disc; A powder supply device comprising a gas powder supply unit having a support body, a second side opening formed on a side of the support body so that the disc is coupled, a gas supply hole to which a gas supply pipe is coupled at an upper portion of the second side opening, and a gas powder injection hole to which a gas powder injection pipe is coupled at a lower portion of the second side opening.

12. In paragraph 11, A powder supply device, wherein the powder storage hole formed on the above plate includes an inclined inner wall whose diameter gradually decreases from the top to the bottom based on a vertical central axis.

13. In paragraph 11, A powder supply device in which the powder storage hole formed on the above plate includes an inner wall having the same diameter from top to bottom based on a vertical central axis.

14. In paragraph 11, A powder supply device, wherein the above-mentioned plate includes a flat upper surface and a flat lower surface opposite to the upper surface, the powder storage hole penetrates the upper surface and the lower surface, and the angle (θ) between the inner wall of the powder storage hole and the lower surface is 30° to 90°.

15. In paragraph 11, A powder supply device, wherein the above-mentioned plate includes a flat upper surface and a flat lower surface opposite the upper surface, and the powder storage hole includes a first inner wall whose diameter gradually decreases from the upper surface toward the lower surface, a second inner wall whose diameter increases horizontally from the first inner wall, and a third inner wall whose diameter is the same from the second inner wall to the lower surface.

16. In paragraph 11, A powder supply device, wherein the gas supply hole of the gas powder supply unit includes a first supply hole having the same diameter from the top to the bottom, and a second supply hole having a diameter that gradually decreases from the first supply hole to the bottom.

17. In paragraph 11, A powder supply device wherein the diameter of the gas powder injection hole is larger than the diameter of the powder storage hole of the disc.

18. In paragraph 11, A powder supply device, the rotational center axis of the above circular head part being coupled to the above housing part.

19. In paragraph 11, A powder supply device, wherein the above plate includes a flat upper surface and a flat lower surface opposite the upper surface, the powder storage hole penetrates the upper surface and the lower surface, and the angle (θ) between the inner wall of the powder storage hole and the lower surface is 90° to 150°.

20. In paragraph 11, A powder supply device, wherein the average particle size of the above dry powder is 1 nm to 25 μm.

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