JP6302703B2 - Film-coated substrate and method for producing the same - Google Patents

Description

  The present invention relates to a coated substrate and a method for producing the same.

  Conventionally, a method of forming a film made of metal nitride on the surface of a substrate has been proposed.

  For example, Patent Document 1 discloses a component for a semiconductor manufacturing apparatus that includes a component main body and a thermal spray coating formed on the surface of the component main body by thermal spraying of aluminum nitride (AlN) particles as a raw material powder. A coating for a semiconductor manufacturing apparatus is described, wherein the coating is formed by depositing 90% or more of nitride powder particles which are not melted. In addition, the generation of fine particles generated from such semiconductor manufacturing equipment components is stably and effectively suppressed, resulting in a decrease in productivity and an increase in parts costs associated with frequent equipment cleaning and parts replacement. It can be applied to the manufacture of highly integrated semiconductor elements, and it can be used for semiconductor manufacturing equipment parts and compound semiconductor manufacturing equipment that can reduce etching and film formation costs by improving the operating rate. It is described that it is possible to provide a manufacturing part, a semiconductor manufacturing apparatus, and a compound semiconductor manufacturing apparatus.

  Further, Patent Document 2 discloses that a flame is generated by igniting a burner using a mixed gas of hydrocarbon and oxygen of fuel in an impact sintering coating apparatus and burning it in a combustion chamber. The flame temperature is lowered below the equivalent of complete combustion, and a powder supply nozzle is installed behind the flame, and it is made up of fine powder (AlN, etc.) coated from the nozzle and a solvent, and a combustion gas. The solid-liquid-gas three-phase mixture is injected from the powder supply nozzle, the amount of combustion gas kept at room temperature is increased, the temperature of the injected fine powder is lowered, and the transformation temperature, sublimation temperature and evaporation temperature of the powder material are below An impact-sintering coating method characterized in that the coating is performed by accelerating and instantaneously sintering by impact is described.

  Further, Patent Document 3 describes an aluminum nitride sprayed member in which a sprayed film made of substantially spherical aluminum nitride particles having an average diameter of 1 μm to 10 μm is formed on a base material. Such an aluminum nitride member is provided with an excellent characteristic of aluminum nitride on the surface of the member by thermal spraying, so that when used in an electrostatic chuck, heater, plasma processing apparatus chamber in the manufacture of semiconductors, etc. Therefore, it is possible to perform the processing stably because it has a high thermal conductivity and can make the in-plane temperature distribution of the wafer uniform. Further, it is described that an insulating substrate having a large area and a thin insulating layer can be easily provided when used as a heat dissipation insulating substrate for a power device.

International Publication No. 2010/027073 Pamphlet JP 2010-242204 A JP 2009-235558 A

  However, in the conventional method, a coated substrate having a metal nitride film excellent in both voltage resistance and thermal conductivity could not be produced. For example, in Patent Document 2, as Example 3, thermal spraying was performed using a mixed powder of aluminum nitride powder and yttrium oxide or magnesium oxide to form a film on the surface of the substrate. The fact that it was mK is described.

An object of the present invention is to solve the above problems.
That is, a method for producing a coated substrate having a metal nitride film on the surface of the substrate having a high withstand voltage (approximately 100 MV / m or more) and high thermal conductivity (approximately 50 W / mK or more) and its production It aims at providing the base material with a film obtained by a method.

The inventor has intensively studied to solve the above-mentioned problems, and has completed the present invention.
The present invention includes the following (1) to (6).
(1) A slurry preparation step of obtaining a slurry by dispersing a raw material powder mainly comprising metal nitride particles having sublimation properties and no melt phase in an organic solvent;
To the frame, the temperature of the raw material powder in the frame ejected from the thermal spraying device is lower than the sublimation temperature of the metal nitride, and the speed of the raw material powder in the frame is 500 to 1500 m / s. A film forming step of supplying the slurry and flame spraying to form a film on the surface of the substrate,
The manufacturing method of the base material with a film | membrane provided with.
(2) In the slurry preparation step, the metal nitride is aluminum nitride,
The manufacturing method of the base material with a film | membrane as described in said (1) which sets the temperature of the said raw material powder in the said flame | frame in the said film formation process as 1900-2500 degreeC.
(3) In the film forming step, after obtaining a mixed gas of an oxygen-containing gas adjusted to a supply pressure of 30 to 150 psi and a main fuel adjusted to a supply pressure of 20 to 140 psi, the obtained mixed gas is ignited Then, the frame is formed, the slurry is added to the frame, auxiliary fuel adjusted to a supply pressure of 15 to 30 psi is supplied, and flame spraying is performed as described in (1) or (2). A method of manufacturing the material.
(4) The manufacturing method of the base material with a film | membrane as described in said (3) whose said auxiliary fuel is acetylene.
(5) The manufacturing method of the base material with a film | membrane as described in any one of said (1)-(4) whose average particle diameter of the particle | grains of the said metal nitride is 0.5-3 micrometers.
(6) The withstand voltage is 100 MV / m or more, and the thermal conductivity is 50 W / mK, which is produced by the method for producing a coated substrate according to any one of (1) to (5) above. The base material with a film which has the film which is the above.

  According to the present invention, a coated substrate having a metal nitride film on the surface of the substrate having a high withstand voltage (approximately 100 MV / m or more) and a high thermal conductivity (approximately 50 W / mK or more). The base material with a film obtained by the method and its manufacturing method can be provided.

It is a schematic sectional drawing which illustrates a flame spraying apparatus. 4 is a graph showing the plasma resistance test results of the coating obtained in Example 1. 3 is a cross-sectional SEM image of the film obtained in Example 2.

The present invention will be described.
The present invention provides a slurry preparation step for obtaining a slurry by dispersing a raw material powder mainly composed of metal nitride particles having sublimation properties and having no molten phase in an organic solvent, and in a frame ejected from a thermal spraying device. Flame spraying is performed by supplying the slurry to the frame so that the temperature of the raw material powder is lower than the sublimation temperature of the metal nitride and the speed of the raw material powder in the frame is 500 to 1500 m / s. And a film forming step of forming a film on the surface of the substrate.
Hereinafter, such a method for producing a film-coated substrate is also referred to as “the production method of the present invention”.

  Each process with which the manufacturing method of this invention is provided is demonstrated.

<Slurry adjustment process>
First, the slurry adjustment step will be described.
In the slurry adjusting step in the production method of the present invention, a raw material powder mainly composed of metal nitride particles having sublimation properties and no melt phase is dispersed in an organic solvent to obtain a slurry.

The raw material powder will be described.
The raw material powder is mainly composed of metal nitride particles having sublimation properties and no melt phase.

  Here, the metal nitride having sublimation property and having no melt phase means a metal nitride which evaporates at a temperature lower than the melting point and exists in a gas at the melting point under normal pressure.

As such a metal nitride, for example, AlN, BN, Si ₃ N ₄ , NbN, GaN, InN, ScN, YN, LaN, Ge ₃ N ₄ , Sn ₃ N ₄ , TiN, ZrN, HfN, Th ₃ N ₄ , VN, TaN, CrN, Mo ₂ N, WN, Fe ₄ N, LaN, CeN, GdN.

The “main component” is 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, more preferably 98% by mass or more, and still more preferably substantially. Means 100% by mass (that is, it contains no metal nitride particles other than the inevitable impurities that can be mixed from the raw materials and the manufacturing process).
In the following description, the term “main component” is used in this sense unless otherwise specified.

The raw material powder may contain the metal nitride as a main component and other than the metal nitride. Examples of components other than the metal nitride that may be included in the raw material powder include metals, metal oxides, metal carbides, and metal hydroxides. When the metal nitride is AlN, other components include CaO, Y ₂ O ₃ , Al ₂ O ₃ , Ln ₂ O ₃ , La ₂ O ₃ , CeO ₂ , Nb ₂ O ₃ , Sm ₂ O ₃ , Gd _2. O ₃ and Dy ₂ O ₃ may also be included.

The raw material powder preferably has a particle size of 0.01 to 30 μm, and more preferably 0.1 to 5 μm.
The raw material powder preferably has an average particle diameter (median diameter) of 0.01 to 30 μm, and more preferably 0.5 to 3 μm.
Here, the particle diameter of the raw material powder is a value determined by measurement using a conventionally known laser diffraction / scattering particle size distribution measuring apparatus.
The average particle diameter of the raw material powder is a value obtained by measuring an integrated particle size distribution (volume basis) using a conventionally known laser diffraction / scattering particle size distribution measuring apparatus.

The slurry will be described.
In the slurry adjusting step, the raw material powder as described above is dispersed in an organic solvent to obtain a slurry.

A conventionally well-known thing can be used for an organic solvent, for example, alcohol can be used. Examples of alcohols include ethyl alcohol, methyl alcohol, and kerosene. It is preferable to use ethyl alcohol as the organic solvent.
When an alcohol is used as the organic solvent (preferably a cooled alcohol is used), the temperature of the frame can be lowered by heat of vaporization when the slurry is supplied into the frame and the organic solvent is vaporized. Then, it becomes easy to form a film while at least a part of the raw material powder is in an unmelted state, and a metal nitride film having a higher withstand voltage and a higher thermal conductivity can be formed on the surface of the substrate. Because it can.

The raw material powder can be added to such an organic solvent and dispersed by stirring or the like using an ultrasonic transmitter or the like as necessary to obtain a slurry.
It is preferable that the content rate of the raw material powder contained in a slurry is 1-90 mass%, and it is more preferable that it is 20-70 mass%.

<Film formation process>
The film forming process will be described.
In the film forming step of the production method of the present invention, the temperature of the raw material powder in the frame ejected from the thermal spraying device is lower than the sublimation temperature of the metal nitride, and the speed of the raw material powder in the frame is 500 to 500. The slurry is supplied to the frame so as to be 1500 m / s and flame sprayed to form a film on the surface of the substrate.

For example, the flame spraying apparatus shown in FIG. 1 can be used as the thermal spraying apparatus that performs the flame spraying.
In FIG. 1, a thermal spraying apparatus 10 has a combustion chamber 12 therein, an oxygen flow path 14 for supplying an oxygen-containing gas to the combustion chamber 12, a main fuel flow path 16 for supplying main fuel, and these And a burner 18 for igniting a mixture of oxygen-containing gas and main fuel. In addition, a hole (gun nozzle 20) for ejecting the frame is formed in the combustion chamber 12 on the side facing the burner 18, and a cylindrical tip tube 22 having a hole in the center on the outside of the gun nozzle 20. Is installed, and the frame can be ejected outward from the holes of the gun nozzle 20 and the tip tube 22. The speed of the frame can be adjusted by adjusting the size of the hole in the tip tube 22.

  A slurry supply channel 24 is formed in the distal end tube 22, and the slurry is supplied from here into the frame. Further, an auxiliary fuel supply channel 26 is further formed in the distal end tube 22, from which auxiliary fuel can be supplied to the frame.

  A compressed air supply passage 28 is formed in the gun nozzle 20, and the compressed air supplied therefrom is supplied so as to flow along the inner side surface of the hole formed in the tip tube 22. Thus, the slurry supplied from the slurry supply channel 24 is configured not to adhere to the inner side surface of the hole of the tip tube 22.

  For example, when the thermal spraying device 10 shown in FIG. 1 is used, in the film forming step, the temperature of the raw material powder in the flame ejected from the thermal spraying device 10 is lower than the sublimation temperature of the metal nitride, and in the flame. Under the condition that the speed of the raw material powder is 500 to 1500 m / s, the slurry is supplied to the frame and flame sprayed.

  Here, the temperature and speed of the raw material powder are set such that the length from the tip of the tip tube to the main surface of the substrate in the flame spraying apparatus is 100%, the tip of the tip tube is 0%, and the main surface of the substrate is 100. In the case of the% position, it means the temperature and speed of the raw material powder existing in the frame in the range from the 65% position to the 85% position. In addition, the temperature and speed | rate of raw material powder can be measured using the conventionally well-known thermal spray particle temperature measuring apparatus (For example, the product made by Osair, spray watch 3i).

Thus, the temperature of the raw material powder measured is made lower than the sublimation temperature of the metal nitride. For example, when the metal nitride is aluminum nitride, the temperature of the raw material powder (aluminum nitride) in the frame is preferably 1900 to 2500 ° C, and more preferably 2030 to 2450 ° C. The temperature of the raw material powder (aluminum nitride) in the frame is preferably 1900 to 2200 ° C. when auxiliary fuel (acetylene or the like) is used, and preferably 2300 to 2500 ° C. when no auxiliary fuel is used. .
As described later, by adjusting the supply pressure of the oxygen-containing gas, the supply pressure of the main fuel, the supply pressure of the auxiliary fuel, etc., the temperature of the raw material powder is adjusted to be lower than the sublimation temperature of the metal nitride. can do.

Moreover, the speed of the raw material powder measured in this way is set to 500 to 1500 m / s. This speed is preferably 600 to 900 m / s.
As described later, by optimizing the supply pressure of the oxygen-containing gas, the supply pressure of the main fuel, the supply pressure of the auxiliary fuel, etc., the speed of the raw material powder can be adjusted to 500 to 1500 m / s. .

  When the thermal spraying apparatus shown in FIG. 1 is used, the film forming process can be performed by flame spraying as follows.

  The oxygen-containing gas and the main fuel are supplied from the oxygen channel 14 and the main fuel channel 16 in the thermal spraying apparatus 10 shown in FIG.

  Here, the oxygen-containing gas may be a gas containing oxygen, for example, air, or a gas in which oxygen and air are mixed. The oxygen-containing gas is preferably oxygen.

  The oxygen-containing gas is preferably supplied at a pressure of 30 to 150 psi, more preferably 55 to 125 psi, more preferably 60 to 90 psi, and even more preferably 65 to 80 psi.

  The oxygen-containing gas is preferably supplied at a flow rate of 400 to 1000 L / min, more preferably 600 to 900 L / min, and even more preferably 700 to 800 L / min.

  The main fuel is preferably supplied at a pressure of 20 to 140 psi, more preferably 40 to 130 psi, more preferably 45 to 120 psi, and even more preferably 47 to 115 psi.

The main fuel is preferably supplied at a flow rate of 100 to 500 ml / min,
It is more preferable to supply at 400 ml / min, and it is more preferable to supply at 200 to 350 ml / min.

  Here, kerosene, acetylene, propylene, propane, ethylene, natural gas, or the like can be used as the main fuel. Among these, the main fuel is preferably kerosene.

The mixing ratio of the oxygen-containing gas and the main fuel is not particularly limited, but is preferably a mixing ratio at which the main fuel is incompletely burned. When incompletely combusted, the flame temperature is lowered by the heat of vaporization when some of the main fuel that has not combusted and the organic solvent (alcohols, etc.) in the slurry is vaporized. It becomes easier to construct a film with a part of it unchanged, and it becomes easier to produce a coated substrate having a metal nitride film having a higher withstand voltage and higher thermal conductivity on the surface of the substrate. It is.
It should be noted that here, only the mixing ratio of the oxygen-containing gas and the main fuel is adjusted so that the main fuel is incompletely burned without considering the auxiliary fuel and oxygen that can be contained in the slurry and compressed air. Is preferred.

In this way, the oxygen-containing gas and the main fuel are supplied to the combustion chamber and mixed, and the resulting mixture is ignited to generate a flame. Then, the slurry is supplied into the frame.
Here, it is preferable that the slurry is mixed with gas and then introduced into the frame. The gas is preferably air. This is because a metal nitride film having higher withstand voltage and higher thermal conductivity can be formed.

The slurry supply amount is preferably 20 to 80 ml / min, and more preferably 30 to 60 ml / min.
The solid content concentration in the slurry is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, more preferably 15 to 40% by mass, and 20 to 38% by mass. Is more preferable, and it is still more preferable that it is 25-35 mass%.

Compressed air may not be used, but when used, the compressed air pressure is preferably supplied as 0.2 to 1.5 MPa, more preferably 0.3 to 0.8 MPa. The compressed air is preferably supplied at a flow rate of 250 to 2000 L / min, and more preferably 400 to 800 L / min.
In some cases, uncompressed gas (for example, air) can be used instead of compressed air.

In the film adjustment step, it is preferable to use auxiliary fuel. Auxiliary fuel can be used to adjust the temperature of the frame.
When the auxiliary fuel is supplied to the frame, the temperature of the frame can be lowered by the heat of vaporization when the auxiliary fuel is supplied into the frame and vaporized. In this case, it is preferable because at least a part of the raw material powder can easily form a film in an unmelted state.

  As the auxiliary fuel, acetylene, methane, ethane, butane, propane, and propylene can be used.

  The auxiliary fuel is preferably supplied at a pressure of 0.05 to 1.0 MPa, more preferably 0.1 to 0.5 MPa. The auxiliary fuel is preferably supplied at a flow rate of 5 to 100 L / min, more preferably 10 to 30 L / min.

  When using the thermal spraying apparatus 10 shown in FIG. 1, it is preferable that the distance from the front-end | tip of the front-end | tip cylinder 22 to the main surface of a base material shall be 10-250 mm, and it is more preferable to set it as 70-150 mm.

The substrate will be described.
The substrate is not particularly limited, and examples thereof include aluminum, stainless steel, glass (such as quartz glass and non-alkali glass), ceramic (such as a sintered body made of Y ₂ O ₃ , AlN, Al ₂ O ₃ , etc.), carbon, and the like. .
In particular, a substrate with a film in which a film made of AlN is formed on the surface of a ceramic substrate made of AlN is extremely excellent in that it has high plasma resistance and extremely high heat dissipation.

  Although the magnitude | size and shape of a base material are not specifically limited, It is preferable that it is a plate-shaped thing. In the manufacturing method of this invention, it is preferable to form a film | membrane on the main surface of such a plate-shaped base material (it is also called a board | substrate).

  In the film forming step, it is preferable to flame spray under the processing conditions for adjusting the organic solvent and the auxiliary fuel, adjusting the kind and supply amount, etc., and forming the film while at least a part of the raw material powder is in an unmelted state.

In the film formation step, after obtaining a mixed gas of an oxygen-containing gas (preferably oxygen) adjusted to a supply pressure of 30 to 150 psi and a main fuel (preferably kerosene) adjusted to a supply pressure of 20 to 140 psi, The obtained mixed gas is ignited to generate the flame, and in addition to the slurry, auxiliary fuel (preferably acetylene) adjusted to a supply pressure of 15 to 30 psi is supplied to the flame, and flame spraying is preferably performed. . Here, the slurry supply amount is preferably 20 to 80 ml / min, and more preferably 30 to 60 ml / min.
When the supply pressure of the oxygen-containing gas, the supply pressure of the main fuel, and the supply pressure of the auxiliary fuel (preferably further the slurry supply amount as described above), the temperature of the raw material powder in the flame ejected from the thermal spraying device Is lower than the sublimation temperature of the metal nitride, and the speed of the raw material powder in the frame can be 500 to 1500 m / s.

  A film can be formed on the surface of the substrate by such a film forming process.

  The thickness of the film is preferably 10 μm or more, more preferably 30 μm or more, and further preferably 50 μm or more. Further, the thickness of the film may be 1000 μm or less, and may be 200 μm or less.

It is preferable that a part of the raw material powder is unmodified in the film.
Therefore, for example, when the raw material powder is AlN, the content of unmodified AlN contained in the film is preferably 80% by mass or more, and more preferably 90% by mass or more. Moreover, this content rate may be 95 mass% or less.

By such a production method of the present invention, a coated substrate having a film on the surface of the substrate can be obtained.
The film in such a film-coated substrate has metal nitride as a main component, has a high withstand voltage, and has a high thermal conductivity.

Moreover, such a substrate with a coating has high plasma resistance. Here, the plasma resistance is not particularly limited in kind, and examples thereof include atmospheric pressure plasma, inductively coupled plasma, capacitively coupled plasma, magnetic field plasma, high frequency plasma, and thermal plasma. Moreover, when the porosity of the film is low, the plasma resistance is high. Specifically, the porosity of the film is preferably 7% or less.
Here, the porosity is a pore area per visual field area obtained by photographing a cross section of a film with a scanning electron microscope or the like and obtained from an image with a magnification of 2000, that is, a pore area / a visual field area × 100 (%). Means the value of

  Thus, since a base material with a film has high plasma resistance, it can be used for a member exposed to a plasma atmosphere. For example, members, such as a semiconductor manufacturing apparatus, a flat panel display manufacturing apparatus, or a solar cell panel manufacturing apparatus, are mentioned. The substrate with a film of the present invention is preferably used for a semiconductor manufacturing apparatus member. Examples of the semiconductor manufacturing apparatus member include a member exposed to a plasma atmosphere in an ion implantation apparatus, an epitaxial growth apparatus, a CVD apparatus, a vacuum deposition apparatus, an etching apparatus, a sputtering apparatus, an ashing apparatus, and the like. For example, chamber, bell jar, susceptor, clamp ring, focus ring, shadow ring, insulating ring, dummy wafer, tube for generating plasma, dome for generating plasma, transmission window, infrared transmission window, monitoring Examples thereof include a window, a lift pin for supporting a semiconductor wafer, a shower plate, a baffle plate, a bellows cover, an upper electrode, a lower electrode, and an electrostatic chuck.

<Example 1>
An aluminum substrate having a thickness of 3 mm was prepared, and flame spraying was performed on the main surface of the substrate using aluminum nitride particles (average particle diameter: 2.3 μm) as a raw material powder to form a film having a thickness of 50 μm. .
The processing conditions in flame spraying are as follows. The flame spraying apparatus shown in FIG. 1 was used.
Flame spray processing conditions Oxygen pressure: 73 psi
Fuel (kerosene) pressure: 65 psi
Auxiliary fuel (acetylene) pressure: 25 psi
Slurry supply amount: 50 ml / min
Distance from tip of tip tube to main surface of aluminum substrate: 100 mm

While performing such flame spraying, the temperature and speed of the aluminum nitride particles in a substantially semi-molten state after being ejected from the flame spraying apparatus until reaching the aluminum substrate or the already formed film. Was measured. Specifically, the length from the tip of the tip tube to the main surface of the aluminum substrate in the flame spraying apparatus is set to 100%, the tip of the tip tube is set to 0%, and the position of 100% of the main surface of the aluminum substrate. In some cases, the temperature and velocity of aluminum nitride particles present in the frame in the range from 65% position to 85% position were measured. A sprayed particle temperature measuring device (manufactured by Osair, spray watch 3i) was used for such temperature and speed measurements.
As a result, the temperature of the aluminum nitride particles was 1800-2200 ° C.
The speed of the aluminum nitride particles was 500-1500 m / s.

<Evaluation of film properties>
Next, the withstand voltage and thermal conductivity of the film formed on the surface of the aluminum substrate were measured.
The withstand voltage was measured using a withstand voltage tester (manufactured by Kikusui Electronics Corporation, TOS8750).
The thermal conductivity was measured using a thermal conductivity measuring device (manufactured by NETZSCH, LFA457) using a laser flash method. And based on the method of measuring the thermal conductivity of JIS H 8453: 2010 thermal barrier coating, the thermal conductivity of only the aluminum substrate and the base material with a coating (aluminum nitride particles are sprayed onto the main surface of the aluminum substrate to a thickness of 50 μm). The thermal conductivity of the film was measured, and the thermal conductivity of only the film was calculated.

  As a result, the withstand voltage was 300 MV / m and the thermal conductivity was 109 W / mK.

<Evaluation of plasma resistance>
Next, the film made of aluminum nitride formed on the surface of the aluminum substrate was exposed to ICP plasma, and the plasma resistance was evaluated. This will be specifically described below.

Plasma exposure was performed using an ICP etching apparatus EIS-700SI manufactured by Elionix Corporation.
The plasma conditions are as follows.
・ Plasma gas O ₂ , CF ₄ , SF ₆
・ Gas ratio O _{2 3} standard cc / min (sccm), CF ₄ 30 sccm, SF ₆ 5 sccm
・ Gas pressure 0.6-0.7Pa (Slight fluctuations are observed)
・ Plasma power 800W (reflection is 0W)
・ Bias voltage: 55 to 63V (80% of the maximum value of the device is set)
-Plasma exposure cycle 20 min exposure-10 min rest for 16 cycles for a total of 8 hours Here, a mask for leaving an unexposed portion was made using an aluminum material, and the surface was black anodized. For reference, the Fukushima Hi-Tech Plaza engineers pointed out that it would be desirable to have nickel plating on the surface.
Since the surface of the sample was brittle with respect to the AlN film and could not be polished, it was subjected to a plasma exposure experiment with the film formed as it was. For comparison, the Y ₂ O ₃ film simultaneously subjected to surface polishing was subjected to a plasma exposure experiment.

About the film | membrane which consists of aluminum nitride after performing the above ICP plasma exposure, the surface shape was measured using the laser displacement meter. The measurement results are shown in FIG.
For comparison, a film (film made of Y ₂ O ₃ ) on a film-coated substrate manufactured using yttria (Y ₂ O ₃ ) as a raw material powder instead of aluminum nitride particles and the other methods in the same manner. ICP plasma exposure was performed under the same conditions, and the surface shape was similarly measured using a laser displacement meter. The measurement results are shown in FIG.

AlN was not significantly etched after 8 cycles of exposure. For comparison, about 5 to 6 μm of etching was observed for the Y ₂ O ₃ film subjected to the exposure test at the same time for comparison.
That is, it can be said that the AlN coating is not inferior to the plasma resistance of the Y ₂ O ₃ coating that is currently in practical use under the plasma conditions of this time.

<Example 2>
An alumina (Al ₂ O ₃ ) substrate having a thickness of 3 mm is prepared, and flame spraying is performed on the main surface of the substrate using aluminum nitride particles (average particle size: 2.3 μm) as a raw material powder. A film having a thickness of about a degree was formed.
The processing conditions in flame spraying are as follows. The flame spraying apparatus shown in FIG. 1 was used.
Flame spraying treatment conditions Oxygen flow rate: 780 L / min
Fuel (kerosene) flow rate: 220 mL / min
Auxiliary fuel (acetylene) flow rate: 12mL / min
Slurry supply amount: 45 ml / min
Distance from tip of tip tube to main surface of aluminum substrate: 80mm

Further, the temperature and speed of the aluminum nitride particles during flame spraying were measured by the same method as in Example 1.
As a result, the temperature of the aluminum nitride particles was 1800-2200 ° C.
The speed of the aluminum nitride particles was 553 m / s.

<Evaluation of film properties>
Next, the withstand voltage and thermal conductivity of the film formed on the surface of the alumina substrate were measured in the same manner as in Example 1.
As a result, the withstand voltage was infinitely high and could not be measured, and the thermal conductivity was 30 to 34 W / mK.

<Calculation of porosity by observation of film cross section>
The obtained film-coated substrate was embedded in a two-component curable epoxy resin, and an observation surface was obtained by polishing with an automatic polishing machine (Buhler, model: ECOMET3 and AUTOMET2), and then a scanning electron microscope (JEOL) A SEM image of the coating surface (coating cross-section) was taken using a model manufactured by Co., Ltd., model: JSM-5600LV. The magnification was set to 2000 times, and the automatic adjustment mechanism of the apparatus was used to adjust the contrast and brightness during shooting. The SEM image (2000 times) of the film cross section is shown in FIG. From the SEM image of FIG. 3, it can be seen that the film obtained in Example 2 has a dense structure.

Next, the SEM image was binarized using MEDIA CYBERNETICS, Image Pro PLUS 3.0. From the image after this image processing, the pore area per visual field area, that is, the pore area / visual field area × 100, was calculated and obtained as the porosity (%).
As a result, the porosity was as extremely low as 0.7%.

<Coating composition analysis>
About the membrane | film | coat in the obtained base material with a membrane | film | coat, the density | concentration of the element which comprises this was measured using the micro part fluorescence X-ray-analysis apparatus (Shimadzu Corporation make, model: XRF-1700).
The measurement conditions are as follows.
X-ray tube target material: Rh
Tube voltage: 40 kV
Tube current: 95 mA
X-ray passage atmosphere: vacuum of 25 Pa or less Analysis diameter (diaphragm): 10 mm
Next, the content of the element contained in the film was determined from the measurement result by the micro fluorescent X-ray analyzer using the FP method. The FP method uses the physical constants (fundamental parameters) such as mass absorption coefficient, fluorescence yield, and spectrum distribution of the X-ray source to determine the theoretical X-ray intensity from the theoretical formula of the fluorescent X-ray intensity, and the measured X-ray This is a method of calculating the concentration of each component by comparing with the intensity.
As a result, it was found that the total mass concentration of Al, N, and O (oxygen) in the film was 98.8% by mass, and was substantially composed of these elements. The molar ratio of these three elements was Al: N: O (oxygen) = 63.5: 25.0: 11.5.
Thereby, it is presumed that most of the components constituting the film are AlN or aluminum oxide such as Al ₂ O ₃ . Here, the value of the molar ratio of the three elements includes a part of the base material derived from Al ₂ O ₃ .

<Crystal structure analysis of particles constituting the film>
About the film | membrane of the obtained base material with a film | membrane, the crystal structure was analyzed using the X-ray-diffraction apparatus (The Shimadzu Corporation make, XRD-6000). The measurement method was performed using the θ-2θ method under the following conditions. The θ-2θ method is a method of scanning while moving the detector unit 2θ when the X-ray source is fixed and the sample stage is moved by θ.
X-ray source: Cu target X-ray source Tube voltage: 40 kV
Tube current: 30 mA
Divergence slit: 1 °
Scattering slit: 1 °
Receiving slit: 0.3mm

As a result, a peak indicating the presence of AlN (peak intensity: 10184 counts) and a peak indicating the presence of Al ₂ O ₃ (peak intensity: 22858 counts) appeared on the chart. In addition, no other peaks indicating the presence were present.
Thus, components constituting the film is estimated to be AlN, and Al ₂ O _3. Here, the peak indicating the presence of Al ₂ O ₃ includes a material derived from Al ₂ O ₃ of the base material. Although details are omitted in this example, it has been found by other experiments that most of the peaks indicating the presence of Al ₂ O ₃ are derived from the base material. Therefore, it is estimated that many of the components constituting the film are AlN.

<Example 3>
Instead of the alumina substrate having a thickness of 3 mm used in Example 2, an AlN substrate having the same thickness was prepared, and similar aluminum nitride particles (average particle diameter: 2.3 μm) were placed on the main surface of the substrate. Flame spraying was performed using the raw material powder to form a film having the same thickness. The processing conditions for flame spraying were all the same as in Example 2.

  When the temperature and speed of the aluminum nitride particles were measured during flame spraying in the same manner as in Example 2, the temperature and speed were the same as in Example 2.

<Evaluation of film properties>
Next, the withstand voltage and thermal conductivity of the film formed on the surface of the AlN substrate were measured in the same manner as in Example 2.
As a result, the withstand voltage was infinitely high and could not be measured, and the thermal conductivity was 30 to 34 W / mK.

<Calculation of porosity by observation of film cross section>
Next, after obtaining an SEM image (2000 times) of the film cross section by the same method as in Example 2, the porosity was determined.
As a result, the porosity was as extremely low as 0.9%.

DESCRIPTION OF SYMBOLS 10 Thermal spray apparatus 12 Combustion chamber 14 Oxygen flow path 16 Fuel flow path 18 Burner 20 Gun nozzle 22 Tip cylinder 24 Slurry supply flow path 26 Auxiliary fuel supply flow path 28 Compressed air supply flow path

Claims (4)

A slurry preparation step of obtaining a slurry by dispersing a raw material powder mainly composed of metal nitride particles having sublimation properties and no melt phase in an organic solvent;
After obtaining a mixed gas of oxygen-containing gas adjusted to a supply pressure of 30 to 150 psi and main fuel adjusted to a supply pressure of 20 to 140 psi, the obtained mixed gas is ignited and a flame is ejected from the thermal spraying device. The slurry to the frame so that the temperature of the raw material powder in the frame is lower than the sublimation temperature of the metal nitride and the speed of the raw material powder in the frame is 500 to 1500 m / s. A film forming step of supplying an auxiliary fuel adjusted to a supply pressure of 15 to 30 psi and flame spraying to form a film on the surface of the substrate;
The manufacturing method of the base material with a film | membrane provided with. In the slurry preparation step, the metal nitride is aluminum nitride,
The manufacturing method of the base material with a film | membrane of Claim 1 which sets the temperature of the said raw material powder in the said flame | frame in the said film formation process as 1900-2500 degreeC.   The manufacturing method of the base material with a film | membrane of Claim 1 or 2 whose said auxiliary fuel is acetylene.   The manufacturing method of the base material with a film | membrane as described in any one of Claims 1-3 whose average particle diameter of the particle | grains of the said metal nitride is 0.5-3 micrometers.