TW200944618A - Member coated with aluminum nitride by thermal spraying and process for producing the same - Google Patents

Abstract

A thermal-spraying deposit of aluminum nitride excellent in thermal conductivity and insulating properties is desired to be formed on members for electrostatic chucks, heaters, and plasma-processing chambers for use in the production of semiconductors, etc. or on members for use in radiating insulating substrates for power devices. A thermal-spraying deposit having a low porosity and a high aluminum nitride content is hence provided. A member coated with aluminum nitride by thermal spraying is also provided which comprises a base and, formed on at least part thereof, a thermal-spraying deposit constituted of fine aluminum nitride particles. This member is characterized in that the thermal-spraying deposit is constituted of fine aluminum nitride particles which are nearly spherical and have a diameter of 1-10 μm on the average. The member may be characterized in that interstices among the aluminum nitride particles are filled with a Group IIIA and/or Group IIA element compound, and that the deposit has a porosity of 15% or lower. This member can be produced by conducting thermal spraying with an aluminum nitride powder having an average particle diameter of 1-10 μm or with a powder mixture obtained by incorporating a Group IIIA and/or Group IIA element compound into the same aluminum nitride powder.

Description

200944618 IX. Description of the invention: [Technical field of invention] Heater plate, surface The present invention relates to a component of an electrostatic head, an additive, a silently processed reaction chamber, or a power component. In particular, in order to impart a high-strength, strong and dense melt film with "(4)(4) as a material to the shot." 9 ❹ [Prior Art] Gasification material (4) High-profile riding material, and fluoroquinone Excellent (: &. therefore chemical vapor deposition in semiconductor manufacturing engineering

Vapc^epQsHiGn' (10) film forming device or electric device...t, and parts requiring such characteristics are used, for example, in an electrostatic holding head of an inner circular substrate, so that the wafer substrate is hooked in the plane. The part that is in contact with the wafer substrate while maintaining a specific temperature, in the heating of the dome-shaped substrate heater, the insulation part integrally formed with the squid electrode is damaged or the electrical code of the 姓 疋 姓Use components and so on. τ 夂 的 的 的 保 熔 熔 熔 熔 熔 熔 熔 熔 熔 熔 熔 熔 熔 熔 熔 熔 熔 熔 熔 熔 熔 熔 。 。 A method of forming an aluminum nitride portion, etc., but from the viewpoint of not forming, etc., that is, forming an aluminum nitride portion, it is preferable to form an aluminum nitride portion by a spray method in an early pure manner. <r L From the machine (1) station part, Youyou: When the conditions are sprayed, it will oxidize and decompose before dissolution, and nitriding: It is not easy to form a change. Therefore, a review of nitrogen and various species. , the town of Wanfa entered

7I05-10I88-PF 200944618 For example, it is reported that there is a method of heat-treating the molten film obtained by alumina, and the method of heat treatment in t (for example, please refer to the patent document 疋 18G (rc degree) The high temperature does not apply to metal substrates. Secondly, there is a method of spraying powder obtained by mixing nitriding chains with oxidized smelting powders (for example, please refer to the material reading, but the presence of Α1Ν in this mouthpiece) The amount of stomata in the spray raft is 47%

The thermal conductivity reported by the multiple is lower than that of the sintered body of the alumina ceramic, and it is desirable to further increase the thermal conductivity. Moreover, it is reported that a ceramic powder in which a metal and a metal nitride and an oxide are mixed, specifically, a mixed powder of a metal #, a nitride dream, and an oxidized dream is sprayed as a primer for a lanthanide pottery gold. A technique in which a cloth layer is formed thereon and a wrong ceramic spray film is formed thereon (for example, refer to Patent Document 2). However, there is a concern that the insulation is lowered due to the mixing of the nitride and the metal. Moreover, it is also reported that the metal aluminum powder or the metal aluminum powder and the aluminum lanthanum nitride are melted in a vacuum with a plasma containing nitrogen. This is carried out by reactive spraying to deposit aluminum nitride (for example, refer to Patent Documents 3 and 4), but since it is a vacuum process, it is not easy to spray a large-sized member, and it is caused by the residue of the metal. Disadvantages of reduced insulation. [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. No. Hei. Non-Patent Document 1] H. Yang, I Luan, ST. Tu

7105-10188-PF 6 200944618 "A1N/A1203 Composite Coating Deposited by Plasma Spray" Proceedings of the 1st Asian Thermal Spray Conference, 41 (2005). [Summary of the Invention] [Problems to be Solved by the Invention]

According to the above description, it is expected that sintering is performed by spraying aluminum nitride on a member such as a film forming apparatus of Gyp or the like for manufacturing a semiconductor element or a static holding head of a plasma etching apparatus, a heater, a reaction chamber, or the like. The high-temperature treatment process required by the method, and imparts direct plasma resistance to the metal substrate, but is not easy to produce a high-productivity spray film to form a dense aluminum nitride film. The S of the present invention provides a spray member which is suitable for the above-mentioned use, forms a dense nitride film which is dense and dense to the substrate, and provides a method for producing the spray member. L. Means for Solving the Problem] As a result of intensive review of the above-mentioned status quo, the inventors of the present invention found that the material of the nitriding (four) material at the end of the specific phase is subjected to normal piezoelectric charging, and the nitriding immediately before reaching the substrate. The powder has a two-collision of only the oxidation of the surface layer, thereby providing a member of the nitriding film which has a good adhesion between the nitride and the substrate, and in addition to the nitriding terminal, The present invention can be completed by using a mixed powder in which the nitriding (tetra) powder and the '/or ancient steroid powder are mixed and dispersed, and the nitrided (four) film can be provided. ', P疋, the invention relates to an aluminum nitride spray member on a substrate

7105-10188-PF 200944618 A lenticular film is formed in which the sputum sputum is composed of slightly spherical aluminum nitride particles having an average diameter of not more than 10 /zm. [Embodiment] The members of the present invention will be described in detail below. Referring to the nitriding member mode of the present invention, as shown in Fig. 1 or Fig. 2, the solvent films 12, 22 are deposited on the substrate u, 21, wherein the films 12, 22 are made of an average diameter! "The above 1Q " the following spheroidal nitride-like particles 13,23. The deposition mechanism of this nitrided particle is considered to be the surface-partial oxidation of the nitrided particles by spraying. The particles are adhered to each other and the molten ruthenium is deposited. The average diameter of the aluminum nitride particles on the substrate is j " the above several centimeters are preferably 2 or more and 8 or less. If the average diameter of the nitriding particles is larger, the decrease in thermal conductivity due to the oxide layer on the surface of the particles due to the spraying process is reduced, but the average diameter of the nitriding particles is too large, and the unoxidized gasification at the center portion is large. When it is sprayed, it does not adhere to the soil plate and rebounds, and it is difficult to form a spray film due to rain. Further, in the present invention, the average diameter refers to the individual average value constituting the refining film, and the measurement of the diameter of the individual particles obtained by the (four) film breaking (four) sw scanning electron diopter, or the observation of the yoke A (electronic line exploration) A needle microanalyzer, an energy dispersive spectroscope, or the like: H, (4) A value measured by a method of measuring the diameter of individual particles or the like. Moreover, the surface of the nitriding particles will oxidize and dissolve on the surface of the spray process.

7105-10188-PF 200944618 Melted with a round shape. Therefore, the slightly spherical shape described in the present invention means a circle having a spherical shape or an elliptical shape. The shape of the aluminum nitride particles can be determined by grinding the surface of the molten film and observing or observing the composition images of nitrogen, oxygen, and aluminum obtained by ruthenium, EDS, or the like. The thickness of the nitriding film is preferably 5 "η or more and 5 Å or less. If it is less than 5 "m, there may be cases where insulation is lacking. If it is thicker than 5 有时, the melted film may be easily peeled off from the substrate. _ The aluminum nitride particles constituting the aluminum nitride spray film form a gap between the particles due to the surface damage only during the dissolution. When a gap is formed in the melted film, there is a concern that the thermal conductivity of the melted film is increased and the insulation is lowered. Here, as shown in FIG. 2, a group IIIA and/or IIA compound 24 is filled in the gap of the nitrided particles μ to reduce pores. Thus, the inventors have considered that the Group IIIA and/or UA compound is melted by spraying and thus deposited as small particles in the gap formed by the aluminum nitride particles. To get nitriding! The good physical properties of g (thermal conductivity, insulation resistance, etc.), and the porosity is preferably 15% or less. The method for measuring the porosity of the present invention can be measured by the following method. The film is peeled off from the substrate, and the density of the body is measured by the Archimedes method, and the ratio of the true density is calculated. The image obtained by observing the spray film by (4) or the like traces the pores and rolls. Kong Deng hurts, and uses the image processing software to measure the gas volume of the heart's division by dividing the area by the area of the pores and the area of the spray film. The cover-compound is preferably a compound of [Methane, Ca, Sr, Ba, etc., which is an insulating compound such as a rare earth metallized human I vapor or a disc acid salt. Soil-spectrum metal oxides, 7105-1 〇] 83_pp 200944618. The content of the above-mentioned ΙΠΑ 1 wt% or more and 30 wt% in the spray film, which is an insulating compound such as a fluoride or a structuring acid group, and/or a IIA compound is preferably as follows. When the amount is less than 1% by weight, the effect of reducing the porosity may be reduced. If the amount is more than 30% by weight, the thermal conductivity may be lowered. (4) The content of the aforementioned mA group and/or IIA compound in the film is more preferably 1 w and more than 25 wt%, for example, it may be heat conduction or steel··molybdenum, aluminum-bismuth, etc.

Further, the material of the present invention has a base material ratio of 100 W/mK or more, a composite metal or alloy of a metal such as a pin, a pin, or a copper, and a metal-ceramic composite material such as aluminum-carbonized niobium or tantalum-niobium carbide. Such surfaces may also be roughened by dicing or hydrofluoric acid or the like. The surface roughness of the surface of the substrate is preferably such that the spray film is easily attached to 0.1 / zm to 15 #m. Here, the surface roughness means the arithmetic mean roughness Ra described in JIS 2001. On the other hand, the aluminum nitride sprayed film preferably has a thermal conductivity of 1 〇 ff/mK or more. As described above, the individual surfaces of the aluminum nitride particles are oxidized and melted to be bonded to the adjacent particles during the spraying process. Fig. 3 shows an example of an x-ray diffraction pattern of the aluminum nitride spray film used in the present invention. The (100) plane of the hexagonal aluminum nitride (2 Θ ·· 33. 256.) can be found in the main peak 31, and the (400) plane of the other phase of alumina 7 (20 ··· 45.789.) can be seen at the peak 32. Moreover, the output of the plasma may have a peak of α-alumina (1〇4) surface (20: 35·103°). In the X-ray diffraction peak intensity of the molten film which is strongly bonded to each other and ensures a certain degree of thermal conductivity, it is preferable to have a peak intensity of the (400) plane and the alumina (1〇4) plane. The ratio of the peak intensity to the aluminum nitride (ι〇〇) surface is 〇. 05 or more 〇·2 or less. Here is less than 〇. 〇5

7105-10188-PF 10 200944618, the combination of nitriding is weak, and sometimes it is better to add the (1) group A and / or IIA compounds to strengthen the bonding between the particles. In the case of 〇.2, there is a case where the thermal conductivity is sacrificed. The aluminum nitride spray member of the present invention can be used for a film holding device or a plasma etching device for CVD or the like in semiconductor manufacturing engineering, an electrostatic holding head for supporting a wafer f plate or a heating substrate for heating a wafer substrate. Heater. Specifically, at least the first melting is formed on the base #41 of the metal ceramic composite material such as the alloy of the alloy, the gold alloy of the alloy, or the metal ceramic composite material of the first carbon stone, the stone, and the carbon cut. The film 42, the metal electrode layer or the heating layer 43, the second spray film 44, the first film, and/or the second film are the above-described nitride film, or nitrided particles and A spray film composed of a steroid and/or a IIA compound. The nitriding member of the present invention can be exposed to the electropolymerized portion of a device such as a film forming apparatus, a plasma etching apparatus, a plasma cleaning apparatus, or an ashing apparatus which is a semiconductor manufacturing process. In part, ❹ further forms the aforementioned aluminum nitride spray film. As an example of the member material formed by the above-mentioned gasification, which is used for the above-mentioned gasification part, a round cover (bell jar), a cylinder (cyHnder) or a surface of the aluminum nitride spray film may be mentioned. The roughness Ra is preferably less than 15 (four) above the melon. These parts will not only be electrically mounted on the surface of the component, but also will deposit a film on the surface of the component due to the engraving, cleaning, and ashing of the wafer. When the electric power is in contact with each other, the dust is generated. The roughness of the oxidized glaze film is Ra. The adhesion of the deposited film is high, and the deposited film is subjected to thermal load due to contact with the electrician. The temperature change is alleviated by the high heat transfer of 71〇5-]〇188_pp 200944618 aluminum nitride spray film, thereby reducing the generation of fine dust. Here, when the arithmetic average roughness Ra exceeds 15, the substrate is used. The average roughness of the arithmetic mean roughness of the molten film to be coated with the aluminum nitride spray film will increase, and the thickness of the raw material will decrease. The base material of the # part can be used in addition to the above-mentioned material having high heat conduction. Titanium or other high-insulation quartz glass, H, etc. And 'use by inwardly from the outer side in conjunction with the sensing means and the introduced high frequency insulating substrate. ❹

The aluminum nitride spray member of the present invention can further serve as a heat release insulating substrate for a power element. In this case, the substrate shown in Fig. 5 is a metal heat-releasing substrate 5 on which an aluminum nitride spray film 52 is formed. As the substrate, a metal ore such as a metal having a conductivity of 100 or more, a metal such as indium or steel, or a composite metal or alloy such as m-shi, such as carbon-cutting or carbonization, can be used. The thermal conductivity of the nitride (tetra) film 52 is preferably 1 () ¥ / rainbow. In order to mount the power element 55 on the surface of the vaporized (four) film 52, the surface thereof is polished, and in order to be intimately coupled with the power element on which the solder 54 is mounted, copper or metal 53 is read or melted. 2. In the nitriding injecting member of the present invention, a substance which seals pores existing in the nitride film can be used. The seal in the present invention means that the pores in the spray film are filled with an arbitrary sealant: for example, an epoxy-based or acrylic-based dream system or a fluorine-based sealant can be used as the sealant. :::: An inorganic oxide coating agent composed of a room-hardening type of tree wax or an organic metal such as a finely divided nitrogen or a mineral. The second:: for example, a method of applying a sealing sword on the surface of the smear film or a immersion in a liquid immersion in a vacuum 熔

7105-10188-PF 12 200944618 A method of hardening a pore agent. By performing the sealing, the strength or thermal conductivity of the glazing film, the dielectric withstand voltage described later, and the like (4) (4) (4) are improved. In the nitriding member of the present invention, the insulating withstand voltage of the nitrided spray film is preferably 0.15 MV/cra or more, more preferably 〇 2 MV/cm or more. Insulation resistance ❹ ❹ 〇 〇 Μ Μ Μ Μ Μ Μ 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在Exothermic. A method for improving the insulation withstand voltage of the nitriding (four) medium may be, for example, a method of raising the density or sealing of the film. The method for producing an aluminum nitride spray member of the present invention is, for example, that a nitrided powder having an average particle diameter of 1 ” or more and 10 Å or less is supplied to a spraying device, and is sprayed on a substrate by a normal piezoelectric slurry. Forming an aluminum nitride spray film, wherein the plasma is sprayed under the condition that the average temperature of the nitrided particles immediately before reaching the substrate is 220 (TC or more, 2280t: or less, and the average flying speed is 4〇〇m/s). The above 600 m/s or less. The temperature or speed at which the aluminum nitride powder is sprayed can be measured, for example, by using "Dpv_2〇〇l (trade name) manufactured by TECNAR, Canada. In the crucible, the temperature of the molten particles or the emission of the molten particles is measured by a two-color thermometer, and the flying speed of the particles is measured by the time that the emitted particles pass through the sensor. The temperature of the particles is less than 220 0 °c. In this case, there is a possibility that the deposition efficiency of the melted film is low, and the adhesion of the film to the substrate is weak, and if it exceeds 2,280 ton, the oxidation and decomposition of the aluminum nitride are promoted. In the aluminum nitride sprayed member of the present invention, The gap between the aluminum nitride particles is filled in the lan and/or II The Group A compound particles, for example, can be supplied to a melting group of 11 u group and/or Iu group 7105-10188-PF 13 200944618 having an average particle diameter of 1 # m or more and 10 " m or less. The shot should be on the aluminum nitride film below 10々®, and the strip of the above-mentioned electric paddle grafting is sprayed by the regular plasma to obtain the average temperature of the molten aluminum particles: 4 is about to reach the substrate. The nitriding rate is as follows: above 600 m/s or less, the average particle diameter of the spray raw material powder used in the present invention is averaged, or the average diameter of the field is preferably 1 (), The flattening 瓞 1 1 η of the image pickup powder of the second end is preferably 2 to 8 (four). If the average a Μ: large powder is used, as previously described, it is possible that the high melting point of the chaotic compound does not melt and cannot be stacked. The film is sprayed. Moreover, the average particle size is less than 1...there is a possibility that the speed of collision with the substrate is deteriorated and the oxidation is promoted, and the ratio of the nitriding is lowered...,! Generally speaking, the melting point of the ceramic is high but The thermal conductivity is low, and it is difficult to obtain the molten state of the uniform sentence, although a finer particle size than the metal powder is used. At the end, if it is too fine, there is a problem that it is difficult to put it into an optimum position in the spray flame, and it is easy to cause trouble during supply. Therefore, an average particle diameter (10) to 5" m is used for normal plasma, and hydrogen stability at a high output and high energy rate is used. For the case of the plasma, use a powder of the degree of ~100 #m (for example, please refer to 冲幸男, etc., and the Japan Spray Association, "Introduction to Spray Technology" (2006), pp. 191-192). The average particle diameter of the raw material powder used by the inventors is a relatively fine powder as compared with the past. The supply of such a fine powder is, for example, a Techn〇serve company using a surface copying type. ΑΜ, -30" (trade name) or "CPF-2HP" (trade name) made by the German company "The 〇] company. 7105-10188-PF 14 200944618 The method of forming a spray film used in the present invention is preferably plasma spray. In particular, it is preferred to perform the sputtering by means of a surface output and a high gas flow. For example, high output A 5 can be cited. Above kW, the high gas flow rate is Μ. SLM (StandardLmerPerMl Saki) plasma. The effect of increasing the output and gas flow rate is not certain, but it is considered that by increasing the gas flow rate, the time during which the nitride powder stays in the plasma is short, and the rain suppresses oxidation and decomposition. Usually, if the gas flow rate is increased, it is difficult to form a molten film because the powder is not melted, but it is considered to be a molten layer by increasing the rotation of the plasma. Further, in the manufacturing method of the present invention, in the M method, the supply of the raw material powder to the melt blast is preferably supplied to the center of the plasma to supply the powder: AXialm (trade name) of ANQrthwestMettech, Canada. This blasting is set at the interval of the circumference of the nozzle to set three plasma electrodes, and dissolves: :puts into (four) the center'. Therefore, when the plasma is a reducing ring (10) such as ... 2, it is possible to prevent the molten powder from being exposed to oxygen. Oxidation. Fig. 6 shows a conventional example of the electric charge dissolving device for supplying powder to the internal state of the plasma. (4) The plasma squeezing device will be connected to the three anodes 61 and the three cathodes 6 of the power source 68. Between the flowing plasma gas = the formed plasma nozzle is concentrated in the collector: Set:: slurry jet as a heat source, will be injected into the center of the spray powder 63: two and melt the molten powder as the flow rate of the electricity gas Collision stacking two materials Q6 'forms a spray film 67. According to the manufacturing method of the present invention, the molten gas when forming the spray film can be

7105-10188-PF 15 200944618 Use an inert gas such as N2 or Ar or a reducing gas such as & If oxygen is present in the molten gas, the nitrogen in the molten raw material powder is oxidized in the spray', so that the nitrogen content in the sprayed film is greatly lowered, so the oxygen concentration in the molten gas is preferably as low as possible, but When the vaporized powder is sprayed in the general environment of normal temperature and normal dust, the surface of the spray powder after high-temperature flight or the powder powder after deposition has a small amount of oxide, which is considered to be responsible for by the increase of the output of the grafting. Link the roles of nitrides to each other. The presence and amount of the nitride in the spray film can be confirmed by the enthalpy diffraction method on the surface of the spray film, and the amount of nitrogen in the spray film can be measured by enthalpy. Further, the amount of the lanthanum and/or m group in the spray enthalpy can be measured by performing fluorescence X-ray analysis or the like. In the manufacturing method of the present invention, the distance between the front end of the spray and the substrate is a spray distance of 65, preferably 4 〇 15 15 。. If the spray distance exceeds 150 (four), the molten powder will be cooled before it adheres to the substrate, and the spray film may not be deposited on the substrate. The spray distance is shorter than 40 and the temperature of both the substrate and the spray film rises. It becomes the cause of cracking of the spray film or the substrate, or sometimes reduces the nitrogen content in the spray film. Further, the firing power of the incident when the (four) (four) is incident on the substrate differs depending on the use of the device, for example, the case of the electropolymerization device shown in Fig. 6, and the melt power can be, for example, 5. More than 150 kW above kw. In the middle of the law, the electricity is output by the high-output, high-gas flow (four). The gasification (four) is the component, but the following is not the case: two! 5. A method of producing an aluminum nitride spray member obtained by another plasma spray method.

7105-10188-PF 16 200944618 That is, '(1) a mixed powder of a lubricant having an average particle diameter of "below nitridation (10) and relative to Μ Μ" ^ (4), or an addition procedure: ❹ The nu and the can compound of the ...: 2: = 1 "10" or more of the following nitriding (4) and the total weight of the powder is °, 1 to 5, the mixed powder of the lubricant as: The powder is supplied to the spraying device and is formed by the method of forming a nitride (tetra) shot on the substrate by using Changbao Electric (4), or (2) by using an average particle size of i ^ or more and 10 (four) or less, or a mixed powder of a mA group and/or a Group IIA compound powder having a particle diameter of i ^ or more and 10 Am or less and an aluminum nitride powder having an average particle diameter of 1 /Z1D or more and 10 Aln or less is disposed outside the sprayed plasma outlet. More than one position is perpendicular to the plasma jet and is supplied oppositely, and a method of forming an aluminum nitride spray film on the substrate by spraying a normal piezoelectric slurry, wherein the condition of the plasma spray is sprayed The distance is 40 mm or more and 70 mm or less. ❹ First, in the manufacturing method of (1), the aluminum nitride powder having an average particle diameter of 1 / zm or more and 1 〇 or less is added and the weight of the aluminum nitride powder is 01 to 5 wt% with respect to the nitriding powder. a mixed powder of a lubricant or a group IIIA and/or steroid powder having an average particle diameter of 1 〇 or more and a nitriding powder having an average particle diameter of ≤ # or more and the like The total weight of the powder is 〇. 1 to 5 wt% of the mixed powder of the lubricant is used as a spray powder. Examples of the lubricant include stearic acid, behenic acid, tetrabasic acid-saturated saturated fatty acid or rocky soil. By adding these lubricants to the melt

7105-10188-PF 17 200944618 In the raw material powder, it is capable of being sprayed without supplying the molten raw material powder to the spray device at a high gas flow rate, and produces a decrease in the supply of the molten raw material powder or a change in the supply amount. The effect of the problem. This principle is believed to reduce the friction of the powders with each other due to the presence of lubricant on the surface of the powder.

The amount of the lubricant is increased by the amount of 氮化.1 to 5 wt% of the weight of the aluminum nitride powder when the aluminum nitride powder is used alone as the molten powder, in the aluminum nitride powder and the IIIA group and/or the IU compound. When the mixed powder is used as a spray powder, an amount of 0 to 1 wt% of the weight of the mixed powder is added. When the amount of the lubricant is less than 0.1, the lubricating effect is reduced, and the problem of the supply is likely to occur. When the amount of the lubricant is 5, the lubricant may remain in the spray film, which may cause a decrease in the film quality of the spray film. Adding a lubricant to an aluminum nitride powder or a method of adding a lubricant to a mixed powder of an aluminum nitride powder and a HU group and/or a steroid, for example, a separate powder and a lubricant in a dry or wet ball mill In order to improve the fluidity, a normal dish feeder (for example, "TwiW" C product name by I Sulzer Metc Co., Ltd.) or "i264p summary ^ Feeder" by praxai^ is used. (product name)), vibrating feeder (for example, ^(10)(10) public (four)" (trade name)), and the fluidized bed feeder (4) is two:: wide. "·········································································· Aluminum nitride component.

7105-10188-PF 18 200944618 On the other hand, in the manufacturing method of (2), the aluminum nitride powder having an average particle diameter of 1 / im or more and 1 or less or an average particle diameter of 1 / a mixed powder of a group IIIA and/or steroid powder having a size of at least 10 or more and an aluminum nitride powder having an average particle diameter of 1 μm or more and 1 〇A m or less, or more than 2 or more outside the plasma outlet of the melted film The position is perpendicular to the electrospray jet and is supplied in the opposite direction, and the condition of the normal piezoelectric slurry is such that the spray distance is 4 〇 or more and 70 mm or less. φ Nitrogen powder, or a mixed powder of lanthanum and / or steroid powder and aluminum nitride powder, sprayed perpendicular to the plasma at two or more positions outside the spray plasma outlet and relative An example of the supply state to the direction is shown in FIG. The molten material powder (121) is supplied by a powder feeder (122) using an inert gas (123) such as He. Dividing into a branch (124) on the way or using two feeders, in two positions (in the case of Fig. 12) perpendicular to the plasma jet portion (125) generated by the self-dissolving shot (126) and relative Supply to the source. Such a spray device is, for example, a spray device such as SG-1 〇〇 (trade name) manufactured by Seiko Co., Ltd., or 9 MB", "F4", or "Triplex" (trade name) manufactured by Sulzer Metc. The supply amount of the inert gas such as He for supplying the molten raw material powder is preferably 5 to 30 SLM. When the supply amount of the inert gas is less than 5 SU, it is difficult to flow at the end of the fineness. When the amount is higher than the 3G SLM, the plasma spray may be weakened. The adhesion amount of the spray film may be reduced or the film quality may be lowered. Further, the reason why the two or more are supplied in the opposite direction is that if the opposite direction is not used, and the electromagnetism is supplied only with respect to the slurry, the powder may penetrate the plasma, but the pair may be used. If the powder is easy to enter the plasma, the special 19 200944618 is easy to enter its center. Then, the melting distance is preferably 40 to 7 Å. If the distance of the spray exceeds that of the coffee, the powder is cooled before the spray powder adheres to the substrate. In some cases, the spray film may not be deposited on the substrate. If the spray distance is shorter than 4 Å, the substrate and the spray film are both The temperature rise of the person may sometimes cause the fracture of the spray film or the substrate, and g may cause a decrease in the nitrogen content or a change in composition of the dissolution medium. ❹ Moreover, such a spraying device forms a molten gas when the molten film is formed, and the main gas is preferably, for example, a red and/or N" auxiliary gas, for example, using heat and electricity of the plasma by using I. The speed of the slurry jet rises, and by making the melt distance 40 to 7 〇1, the surface of the spray powder and the powder powder after the deposition become high temperature, and a part of the change is oxide. It is considered that the role of the nitrides is connected to each other. The gas flow rate of Ar and/or N2 of the main gas and the Hz of the sub-gas varies somewhat depending on the melting device, but it is preferably 6 〇 or more, φ 1 to 15 SLM. The molten material powder containing the moisturizing/bone agent can of course be applied to the invention of (2). [Effects of the Invention] The nitriding member of this month is held by the nitrite by the spray. The excellent characteristic imparting member table* has insulating properties and high thermal conductivity when used in an electrostatic solid head made of a semiconductor or the like, a heater, or a plasma processing apparatus reaction chamber, and can be used to divide the in-plane temperature of the wafer. Uniform, so stable Execution S. And in the heat-dissipating insulating substrate used for the power component

7105-10188-PF 20 200944618 When an insulating substrate having a large area and a thin insulating layer can be easily provided. [Examples] The present invention is described in detail based on the examples, but the present invention is not limited to the examples. In addition, the average diameter, porosity, and insulation withstand voltage of the powder constituting the molten film of the comparative example of the following Example were measured as follows. (1) Average diameter _ , The observed image was observed from the magnification of the SEM# 1,000-fold magnification of the melt film section, and the diameter of the observed individual particles was measured, and the average value was obtained. (2) Porosity The image obtained by observing the pores at a magnification of 1000 times from the SEM of the cross section of the melt film was traced. The area of the tracked vent portion was measured using "Nanohiinter" (trade name) of NO System. Further, the area of the entire molten film containing the pores was measured, and the area of the pore portion was divided by the area of the sprayed film to determine the porosity. (3) Insulation withstand voltage As shown in Figure 7, is there a 1〇〇 aluminum melt film deposited? The graphite 73 of 2 is pressed with an electrode 74 of a diameter (4) on the aluminum nitride spray film 71 as a molten base material, and the graphite is also connected to the electrode, and a withstand voltage tester 75 "TOS8750" manufactured by Kikusui Electronics Co., Ltd. is used. (Product name), the voltage was gradually increased to 5 ” under the condition of \ ^ to measure the dielectric breakdown voltage. Example 1 , Aluminum nitride powder made of Toyo Aluminum Co., Ltd. FLC (average particle diameter) 4.2 The sprayer "Axial ΙΠ" 7105-1 〇i°88-PF 01 200944618 (trade name) manufactured by Northwest Mettech Co., Ltd. was sprayed onto a quartz glass substrate. The powder was supplied by the company Thennico, Germany. CPF_2flp" (trade name). For the quartz glass substrate to be sprayed, the surface roughness is obtained by using quartz glass having a surface roughness Ra of 5 m by sand blasting and then treating with 5% gas acid for 2 hours. Quartz glass with degree h is 8. ❹ The spraying conditions at this time are at normal pressure, the melting distance is 1 〇〇, the plasma power is 95 kW, and the Ar, 沁 and h gases are combined as the spray gas. SLM maneuver, the above aluminum nitride powder flows at a supply of 15 g/min, and the spray is robbed 400 is moved at a speed of /second, and is sprayed at 2 passes. The speed and temperature of the particles in this spray are measured by DPV 2000" (trade name) manufactured by TE Company of Canada, which is 59 melons. , seconds, Norday. The film thickness of the film formed by this film is 12 〇 ", and the surface roughness is 9 (four) 1 X-ray diffraction method to analyze the phase of the structure.] The hexagonal nitriding chain and the r-oxidation are observed. The peak intensity ratio of the X-ray diffraction of the surface of the oxidized (1〇〇) surface and the oxidized (deleted) surface is °·11. Moreover, the cross section of the glare film is observed by SEM, and the average diameter is 4 (four). The degree of spherical particles is composed, = the image obtained by observing the cross section by SEM, and the porosity by the image analysis method is 'the porosity is 27%. Example 2. The spraying condition is changed to the plasma gas flow rate to (10) to 28 〇_, the output was changed to 6° to 1 (four), and the spray distance was changed to 6. 14.14 〇^, and the same conditions as in Example 1 were carried out, and the film thickness during the flight, the speed and the film thickness of the spray were measured, and the hexagonal As shown by the strong peak production of crystallization, the film thickness of the spray film follows the powder temperature in flight:

71〇5-]〇188-PF 22 200944618 rises and rises together, but when it exceeds 2280 °C, the ratio of alumina increases, and the ratio of hexagonal aluminum nitride decreases rapidly. Further, when it is less than 2 2 〇〇 <) (: 'the deposition of the molten film is small. Example 3 Using graphite having an aluminum melted film deposited thereon by sand blasting as a molten base material, the mixing ratio is used. A mixed powder of changed aluminum nitride powder and cerium oxide (4N, average particle size 4 em) or magnesium oxide (high purity chemical ❹ 2N average particle 4 vm) as a powder for spraying, and examples 1 The same conditions were used for the spraying. For this molten film, the amount of cerium oxide or magnesium oxide in the molten film was measured by fluorescent X-ray analysis, and the image obtained by observing the cross section of the molten film by sem was analyzed by image analysis. The porosity was measured, and the thermal conductivity was measured by "LaserpjT" (trade name) manufactured by ULPAC Co., Ltd. The results are shown in Table 1. The content of yttrium oxide in the spray film is 7 to 30% by weight, and oxidation is performed. The content of magnesium is 8% by weight, the porosity is 11-13%, the peak intensity ratio of hexagonal aluminum nitride is 〇11_〇12, and the heat conduction rate is U_46 W/mK. Moreover, any of the spray films is also The average diameter is composed of spherical particles of about 4 m. Oxidation (4) The SEM image of 7 wt% of the solute_face is shown in Fig. 9. The content of the gasification zone is 3, and the distribution of the A1, N, and Y of the cross section of the solvent is shown in Fig. 1A. The particulate ai, N The portion having a high γ concentration in the gap confirmed that there was an oxidation period between the gaps of the aluminum nitride particles.

7105-10188-PF 23 200944618 Table 1 Y203 content (% by weight) Porosity (%) Thermal conductivity (W/mK) A1203/A1NC-) 7 13 43 0. 12 21 11 46 0. 11 30 11 11 0.11 MgO content (% by weight) Porosity (%) Thermal conductivity (ff/mK) A1203/A1NC-) 10 11 34 0.11

[Embodiment 4] The surfaces of the quartz bell jar U1& and the annular insulating base 112 of the plasma cleaning apparatus shown in Fig. 11 were sandblasted so that the surface roughness was individually m. The same aluminum nitride powder and cerium oxide powder as in Example 3 were used, except that the mixing ratio of the cerium oxide powder was 2 wt%, and the number of passes was only 15, and the same conditions as in the Example] were carried out to obtain an average value. A nitride (tetra) projecting member having a film thickness of 90 p. The surface roughness of the bell jar lu and the annular insulating base 112 is 8, 8, and 4, respectively. The necessary components are ultrasonically cleaned by ultrapure water, and the reaction chamber of the electric paddle cleaning device is used. Example 5 is in m. After drying these components and other cleaning ovens, the electrochemical carbonization prepared as a substrate is prepared on the surface of the surface by the same conditions as those of the "US" (10).舆 膜 。 量 量 量 量 量 量 量 量 量 量 量 量 量 量 量 量 量 量 量 量 量 量 量 量 量 量 量 量 量 量 量 量

7105-10188-PF 24 200944618 A pulverized resin composed of a oxy-stone compound such as "Permeate HS-10 0 clear" (trade name) manufactured by D&D Co., Ltd., a mixture of epoxy resin and hardened material such as PELN0X Co., Ltd. made a mixture of "peinox WE-1263" and "Pelcure HV-126" (trade name), which is made by Clariant in Japan Co., Ltd. as a coating agent for silica dioxide. Aquamika" (trade name). The sealing method is that the vacuumed sample is immersed in permeate 10 0 clear, left at room temperature, and the vacuumed sample is immersed in a mixture of PelnQx WE-1263/Pelcure HV-126 and hardened by i3〇°c for 2 hours. . Aquamika is sprayed on the surface of the spray film at 15 (rc hardening for 1 hour, this process is carried out by spraying to hardening twice. The porosity of the sample before sealing is 10%, no one after sealing. Porosity. The aluminum nitride spray film that has been sealed and the aluminum nitride spray film that is not sealed are ground so that the surface of the ground aluminum nitride spray film has a thickness of #m, and is insulated. Pressure test. The performance of the insulation withstand tester is up to 5 Ο M, but the samples that have been sealed are all over 5 kV and above 0.25 MV/cm. The insulation resistance of the unsealed aluminum nitride spray film The pressure is M16 Mv/cm. Example 6 As a mixed powder of 9 〇wt% of aluminum nitride powder and 1 〇wt% of cerium oxide powder (Japanese armor 4N + average particle size 4 " m) The hard fat of the lubricant, 0 ° · 3 2 ' 4, 6 wt% was added, and the mixture was separately mixed in a dry ball mill to prepare the molten material powder, and the 5 MPE" (trade name) manufactured by Sulzer Metco Co., Ltd. Let the history of At ^ s* λα tr * as the supply of the steroids flow at 25 L/min. to perform the supply test, and take the 杳 丨 丨 , , , , , , , , , , , 实施 实施 实施The same conditions form a melting

7105-10188-PF 25 200944618 Film. The evaluation method of the supply is to confirm the flow (pulsation) of the flow rate of the powder in the supply and the continuity of the powder supply. Further, the appearance of the spray film was observed. The results are shown in Table 2. All of the stearic acid-added powders did not have a change in the flow rate of the powder, and the continuity of the supply was confirmed, and it was possible to supply 1 Gmin or more. Occasionally (〇ceasiQnally) pulsation was seen in the absence of stearic acid. The spray film formed by adding a powder of 6 (tetra) stearic acid was colored in a pale brown color. Table 2 Stearic acid addition amount (wt%) 0 Q.3 〇——-_ 〇4 〇〇Powder flow change △ There is pulsation one---- Normal normal normal normal spray film appearance 〇〇〇〇△ Good Good and good coloring

Example 7 In addition to the use of stone ants of 1 (melting point 68 to 7 〇. 〇, the powder supply test was carried out in the same manner as in Example 6. The powder flow rate of the powder of the added stone ant was not changed') Continuously, it can be supplied for 10 minutes or more. Example 8: aluminum nitride powder of 90 wt/0 and cerium oxide powder of 1 〇 wt% (Japan: 4N, mixed powder of average particle diameter 4, added A powder of a mixture of a hard fat and a dry ball mill is used as a powder for spraying the raw material.

7105-10188-PF 26 200944618 The molten material powder was sprayed onto a quartz glass substrate using a rF4" (trade name) spray device manufactured by SiUzer Metco Co., Ltd. The powder was supplied by using r 5MPE (trade name) manufactured by Sulzer Metco Co., Ltd., and supplied as a supply gas at 25 L/min, and the above aluminum nitride powder, cerium oxide powder and stearic acid were 24 g/min. The supply amount flows, and the opposite direction supply of the two positions is performed at the melt blast exit. The spraying conditions are: the spray distance is 5〇mm, the plasma is grabbed as rainbow: 6〇slm, ❹ 0 5 10 13 15 SLM' spray is moved at a speed of 4〇〇mm/sec, and 20 passes are melted. Shoot. The results are as follows: _ ^ The results are as shown in Table 3. The entire flow rate is attached to the film, but if it is "LM, the adhesion of the film is weak, and if it is 15 SLM, the surface of the film is raised.

table 3

Example 9

"The teeth, J 80 mm, p U 〇 LM shown in 4, and the spray distance are outside" are sprayed under the same conditions as in the case of Example 8. If the penetration distance of the body is difficult to 80, the adhesion may be weak. But other good

7105-10188-PF 27 200944618 Comparative Example 1 Aluminum nitride powder (Ammonia aluminum powder FLX (average particle diameter: 18" "m)) having an average particle diameter of 15 and Example i, 2 The same conditions were used for the spraying, and the spray film was not attached. Comparative Example 2 The quartz bell jar of the plasma cleaning device and the surface of the ring insulating abutment were sandblasted so that the surface roughness was individually 7, 6, 3 V m . The components ❿ and other necessary components were ultrasonically washed with ultrapure water, and dried in a cleaning oven to be installed in the reaction chamber of the plasma cleaning apparatus. The continuous use test of the members of Example 4 and Comparative Example 2 The plasma cleaning device shown in FIG. 11 supplies power from the antenna power high-frequency power source i丄6 to the high-frequency coil 117, and the self-bias power high-frequency power source 118 supplies power to the electrodes provided on the wafer 113 via the electric grid. Thus, Ar gas in the reaction chamber was generated to generate Ar ions 114' and 'the plasma cleaning apparatus of the reaction chambers of Example 4 and Comparative Example 2 was continuously used in the semiconductor process, and the deposit Π5 due to sputtering_ion_sputtering was started. Stacked on the surface of the bell U1, Comparative Example 2 after 3 days When the particles were increased, the particles were increased after 2 days, and the members such as the bell jar and the ring insulating machine were taken out and exchanged, and the effect of reducing the particles of the aluminum nitride spray member of the present invention was exhibited. Fig. 1 is a view showing an example of a schematic view of an aluminum nitride spray member. Fig. 2 is a view showing an example of a pattern of an aluminum nitride spray member. Fig. 3 is a view showing an aluminum nitride spray. A diagram of an example of a sinusoidal diffraction pattern.

7105-10188-PF 28 200944618 Fig. 4 is a view showing an example of the structure of a heater and an electrostatic holding head of a nitriding melt-casting member. Fig. 5 is a view showing an example of the structure of a heat releasing insulating substrate of an aluminum nitride spray member. Fig. 6 is a view showing an example of a plasma spray device. Fig. 7 is a view showing an example of an insulation withstand voltage test. Fig. 8 is a graph showing the peak intensity ratio of the hexagonal aluminum nitride in the temperature of the aluminum nitride particles in flight and the adhesion efficiency of the melted film. Figure 9 is a SEM image of a cross section of the produced aluminum nitride spray film. The figure shows the images of the A1, Ν, and γ obtained from the cross section of the produced aluminum nitride spray film. Fig. 11 is a view showing an example of a schematic of a plasma cleaning device. Fig. 12 is a view showing an example of a form in which the molten material powder is supplied oppositely from the two positions with respect to the plasma jet. ❹ [Main component symbol description] 11 : Substrate 12 : Spray film 13 : Aluminum nitride particles 21 : Substrate 22 : Spray film 2 3 : Aluminum nitride particles 24 : Group IIIA and / or IIA compounds, 41 :Metal substrate 7105-10188-PF 29 200944618

42 : First spray film 43 : Metal electrode film or heating layer 44 : Second spray film 51 : Metal heat release substrate 52 : Aluminum nitride spray film 53 : Metal gold plating or spray film 54 : Welding material 55 : Power Element 60 : Cathode 61 : Anode 62 : Plasma Gas 63 : Spray Powder (Supply Port) 64 : Aggregator 65 : Melting Distance 66 : Substrate 67 : Molding Die 68 : Power Supply 72 : Aluminum Spray Film 73 : Graphite 74 : Electrode 75 : Financial test machine 111 : Bell cover 112 : Annular insulation machine 113 . Broken wafer 30

7105-10188-PF 200944618 114 : Ar ion 115: deposit due to Ar ion sputtering 11 6 : Antenna power high frequency power supply 11 7 : high frequency coil 118 : bias power high frequency power supply 121 : molten raw material powder 122 : Powder Supply Machine 123: Inert Gas Cylinder 124: Bifurcation to Two Branches 125: Plasma Jet 126: Spray Shot

31

7105-10188-PF

Claims (1)

200944618 X. Patent application: 1. A kind of nitriding chain melting member 'forms a melting family on the substrate, wherein the above-mentioned solvent film is made of a slightly spherical nitridation with an average diameter of i"above the heart (four) 2. A composition of aluminum particles. 2. A nitrided spray member having a spray film formed on a substrate, wherein the spray film is formed by a slightly spherical nitrided particle having an average diameter of 41" or more and 1/4 or less. And / or steroids.氮化 ❹. The nitriding 33 solute member according to claim 2, wherein in the gap of the nitriding particles, the π ΐΑ and/or IIA compound It is 15% or less. 4. The nitriding member according to claim 2, wherein the content of the aforementioned lanthanum and/or steroid compound in the precursor film is 1 wt% or more and 30 wt% or less. The nitriding spray member according to any one of the items 1 to 4, wherein the surface of the nitriding particles is individually oxidized, and I is fused to the particles. ... in the nitriding 33 spray member described in item 5 of the monthly patent range, in the x-ray diffraction of the aforementioned spray film, the intensity of the 咏Van 射 peak, r 虱 aluminum (4 〇〇) surface ^ oxidation Ming The ratio of the peak intensity of the (1〇4) plane to the peak intensity of the nitride (10) plane is 0.05 or more and 〇.2 or less. The first film, the metal electrode layer or the heating layer, and the second, molten film are formed on the substrate at least sequentially, and the first spray film and/or Washing the Li. The Omachi and/or the second spray film consists of slightly spherical aluminum nitride particles with an average diameter of 1 7105-10188-PF 32 200944618 sec m above 1 〇 " m π μ. The 1 J film and the aluminum nitride spray member are formed with at least a >, a metal electrode layer or a heating layer, and a second melt film on the substrate, wherein the first melt film is And/or the second melt film is composed of a slightly spherical aluminum nitride particle having an average diameter of i or more and 10 or less and a group and/or a group IIA compound. The nitriding injecting member according to claim 8, wherein the η IA group and/or the steroid compound are present in the gap of the aluminum nitride particles, and the porosity of the molten film is 15% or less. The aluminum nitride sprayed member according to claim 8 or wherein the content of the Group IIIA and/or IIA compound in the spray film is from 1 wt% to 30 wt%. The aluminum nitride spray member according to any one of claims 7 to 10, wherein the surface of the aluminum nitride particles is oxidized individually and bonded to adjacent particles. 12. The aluminum nitride spray member according to claim n, wherein in the X-ray diffraction peak intensity of the aforementioned spray film, the τ alumina (400) surface and the α alumina (104) surface The ratio of the peak intensity to the peak intensity of the aluminum nitride (1 Å) plane is 0.05 or more and 0.2 or less. The nitriding member as described in any one of claims 1 to 12, wherein the aluminum nitride spray film is formed on a portion exposed to the plasma. 14. The aluminum nitride spray 7105-10188-PF 33 200944618 member according to claim 2, 8 or 9 wherein the portion exposed to the plasma is formed of the aforementioned aluminum nitride and the aforementioned IIU group And / or a film of the IIA compound. 15. The aluminum nitride spray member according to claim 13 or 14, wherein the aluminum nitride spray member is a dome, a cylinder, or a ring, and the aluminum nitride spray film The surface roughness of the above-mentioned substrate is a metal having a thermal conductivity of 100 W/mK or more. The aluminum nitride spray member according to any one of the preceding claims, wherein the substrate is a metal having a thermal conductivity of 100 W/mK or more. Or the exothermic substrate of the metal-ceramic retanning, the thermal conductivity of the nitriding film is 10 W/mK or more. 17· The nitriding shot according to any one of the claims 1-5 to 16 The member, wherein the foregoing nitriding film is sealed. 18. The nitriding member according to any one of claims 1 to 17 wherein the insulating property of the nitriding film is 〇15 ΜV/cm or more. ❹ , 19. A method for producing an aluminum nitride spray member, which comprises the aluminum nitride spray member according to claim 1 or 7, which has an average particle diameter of 1 Am aluminum powder of less than 1 〇 is supplied to the spraying device, and is sprayed by ordinary piezoelectric violet Forming a nitrided fused film on the substrate, wherein the plasma is sprayed under the condition that the average temperature of the aluminum nitride particles immediately before reaching the substrate is 2200t or more and 2281TC or less, and the average flying speed is 400 m/s or more. 〇〇m/s or less., a manufacturing method of a nitriding smelting member, and an aluminum nitride absorbing member according to the second or eighth aspect of the application of the patent No. 7105-10188-PF 34 200944618, characterized in that : The average particle size is i ′′ or more and 1 〇” below & ΠΙΑ and/or steroid powder and average granules are obtained as 丄 以上 以上 〇 〇 以下 以下 以下 以下 以下 以下 以下 以下 以下 以下 以下 以下 以下 以下 以下 以下 以下The 飞行 Μ Μ Μ 在 在 Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ 400 m / s or more and 6 〇〇 m / s or less. 21. A method for producing a nitriding melt-casting member, which comprises manufacturing an aluminum nitride spray member according to claim 1 or claim 7, wherein: an average particle diameter of 1 is applied to 10... The nitriding powder and the mixed powder of G1~5 w(iv) lubricant with respect to the end of the nitriding (tetra) are supplied as a spray powder to the spray skirt, and are nitrided on the substrate by normal piezoelectric slurry. Aluminum spray film. 22. A method for producing a nitrided immersion member, which comprises producing an aluminum nitride spray member according to claim 2 or claim 8, wherein: an average particle diameter of i "above 1" (four) or less is added. a mixed powder of a powder of an ιπΑ family and/or a group IIA compound and an average particle diameter of (approximately 1-5 Å or less) and a lubricant having a total weight of 〇1 to 5 % by weight relative to the powders The shot powder is supplied to the glare device, and is sprayed on the substrate by the normal piezoelectric slurry to form an aluminum nitride spray 骐. 23. A method for manufacturing an aluminum nitride spray member, which is manufactured as claimed in the patent 7105-1018S - PF 35 200944618 The aluminum nitride spray member of the first or seventh aspect, characterized in that the average particle diameter is 1 # τη or more and is supplied to the outside of the plasma outlet of the shot to be supplied in two directions and opposed to each other. And borrowed into a nitride film, wherein the above electricity is 40 mm or more and 70 mm or less. 1 氮化# m of aluminum nitride powder, more than one position perpendicular to the plasma spray from the normal piezoelectric slurry sprayed on the substrate The condition of the spray and the spray is that the spray distance is ❹ 24. A method for producing an aluminum nitride spray member, which is characterized in that the aluminum nitride spray member according to claim 2 or 8 is characterized in that: ΠΙΑ having an average particle diameter A 1 Μ or more and 10 Am or less a mixed powder of a family and/or steroid powder and an aluminum nitride powder having an average particle diameter of i or more and less than or equal to 10 Å, and is sprayed perpendicularly to the plasma at a position of two or more outside the sprayed plasma outlet. The aluminum nitride spray film is formed on the substrate by normal piezoelectric poly-solubilization, wherein the electropolymerization conditions are such that the spray distance is less than or equal to 1 mm. 7105-1O188-PF 36