Film-forming material, film-forming slurry, sprayed film, and spraying member

Abstract

A coating film is formed using a film-forming material containing particles including a crystal phase of a rare earth element fluoride, particles including a crystal phase of a rare earth element oxide, and particles including a crystal phase of a rare earth element ammonium bifluoride complex salt, or a film-forming material containing particles including a crystal phase of a rare earth element fluoride and particles including a crystal phase of a rare earth element oxide and a crystal phase of a rare earth element ammonium bifluoride complex salt. In the film-forming material or film-forming slurry of the present application, particularly if a spray coating film is formed using the film-forming material or film-forming slurry using spraying, a rare earth element oxyfluoride spray coating film can be formed without requiring excess heat, so that even under the atmosphere, the progress of an oxidation reaction caused by spraying heat is suppressed, while a rare earth element oxyfluoride spray coating film having little rare earth element fluoride and rare earth element oxide is obtained, and in addition, film peeling caused by excess heat can be suppressed.

Description

Technical Field

[0001] The present invention relates to film-forming materials and film-forming slurries for forming films such as excellent spray coatings capable of forming corrosion-resistant coatings for components of semiconductor manufacturing apparatuses, spray coatings obtained by spraying the same, and spray coating components having the spray coatings. Background Technology

[0002] In recent years, with the continuous development of semiconductor integration, the linewidth requirement for forming on wafers using dry etching has gradually become below 10nm, and there is a need to reduce particles generated during semiconductor manufacturing processes. To date, research has been conducted on rare earth element oxyhalide films formed using atmospheric plasma spraying (APS) as a low-particle film required for corrosion-resistant films for components used in semiconductor manufacturing apparatuses. For example, International Patent Publication No. 2014 / 002580 (Patent Document 1) discloses a spraying material containing yttrium oxyfluoride.

[0003] In response, there is a growing interest in developing coatings containing rare-earth element oxyfluorides formed using atmospheric suspended plasma spraying (SPS) with improved low particle content. As a spraying material for this purpose, International Patent Publication No. 2015 / 019673 (Patent Document 2) discloses a spraying slurry containing particles of rare-earth element oxyfluorides and a dispersion medium. However, spray coatings formed using atmospheric suspended plasma spraying are obtained through a high-power spray plume. Therefore, compared to atmospheric plasma spraying, the oxidation reaction occurs faster in the atmospheric spraying atmosphere, resulting in a problem of a large amount of oxides forming in the resulting spray coating.

[0004] Previously, to obtain a rare earth element oxyfluoride coating, rare earth element fluorides, rare earth element oxyfluorides, and rare earth element oxides were sprayed individually or in mixtures. When rare earth element fluorides are sprayed, for example, using atmospheric suspension plasma spraying, even if a rare earth element oxyfluoride coating is obtained, a large amount of rare earth element fluoride remains in the coating. Furthermore, even with rare earth element oxyfluorides, an atmospheric oxidation reaction occurs during the spraying process, resulting in a large amount of rare earth element oxides as byproducts in the coating. On the other hand, for mixtures of rare earth element fluorides and rare earth element oxyfluorides, or mixtures of rare earth element fluorides and rare earth element oxides, to obtain a rare earth element oxyfluoride coating by reacting them in a short time during the spraying process, high-power conditions are required for spraying. In this case, the oxidation and reaction of molten particles occur simultaneously, resulting in a large amount of rare earth element oxides as byproducts in the coating. These residues and byproducts are considered to be one of the reasons for particle generation.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: International Publication No. 2014 / 002580

[0008] Patent Document 2: International Publication No. 2015 / 019673 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] The present invention was made in view of the above-mentioned actual situation, and its object is to provide a film-forming material suitable as a spraying material, etc., that suppresses the residue or by-product of rare earth element oxides and rare earth element fluorides in the sprayed film even during film formation, especially under atmospheric spraying such as atmospheric plasma spraying (APS) or atmospheric suspended plasma spraying (SPS), and is capable of forming a rare earth element oxyfluoride sprayed film with a low presence ratio of rare earth element oxides and rare earth element fluorides, and a film-forming slurry suitable as a spraying slurry. Furthermore, the present invention aims to provide a rare earth element oxyfluoride sprayed film with a low presence ratio of rare earth element oxides and rare earth element fluorides and low particulate matter, and a spraying component having the sprayed film.

[0011] Methods for solving problems

[0012] To achieve the above objectives, the inventors conducted repeated and in-depth research, and as a result, discovered the following: film-forming materials containing particles of crystalline phases comprising rare earth element fluorides, particles of crystalline phases comprising rare earth element oxides, and particles of crystalline phases comprising rare earth element ammonium fluoride complex salts; particularly film-forming materials in which particles of crystalline phases comprising rare earth element oxides and particles of crystalline phases comprising rare earth element ammonium fluoride complex salts form mutually dispersed composite particles; or film-forming materials containing particles of crystalline phases comprising rare earth element fluorides, particles of crystalline phases comprising rare earth element oxides, and particles of crystalline phases comprising rare earth element ammonium fluoride complex salts; particularly film-forming materials containing rare earth elements... The film-forming material is excellent as a film-forming material, which is a composite particle consisting of particles containing the crystal phase of rare earth oxides and the crystal phase of rare earth element ammonium fluoride double salts, with particles containing the crystal phase of rare earth element oxides as the matrix, and in which particles or layers containing the crystal phase of rare earth element ammonium fluoride double salts are dispersed on the surface and / or inside the particles containing the crystal phase of rare earth element oxides. It is particularly excellent as a spraying material that can easily form rare earth element fluoride spray coating films with few rare earth element oxides. In addition, the film-forming slurry containing such a film-forming material is excellent as a spraying slurry, thereby completing the present invention.

[0013] Therefore, the present invention provides the following film-forming materials, film-forming slurries, spray coatings, and spray components.

[0014] 1. A film-forming material, characterized in that it contains: particles comprising a crystalline phase of rare earth element fluorides, particles comprising a crystalline phase of rare earth element oxides, and particles comprising a crystalline phase of rare earth element ammonium fluoride double salts.

[0015] 2. The film-forming material according to claim 1, characterized in that the particles of the crystalline phase containing rare earth element oxides and the particles of the crystalline phase containing rare earth element ammonium fluoride double salts form mutually dispersed composite particles.

[0016] 3. The film-forming material according to 1 or 2, characterized in that the particles of the crystalline phase containing rare earth element oxides are rare earth element oxide particles, and the particles of the crystalline phase containing rare earth element ammonium fluoride double salts are rare earth element ammonium fluoride double salt particles.

[0017] 4. A film-forming material, characterized in that it contains: particles comprising a crystalline phase of rare earth element fluorides, and particles comprising a crystalline phase of rare earth element oxides and a crystalline phase of rare earth element ammonium fluoride double salts.

[0018] 5. The film-forming material according to 4, characterized in that the particles containing the rare earth element oxide crystal phase and the rare earth element ammonium fluoride double salt crystal phase are formed by using the particles containing the rare earth element oxide crystal phase as a matrix, forming the particles containing the rare earth element ammonium fluoride double salt crystal phase or composite particles dispersed on the surface and / or inside the particles containing the rare earth element oxide crystal phase.

[0019] 6. The film-forming material according to 4 or 5, characterized in that the particles of the crystalline phase containing rare earth element oxides are rare earth element oxide particles, and the particles or layers of the crystalline phase containing rare earth element ammonium fluoride double salts are rare earth element ammonium fluoride double salt particles or layers.

[0020] 7. The film-forming material according to any one of 1 to 6, characterized in that the particles of the crystalline phase containing rare earth element fluorides are rare earth element fluoride particles.

[0021] 8. The film-forming material according to any one of 1 to 7, characterized in that it does not contain a crystalline phase of rare earth element oxyfluorides.

[0022] 9. The film-forming material according to any one of 1 to 8, characterized in that the rare earth element ammonium fluoride double salt comprises a component selected from (NH4)3R. 3 F6, NH4R 3 F4, NH4R 3 2F7 and (NH4)3R 3 One or more of 2F9, where R 3 Each element is selected from one or more rare earth elements containing Sc and Y.

[0023] 10. The film-forming material according to any one of 1 to 9, characterized in that the oxygen content is 0.3 to 10% by mass.

[0024] 11. The film-forming material according to any one of 1 to 10, characterized in that, in X-ray diffraction using CuKα rays as characteristic X-rays, the X-ray concentration of the diffraction peaks of the crystalline phase detected in the range of diffraction angle 2θ = 10 to 70° is calculated according to the following formula. F0 The value is above 0.01.

[0025] X F0 =I(RNF) / (I(RF)+I(RO))

[0026] In the formula, I(RNF) is the integrated intensity value of the largest peak of the diffraction peak belonging to the rare earth element ammonium fluoride double salt, I(RF) is the integrated intensity value of the largest peak of the diffraction peak belonging to the rare earth element fluoride, and I(RO) is the integrated intensity value of the largest peak of the diffraction peak belonging to the rare earth element oxide.

[0027] 12. The film-forming material according to any one of 1 to 11, characterized in that the average particle size D50(F1) of the particles of the crystalline phase containing rare earth element fluoride is 0.5 to 10 μm, and the average particle size D50(F1) is the cumulative 50% diameter (median diameter) in the volume-based particle size distribution determined by mixing in 30 mL of pure water and subjecting it to ultrasonic dispersion at 40 W for 1 minute.

[0028] 13. The film-forming material according to any one of 1 to 12, characterized in that, in the particle size distribution of the crystalline phase containing rare earth element fluorides, P is calculated according to the following formula. D The value is below 4.

[0029] P D =((D90(F1)-D10(F1)) / D50(F1)

[0030] In the formula, D90(F1) is the cumulative 90% diameter of the particle size distribution of the volume reference, which is determined by ultrasonic dispersion treatment under conditions of 40W and 1 minute after mixing in 30mL of pure water; D10(F1) is the cumulative 10% diameter of the particle size distribution of the volume reference, which is determined by ultrasonic dispersion treatment under conditions of 40W and 1 minute after mixing in 30mL of pure water; and D50(F1) is the cumulative 50% diameter (median diameter) of the particle size distribution of the volume reference, which is determined by ultrasonic dispersion treatment under conditions of 40W and 1 minute after mixing in 30mL of pure water.

[0031] 14. The film-forming material according to any one of 1 to 13, characterized in that the BET specific surface area of ​​the particles comprising the rare earth element fluoride crystalline phase is 10 m². 2 / g or less.

[0032] 15. The film-forming material according to any one of 1 to 14, characterized in that the loose packing density of the particles comprising the rare earth element fluoride crystalline phase is 0.6 g / cm³. 3 above.

[0033] 16. The film-forming material according to any one of 1 to 15, characterized in that the film-forming material is in powder or granular form.

[0034] 17. The film-forming material according to 16, characterized in that the cumulative 50% diameter (median diameter), i.e., the average particle size D50(S0), in the volume-based particle size distribution is 10 to 100 μm.

[0035] 18. A film-forming slurry, characterized in that it comprises a film-forming material according to any one of 1 to 15 and a dispersion medium.

[0036] 19. The film-forming slurry according to 18, characterized in that the slurry concentration is 10-70% by mass.

[0037] 20. The film-forming slurry according to 18 or 19, characterized in that the dispersion medium comprises a non-aqueous solvent.

[0038] 21. The film-forming slurry according to any one of 18 to 20, characterized in that the cumulative 50% diameter (median diameter), i.e., the average particle size D50(S1), in the volume-based particle size distribution determined by mixing in 30 mL of pure water and ultrasonically dispersing at 40 W for 1 minute, is 1 to 10 μm.

[0039] 22. The film-forming slurry according to any one of 18 to 21, characterized in that P is calculated by the following formula based on the average particle size D50(S1) and the average particle size D50(S3). SA The value is above 1.04.

[0040] P SA =D50(S1) / D50(S3)

[0041] Wherein, D50(S1) is the cumulative 50% diameter (median diameter) of the particle size distribution of the volume reference, which is determined by ultrasonic dispersion treatment at 40W for 1 minute after mixing in 30 mL of pure water, and D50(S3) is the cumulative 50% diameter (median diameter) of the particle size distribution of the volume reference, which is determined by ultrasonic dispersion treatment at 40W for 3 minutes after mixing in 30 mL of pure water.

[0042] 23. The film-forming slurry according to any one of 18 to 22, characterized in that the film-forming material has a thermal loss of 0.5% by mass or more under atmospheric conditions at 500°C for 2 hours.

[0043] 24. The film-forming material according to any one of 1 to 17, characterized in that the film-forming material is a spraying material.

[0044] 25. The film-forming slurry according to any one of 18 to 23, characterized in that the film-forming slurry is a spraying slurry.

[0045] 26. A sprayed film, characterized in that it is obtained by spraying a film-forming material according to 24 or a film-forming slurry according to 25.

[0046] 27. A sprayed component, characterized in that the sprayed component has a sprayed coating on a substrate according to 26.

[0047] 28. The spraying component according to 27, wherein the spraying component is a component for a semiconductor manufacturing apparatus.

[0048] The effects of the invention

[0049] According to the film-forming material or film-forming slurry of the present invention, especially when a spray coating is formed by spraying using the film-forming material or film-forming slurry, a rare earth element oxyfluoride spray coating can be formed without the need for excessive heat. Therefore, even under atmospheric conditions, the oxidation reaction caused by spraying heat is suppressed, and a rare earth element oxyfluoride spray coating with less rare earth element fluoride and rare earth element oxide can be obtained. In addition, the film peeling caused by the influence of excessive heat can be suppressed. Attached Figure Description

[0050] Figure 1 This is a scanning electron microscope image of the film-forming material obtained in Example 1.

[0051] Figure 2 The X-ray diffraction distribution of the film-forming material obtained in Example 1 is shown. Detailed Implementation

[0052] The present invention will now be described in more detail.

[0053] The film-forming material of the present invention contains: a crystalline phase of rare earth element fluorides, a crystalline phase of rare earth element oxides, and a crystalline phase of rare earth element ammonium fluoride double salts. The film-forming material of the present invention can be used in solid forms such as powder or granules for film formation in processes such as spraying, physical vapor deposition (PVD), and aerosol deposition (AD). In the case of spraying, it is suitable for atmospheric plasma spraying (APS). Furthermore, the film-forming material of the present invention can be formulated into a film-forming slurry comprising the film-forming material and a dispersion medium. When used in slurry form, the film-forming material is suitable as a spraying slurry, which is suitable for atmospheric suspension plasma spraying (SPS).

[0054] The film-forming material of the present invention comprises: a film-forming material containing particles of a crystalline phase comprising rare earth element fluorides, particles of a crystalline phase comprising rare earth element oxides, and particles of a crystalline phase comprising rare earth element ammonium fluoride double salts (the film-forming material of the first embodiment). Preferably, the film-forming material of the first embodiment forms composite particles (the composite particles of the first embodiment) in which particles of a crystalline phase comprising rare earth element oxides and particles of a crystalline phase comprising rare earth element ammonium fluoride double salts are mutually dispersed. Furthermore, the film-forming material of the first embodiment is preferably a mixture of particles of a crystalline phase comprising rare earth element fluorides and composite particles of the first embodiment, or granulated particles. Moreover, in the case of the film-forming material of the first embodiment, it is preferable that the particles of a crystalline phase comprising rare earth element fluorides are rare earth element fluoride particles, it is preferable that the particles of a crystalline phase comprising rare earth element oxides are rare earth element oxide particles, and it is preferable that the particles of a crystalline phase comprising rare earth element ammonium fluoride double salts are rare earth element ammonium fluoride double salt particles.

[0055] Furthermore, the film-forming material of the present invention comprises: a film-forming material containing particles of a crystalline phase comprising rare earth element fluorides, and particles containing crystalline phases of rare earth element oxides and crystalline phases of rare earth element ammonium fluoride complex salts (the film-forming material of the second embodiment). Preferably, the film-forming material of the second embodiment comprises particles containing crystalline phases of rare earth element oxides and crystalline phases of rare earth element ammonium fluoride complex salts, with particles containing crystalline phases of rare earth element oxides serving as a matrix, forming composite particles (the composite particles of the second embodiment) on the surface and / or within the particles containing crystalline phases of rare earth element oxides, where particles or layers containing crystalline phases of rare earth element ammonium fluoride complex salts are dispersed. Alternatively, the film-forming material of the second embodiment is preferably a mixture or granulated particles of particles containing crystalline phases of rare earth element fluorides and composite particles of the second embodiment. Furthermore, in the case of the film-forming material of the second scheme, it is preferable that the particles of the crystal phase containing rare earth element fluoride are rare earth element fluoride particles, it is preferable that the particles of the crystal phase containing rare earth element oxide are rare earth element oxide particles, and it is preferable that the particles or layers of the crystal phase containing rare earth element ammonium fluoride double salt are rare earth element ammonium fluoride double salt particles or layers.

[0056] Therefore, in the film-forming materials of both the first and second embodiments, the composite particles contain both the crystalline phases of rare earth element oxides and rare earth element ammonium fluoride complex salts. Furthermore, in the film-forming materials of both the first and second embodiments, it is preferable that the particles containing the crystalline phases of rare earth element fluorides are particles composed solely of rare earth element fluorides without any other components, and it is even more preferable that the crystalline phase is essentially composed of rare earth element fluorides. In this case, it is advantageous that particles or layers of rare earth element ammonium fluoride complex salts are abundant near the particles containing the crystalline phases of rare earth element oxides. Furthermore, in the film-forming materials of both the first and second embodiments, as long as the composite particles (the composite particles of the first and second embodiments) are in small quantities, they can contain components other than rare earth element oxides and rare earth element ammonium fluoride complex salts, preferably particles composed essentially only of rare earth element oxides and rare earth element ammonium fluoride complex salts, and preferably particles with crystalline phases essentially composed of rare earth element oxides and rare earth element ammonium fluoride complex salts.

[0057] The film-forming material of the present invention preferably does not contain rare earth element oxyfluorides. Compared with rare earth element fluorides and rare earth element oxides, rare earth element oxyfluorides are unstable compounds. If rare earth element oxyfluorides are included in the film-forming material, for example in the case of spraying, the oxidation reaction of rare earth element oxyfluorides will preferentially occur in the spraying process, and sometimes the amount of rare earth element oxides in the sprayed film obtained by spraying the film-forming material will increase.

[0058] In this invention, R can be listed as a rare earth element fluoride. 1 F2, R 1 F3 (where R is in the formula) 1 It is selected from one or more rare earth elements containing Sc and Y. Rare earth element fluorides can be one element or a mixture of two or more. Additionally, R... 1 It can be common in some or all rare earth element fluorides, or it can be different in various rare earth element fluorides.

[0059] In this invention, R can be listed as a rare earth element oxide. 2 O, R 2 2O3(R 2 It is selected from one or more rare earth elements including Sc and Y. Rare earth element oxides can be one or a mixture of two or more. Additionally, R... 2 It can be common to some or all of the rare earth element oxides, or it can be different in various rare earth element oxides.

[0060] In this invention, (NH4)3R can be listed as a rare earth element ammonium fluoride double salt. 3 F6, NH4R 3 F4, NH4R3 2F7、(NH4)3R 3 2F9 (where R is the formula) 3 Each is selected from one or more rare earth elements containing Sc and Y. (e.g., rare earth element ammonium fluoride double salts can be one or a mixture of two or more. Additionally, R...) 3 It can be common in some or all rare earth element ammonium fluoride double salts, or it can be different in various rare earth element ammonium fluoride double salts.

[0061] In this invention, R can be listed as a rare earth element oxyfluoride. 4 OF(R 4 1O1F1)R 4 4O3F6, R 4 5O4F7, R 4 6O5F8, R 4 7O6F9, R 4 17 O 14 F 23 R 4 O2F, R 4 OF2 (where R is in the formula) 4 It is selected from one or more rare earth elements containing Sc and Y. Rare earth element oxyfluorides can be one type or a mixture of two or more types. Additionally, R... 4 It can be common in some or all rare earth element oxyfluorides, or it can be different in various rare earth element oxyfluorides.

[0062] For the film-forming material of the present invention, as long as it does not impair the effects of the present invention, other components may include rare earth element compounds or particles other than rare earth element fluorides, rare earth element oxides and rare earth element ammonium fluoride double salts, rare earth element hydroxides, rare earth element carbonates, etc., as well as compounds or particles of other elements. The content of other components is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, particularly preferably 1% by mass or less, and most preferably substantially free of other components.

[0063] Furthermore, in the case where the film-forming material, as in the first and second embodiments, contains rare earth element oxides and rare earth element ammonium fluoride complex salts as composite particles, it may contain rare earth element oxide particles consisting only of rare earth element oxides without other components, and rare earth element ammonium fluoride complex salt particles consisting only of rare earth element ammonium fluoride complex salts without other components. The total content of rare earth element oxide particles and rare earth element ammonium fluoride complex salt particles relative to the composite particles is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, particularly preferably 1% by mass or less, and most preferably substantially free of these rare earth element oxide particles and rare earth element ammonium fluoride complex salt particles.

[0064] In this invention, the rare earth elements include Sc (scandium), yttrium (y), and lanthanides (elements with atomic numbers 57-71). Y, Sc, erbium (Er), and ytterbium (Yb) are particularly preferred as rare earth elements.

[0065] The film-forming material of the present invention preferably has an oxygen content of 0.3% by mass or more. If the oxygen content is 0.3% by mass or more, for example, when used in spraying, the amount of rare earth element fluorides in the sprayed film obtained by spraying the film-forming material can be reduced, which is advantageous. Furthermore, it is advantageous in reducing the surface roughness of the sprayed film. The oxygen content is more preferably 0.5% by mass or more, further preferably 1% by mass or more, and particularly preferably 2% by mass or more. On the other hand, the film-forming material of the present invention preferably has an oxygen content of 10% by mass or less. If the oxygen content is 10% by mass or less, for example, when used in spraying, the amount of rare earth element oxides in the sprayed film obtained by spraying the film-forming material can be reduced, which is advantageous. The oxygen content is more preferably 9% by mass or less, further preferably 8% by mass or less, and particularly preferably 7% by mass or less. To ensure that the oxygen content of the film-forming material is within the above range, the oxygen content relative to the total components constituting the film-forming material can be appropriately adjusted during the manufacturing of the film-forming material. Specifically, the ratio of composite particles (composite particles of the first or second scheme) in the film-forming material can be adjusted, or the ratio of particles containing rare earth oxide crystalline phases in the composite particles can be adjusted.

[0066] The preferred film-forming material of the present invention is the X-ray diffraction material obtained from the diffraction peaks of the crystalline phase detected in X-ray diffraction using CuKα rays as characteristic X-rays, within the diffraction angle range of 2θ = 10 to 70°, calculated according to the following formula. FO The value is above 0.01.

[0067] X F0 =I(RNF) / (I(RF)+I(RO))

[0068] (In the formula, I(RNF) is the integrated intensity of the largest peak of the diffraction peak belonging to the rare earth element ammonium fluoride double salt, I(RF) is the integrated intensity of the largest peak of the diffraction peak belonging to the rare earth element fluoride, and I(RO) is the integrated intensity of the largest peak of the diffraction peak belonging to the rare earth element oxide.)

[0069] In cases where two or more compounds are present in rare earth element ammonium fluoride double salts, rare earth element fluorides, and rare earth element oxides, I(RNF), I(RF), and I(RO) are the sum of the integrated intensities of the maximum peaks of the respective diffraction peaks of the two or more compounds. Since the NH3 gas produced by the decomposition and dissociation of rare earth element ammonium fluoride double salts has the property of combustion at high temperatures, although not specifically limited, it is considered that X... F0 The higher the value, the more oxygen is consumed from the surrounding air, thus inhibiting the oxidation of rare earth element fluorides. F0 The value of X is more preferably 0.02 or higher, even more preferably 0.05 or higher, and particularly preferably 0.08 or higher. On the other hand, X F0 The value of X is preferably less than or equal to 1. F0 When the value is 1 or less, it is particularly advantageous in suppressing the increase in viscosity of the slurry, especially when the film-forming material is used in the form of a film-forming slurry. F0 The value is more preferably 0.8 or less, further preferably 0.6 or less, and particularly preferably 0.4 or less.

[0070] The preferred film-forming material of the present invention is the X-ray diffraction material obtained from the diffraction peaks of the crystalline phase detected in X-ray diffraction using CuKα rays as characteristic X-rays, within the diffraction angle range of 2θ = 10 to 70°, calculated according to the following formula. F The value is above 0.01.

[0071] X F =I(RNF) / I(RF)

[0072] (In the formula, I(RNF) is the integrated intensity of the largest peak of the diffraction peak belonging to the rare earth element ammonium fluoride double salt, and I(RF) is the integrated intensity of the largest peak of the diffraction peak belonging to the rare earth element fluoride.)

[0073] In cases where two or more compounds are present in rare earth element ammonium fluoride double salts and rare earth element fluorides, I(RNF) and I(RF) are the sum of the integrated intensities of the maximum peaks of the respective diffraction peaks of the two or more compounds. If X FA value of 0.01 or higher increases the proportion of rare earth element ammonium fluoride complex salts in the film-forming material. For example, in spray coating applications, this is effective in suppressing oxidation reactions during the spraying process. Rare earth element ammonium fluoride complex salts decompose and dissociate within a short time in the spray chamber, producing HF and NH3 gases. There is no particular limitation on the produced HF gas; it is assumed to react instantaneously with the rare earth element oxides contained in the film-forming material to form rare earth element oxyfluorides. F The value of X is more preferably 0.02 or higher, even more preferably 0.05 or higher, and particularly preferably 0.08 or higher. On the other hand, X F The value is preferably 1 or less. In the case of a film-forming material containing a rare earth element ammonium fluoride complex salt as a composite particle with particles containing a rare earth oxide crystalline phase, if the ratio of the rare earth element ammonium fluoride complex salt in the rare earth element film-forming material increases, the ratio of rare earth oxides in the rare earth element film-forming material also increases. As a result, for example, in the case of spraying, sometimes the amount of rare earth element oxides contained in the spray film obtained by spraying the film-forming material increases. F The value is more preferably 0.8 or less, further preferably 0.6 or less, and particularly preferably 0.4 or less.

[0074] The preferred film-forming material of the present invention is the X-ray diffraction material obtained from the diffraction peaks of the crystalline phase detected in X-ray diffraction using CuKα rays as characteristic X-rays, within the diffraction angle range of 2θ = 10 to 70°, calculated according to the following formula. O The value is above 0.01.

[0075] X0 = I(RNF) / I(RO)

[0076] (In the formula, I(RNF) is the integrated intensity of the largest peak of the diffraction peak belonging to the rare earth element ammonium fluoride double salt, and I(RO) is the integrated intensity of the largest peak of the diffraction peak belonging to the rare earth element oxide.)

[0077] In cases where two or more compounds are present in both rare earth element ammonium fluoride complex salt and rare earth element oxides, I(RNF) and I(RO) are the sum of the integrated intensity values ​​of the maximum peaks of the diffraction peaks of the two or more compounds. If the value of X0 is 0.01 or higher, the ratio of rare earth element ammonium fluoride complex salt contained in the film-forming material, especially in the case of a film-forming material containing rare earth element ammonium fluoride complex salt as a composite particle with particles containing a crystalline phase of rare earth oxides, increases the ratio of rare earth element ammonium fluoride complex salt contained in the composite particle. For example, in the case of use in spraying, this increases the reaction efficiency of rare earth element ammonium fluoride complex salt in the spraying process, which is effective in reducing the amount of rare earth element oxides contained in the spray film obtained by spraying the film-forming material. The value of X0 is more preferably 0.02 or higher, further preferably 0.05 or higher, and particularly preferably 0.08 or higher. On the other hand, the value of X0 is preferably 1 or lower. If the value of X0 is 1 or less, for example, in the case of use in spraying, it can serve as an oxygen supply source for reacting rare earth element oxides with rare earth element fluorides or rare earth element ammonium fluoride double salts to obtain a spray film containing rare earth element oxyfluorides in the film obtained by spraying the film-forming material, thus enabling the rare earth element oxides to function effectively. The value of X0 is more preferably 0.8 or less, further preferably 0.6 or less, and particularly preferably 0.4 or less.

[0078] In the case of rare earth elements such as yttrium (Y), the maximum peak of yttrium ammonium fluoride (NH4Y2F7) in its cubic crystal system is not particularly limited, and generally becomes a diffraction peak belonging to the (541) plane of the crystal lattice. This diffraction peak is usually detected around 2θ = 27.3°. Similarly, the maximum peak of yttrium fluoride (YF3) is not particularly limited, and generally becomes a diffraction peak belonging to the (111) plane of the crystal lattice. This diffraction peak is usually detected around 2θ = 27.9°. The maximum peak of yttrium oxide (Y2O3) is not particularly limited, and generally becomes a diffraction peak belonging to the (222) plane of the crystal lattice. This diffraction peak is usually detected around 2θ = 29.2°.

[0079] The film-forming material of the present invention can be used in film formation processes such as spraying, physical vapor deposition (PVD), and aerosol deposition (AD) in solid form, such as powder or granules. Regarding the rare earth element ammonium fluoride double salt in the film-forming material, decomposition occurs if the temperature exceeds 200°C; therefore, it is preferable that the film-forming material is not sintered at temperatures exceeding 200°C. The film-forming material of the present invention, for example, when manufactured by granulation, can be dried at temperatures below 200°C. Furthermore, in the case of a film-forming material manufactured by granulation, it may contain a binder or other binder added as needed during granulation.

[0080] When the film-forming material of the present invention is used in a solid form such as powder or granules, the average particle size D50(S0) of the cumulative 50% diameter (median diameter) in the particle size distribution based on volume is preferably 100 μm or less. The average particle size D50(S0) is the average particle size obtained by measuring the particle size distribution of the film-forming material in its original state without any pretreatment such as ultrasonic dispersion for particle size distribution measurement. The smaller the particle size of the film-forming material, for example, in the case of spraying, the smaller the diameter of the spatter formed by the collision of molten particles with the substrate or the film formed on the substrate, which can reduce the porosity of the formed spray film and suppress cracks generated in the spatter. The average particle size D50(S0) is more preferably 80 μm or less, further preferably 60 μm or less, and particularly preferably 50 μm or less. On the other hand, the average particle size D50(S0) is preferably 10 μm or more. The larger the particle size of the film-forming material, the greater the momentum of the molten particles, for example, in the case of spraying, which is advantageous in that it is easier to form splatter when colliding with the substrate or the film formed on the substrate, and also in that the flowability of the film-forming material (spraying material) is improved when it is supplied from the spraying material supply device to the spray gun. The average particle size D50(S0) is more preferably 12 μm or more, further preferably 15 μm or more, and particularly preferably 18 μm or more.

[0081] The film-forming material of the present invention can be dispersed in a dispersion medium and used for film formation in the form of a slurry. When using the film-forming material in the form of a slurry, the film-forming slurry is preferably used as a spraying slurry. The slurry concentration (the content of the film-forming material relative to the total slurry) is preferably 70% by mass or less. If the content of the film-forming material exceeds 70% by mass, for example, in the case of use in spraying, the slurry may sometimes become blocked in the supply device during spraying, and a sprayed film may not be formed. The lower the content of the film-forming material in the film-forming slurry, the more active the movement of particles in the slurry, and the better the dispersibility. In addition, the lower the content of the film-forming material in the film-forming slurry, the better the flowability of the slurry, and the more suitable it is for slurry supply. The slurry concentration is more preferably 65% ​​by mass or less, further preferably 60% by mass or less, and particularly preferably 55% by mass or less. When higher flowability is required, the slurry concentration can be further reduced, in which case it is preferably 45% by mass or less, more preferably 40% by mass or less, and further preferably 35% by mass or less. On the other hand, the slurry concentration is preferably 10% by mass or more. The higher the content of film-forming materials in the film-forming slurry, for example, in the case of spraying, the faster the film-forming speed of the sprayed film formed by spraying the slurry is increased, thereby improving productivity. Furthermore, the slurry concentration is more preferably 15% by mass or more, even more preferably 20% by mass or more, and particularly preferably 25% by mass or more.

[0082] The film-forming slurry includes a dispersion medium, which can be used alone or in combination with two or more. The dispersion medium preferably includes a non-aqueous dispersion medium, i.e., a dispersion medium other than water. There are no particular limitations on the non-aqueous dispersion medium; examples include alcohols, ethers, esters, and ketones. More specifically, preferred non-aqueous dispersion media include mono- or di-alcohols with 2 to 6 carbon atoms such as ethanol and isopropanol; ethers with 3 to 8 carbon atoms such as ethyl cellosolve; glycol ethers with 4 to 8 carbon atoms such as dimethyl diethylene glycol (DMDG); glycol esters with 4 to 8 carbon atoms such as ethyl cellosolve acetate and butyl cellosolve acetate; and cyclic ketones with 6 to 9 carbon atoms such as isophorone. More preferably, the non-aqueous dispersion medium is a water-soluble non-aqueous dispersion medium that is miscible with water. When using a mixture of a non-aqueous dispersion medium and water, water may be included as long as it does not impair the effects of the present invention. The amount of water mixed in the non-aqueous dispersion medium relative to the dispersion medium as a whole is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 10% by mass or less, particularly preferably 5% by mass or less, and most preferably the dispersion medium is substantially free of dispersion medium other than the non-aqueous dispersion medium (i.e., substantially free of water).

[0083] When the film-forming material of the present invention is used in slurry form, it is preferable that the average particle size D50(S1) of the cumulative 50% diameter (median diameter) in the volume-based particle size distribution, measured by ultrasonic dispersion treatment at 40W for 1 minute after mixing in 30 mL of pure water, is 10 μm or less. The smaller the particle size of the film-forming material, for example, when used in spraying, the smaller the diameter of the spatter formed by the collision of molten particles with the substrate or the film formed on the substrate during spraying, the lower the porosity of the formed spray film and the suppression of cracks generated in the spatter. The average particle size D50(S1) is more preferably 9 μm or less, further preferably 8 μm or less, and particularly preferably 7 μm or less. On the other hand, the average particle size D50(S1) is preferably 1 μm or more. The larger the particle size of the film-forming material, for example, when used in spraying, the greater momentum of the molten particles makes it easier to form spatter upon collision with the substrate or the film formed on the substrate. The average particle size D50(S1) is more preferably 1.5 μm or more, further preferably 2 μm or more, and particularly preferably 2.5 μm or more. Thus, a film-forming material with an average particle size D50(S1) of 1 to 10 μm is effective as a film-forming slurry in order to improve the supply of film-forming materials.

[0084] When the film-forming material of the present invention is used in slurry form, the preferred ratio is the ratio of the average particle size D50(S1) to the average particle size D50(S3), which is the cumulative 50% diameter (median diameter) of the volume-based particle size distribution measured by ultrasonic dispersion at 40W for 3 minutes after mixing in 30 mL of pure water.

[0085] P SA =D50(S1) / D50(S3)

[0086] It is above 1.04. SA The higher the value, the more the particles in the film-forming material maintain an appropriate state of aggregation. When the film-forming material of the present invention is used in the form of a film-forming slurry, it can prevent compaction caused by gravity during sedimentation and improve the redispersibility of the slurry. SA The value of is more preferably 1.05 or higher, even more preferably 1.07 or higher, and particularly preferably 1.09 or higher. On the other hand, for P... SA There is no particular limitation on the value of , but from the viewpoint of improving the fluidity of the slurry, it is preferably 1.3 or less, more preferably 1.28 or less, even more preferably 1.26 or less, and particularly preferably 1.24 or less.

[0087] The film-forming material of the present invention preferably exhibits a heat loss of 0.5% by mass or more under atmospheric conditions at 500°C for 2 hours. A smaller heat loss generally results in less impurities and is therefore considered preferable. However, in the film-forming material of the present invention, it is advantageous not only in this respect but also in the following aspects: if the heat loss under atmospheric conditions at 500°C for 2 hours is 0.5% by mass or more, particularly when the film-forming material is used as a film-forming slurry, the redispersibility (de-flocculation) of the slurry can be improved. While not particularly limited to this, it is believed that the ammonium fluoride component of the rare earth element ammonium fluoride complex salt contained in the film-forming material forms an energy barrier between particles of the rare earth element fluoride crystalline phase, particles of the rare earth element oxide crystalline phase, or composite particles, or between particles of the rare earth element fluoride crystalline phase and particles of the rare earth element oxide crystalline phase or composite particles, preventing particle aggregation and facilitating easy redispersibility even after precipitation occurs due to particle settling. The heat loss is more preferably 1% by mass or more, further preferably 2% by mass or more, and particularly preferably 3% by mass or more. On the other hand, there is no particular limitation on the heat loss, but from the perspective of its influence on the properties of the coating film (reduction of impurities), it is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less.

[0088] The average particle size D50(F1) of the particle size distribution of the rare earth element fluoride-containing crystalline phase contained in the film-forming material of the present invention is preferably 10 μm or less, based on the cumulative 50% diameter (median diameter) of the particle size distribution measured by ultrasonic dispersion treatment at 40 W for 1 minute in 30 mL of pure water. The smaller the particle size of the rare earth element fluoride-containing crystalline phase particles, for example, in the case of spraying, the smaller the diameter of the spatter formed when the molten particles collide with the substrate or the film formed on the substrate during spraying, which can reduce the porosity of the formed spray film and suppress cracks generated in the spatter. The average particle size D50(F1) is preferably 9 μm or less, more preferably 8 μm or less, and particularly preferably 7 μm or less. On the other hand, the average particle size D50(F1) is preferably 0.5 μm or more. As the particle size of the film-forming material increases, for example, in the case of spraying, the molten particles, having greater momentum, are more likely to collide with the substrate or the film formed on the substrate, thus easily forming splatter, which is advantageous. Furthermore, a larger particle size reduces the formation of convex protrusions on the surface of the sprayed film, which is also advantageous. The average particle size D50(F1) is more preferably 1 μm or more, further preferably 1.5 μm or more, and particularly preferably 2 μm or more.

[0089] For the particles containing rare earth element fluorides in the film-forming material of the present invention, the particle size distribution is preferably determined by the cumulative 90% diameter (D90(F1)) of the volume-based particle size distribution measured by mixing in 30 mL of pure water and ultrasonically dispersing at 40 W for 1 minute, and the cumulative 10% diameter (D10(F1)) of the volume-based particle size distribution measured by mixing in 30 mL of pure water and ultrasonically dispersing at 40 W for 1 minute, according to the following formula.

[0090] P D =((D90(F1)-D10(F1)) / D50(F1)

[0091] Calculated P D The value is below 4. P D The smaller the value, the narrower the particle size distribution and the more uniform the particle size. For example, in the case of spraying, it can suppress fluctuations in the properties of the sprayed film obtained by spraying the film-forming material. D The value of is more preferably 2 or less, further preferably 1.5 or less, and particularly preferably 1.3 or less. D Ideally, the lower limit of the value should be above 0, but in practice it is usually above 0.1, and preferably above 0.5.

[0092] The particles of the rare earth element fluoride crystalline phase contained in the film-forming material of the present invention are preferably, in terms of particle size distribution, the cumulative 50% diameter (median diameter) of the particle size distribution on a volume basis, measured by the average particle size D50(F1) and the average particle size D50(F3), which is determined by ultrasonic dispersion treatment at 40W for 3 minutes in 30 mL of pure water, according to the following formula.

[0093] P FA =D50(F1) / D50(F3)

[0094] Calculated P FA The value is below 1.05. P FA The smaller the value of P, especially when the film-forming material is used as a film-forming slurry, the better the slurry's fluidity can be improved. FA The value of is more preferably 1.04 or less, even more preferably 1.03 or less, and particularly preferably 1.02 or less. FA Ideally, the lower limit of the value is above 1, but in practice it is usually above 1.01.

[0095] The particles containing rare earth element fluorides in the film-forming material of the present invention preferably have a specific surface area of ​​10 m². 2 / g or less. Specific surface area is usually measured using the BET method. A smaller specific surface area, for example in spray coating applications, reduces the amount of microparticles that adhere to the surface of the formed spray film without entering the spray frame, thus causing particulate contamination; it also reduces the amount of microparticles that evaporate due to excess spray heat if they enter the spray beam. A more preferred specific surface area is 5m². 2 / g or less, further preferably 2m 2 / g or less, especially preferably 1m 2 / g or less. On the other hand, there are no particular limitations on the comparative surface area, but 0.01m² is preferred. 2 / g or more. A larger specific surface area, for example in spray coating applications, allows the heat from the spray booth to easily penetrate the particles during spraying. When the molten particles collide with the substrate or the film formed on the substrate, forming splatter, the film tends to become denser, and the bonding between the splatter particles becomes stronger, which is advantageous. A specific surface area of ​​0.05m² is more preferably preferred. 2 / g or more, further preferably 0.1m 2 / g or more, with 0.3m being particularly preferred. 2 / g or more.

[0096] The preferred bulk density of the crystalline phase containing rare earth element fluorides in the film-forming material of the present invention is 0.6 g / cm³. 3The above. Bulk density is generally used when referring to loose bulk density. Higher bulk density is advantageous, for example, in applications like spraying, where it facilitates the formation of splatter during plasma spraying, and makes it easier to achieve a denser coating film. Furthermore, since there is less gas content within the interparticle voids, the risk of deterioration in the properties of the resulting coating film is reduced. A bulk density of 0.65 g / cm³ is more preferred. 3 The above is further preferred to be 0.7 g / cm³. 3 The above, especially preferred, is 0.75 g / cm³. 3 above.

[0097] By using the film-forming material or film-forming slurry of the present invention for spraying, a spray coating film (surface coating film) containing rare earth element oxyfluoride, preferably used in components for semiconductor manufacturing apparatuses, can be formed on a substrate (e.g., directly or via a base coating film (lower coating film)). This enables the manufacture of spray-coated components including the spray coating film (surface coating film) formed on a substrate, for example, directly or via a base coating film (lower coating film). This spray-coated component is suitable as a component for semiconductor manufacturing apparatuses. The film thickness of the spray coating film (surface coating film) of the present invention is preferably 10 μm or more, more preferably 30 μm or more. Furthermore, the upper limit of the film thickness of the spray coating film (surface coating film) is preferably 500 μm or less, more preferably 300 μm or less.

[0098] There are no particular limitations on the material used as the substrate. Examples include stainless steel, aluminum, nickel, chromium, zinc, and their alloys, as well as inorganic compounds (ceramics) such as alumina, zirconium oxide, aluminum nitride, silicon nitride, silicon carbide, and quartz glass. The preferred material is selected based on the intended use of the component being coated (e.g., for semiconductor manufacturing equipment). For example, in the case of an aluminum metal or aluminum alloy substrate, a substrate with an alumina film treatment that provides acid resistance is preferred. Regarding the shape of the substrate, examples include substrates with planar or cylindrical shapes, and there are no particular limitations.

[0099] When forming a spray coating on a substrate, it is preferable to, for example, degrease the surface of the substrate on which the spray coating will form with acetone, or roughen it using an abrasive such as corundum, to increase the surface roughness (Ra). By roughening the substrate, peeling of the coating caused by the difference in the coefficients of thermal expansion between the spray coating and the substrate can be effectively suppressed after spraying. The degree of roughening can be appropriately adjusted according to the material of the substrate.

[0100] Before forming the spray coating film, a lower coating film can be pre-formed on a substrate, and the spray coating film can be formed via the base coating film. The thickness of the base coating film can be, for example, 50 to 300 μm. If the spray coating film is preferably formed on the lower coating film in contact with it, the base coating film can be formed as the lower coating film, and the spray coating film can be formed as the top coating film, making the coating film formed on the substrate a double-layer structure.

[0101] Materials used as substrate coatings include, for example, rare earth element oxides, rare earth element fluorides, and rare earth element oxyfluorides. Rare earth elements constituting the substrate coating can be the same rare earth elements used in the film-forming materials. The substrate coating can be formed, for example, by atmospheric plasma spraying under normal pressure or suspended plasma spraying.

[0102] The porosity of the substrate film is preferably 5% or less, more preferably 4% or less, and even more preferably 3% or less. Furthermore, there is no particular limitation on the lower limit of the porosity, which is generally 0.1% or more. Additionally, the surface roughness Ra of the substrate film is preferably 10 μm or less, more preferably 6 μm or less. Regarding the lower limit of the surface roughness Ra, the lower the better, which is generally 0.1 μm or more. If a sprayed film is preferably formed in contact with the substrate film as a surface film on a substrate film with low surface roughness Ra, the surface roughness Ra of the surface film can also be reduced, which is therefore preferable.

[0103] There are no particular limitations on the method for forming a substrate film with such low porosity and low surface roughness Ra. For example, as a raw material, single-particle powder or granulated spraying powder with an average particle size D50 of 0.5 μm or more, preferably 1 μm or more, 50 μm or less, preferably 30 μm or less can be used. Plasma spraying, explosive spraying, or similar methods can be employed to fully melt the particles and then spray them, thereby forming a dense substrate film with low porosity and surface roughness Ra. Single-particle powder refers to powder in the form of spherical powder, square powder, pulverized powder, etc., that is filled with (solid) particles. When using single-particle powder, since it is composed of fine particles with a particle size smaller than that of granulated spraying powder and is filled with particles, a substrate film with a small spatter diameter and suppressed crack formation can be formed.

[0104] In addition, regarding the substrate coating, surface roughness (Ra) can be reduced through surface processing such as mechanical grinding (surface grinding, inner cylinder machining, mirror finishing, etc.), sandblasting using micro-beads, and hand grinding using diamond pads.

[0105] The coating of the present invention is preferably obtained by using CuKα rays as the characteristic X-ray in X-ray diffraction, and by calculating the X-rays based on the following formula from the diffraction peaks of the crystalline phase detected in the range of diffraction angle 2θ = 10 to 70°. ROF The value is 1.2 or higher.

[0106] X ROF =I(ROF) / (I(RF)+I(RO))

[0107] (In the formula, I(ROF) is the integrated intensity of the largest peak of the diffraction peak belonging to rare earth element oxyfluorides, I(RF) is the integrated intensity of the largest peak of the diffraction peak belonging to rare earth element fluorides, and I(RO) is the integrated intensity of the largest peak of the diffraction peak belonging to rare earth element oxides.)

[0108] Where two or more compounds exist in each of the rare earth element oxyfluorides, rare earth element fluorides, and rare earth element oxides, I(ROF), I(RF), and I(RO) are the sum of the integrated intensity values ​​of the maximum peaks of each diffraction peak of the two or more compounds. X ROF The higher the value, the higher the proportion of rare earth element fluorides in the sprayed coating, and the lower the proportion of rare earth element fluorides and rare earth element oxides. Therefore, from the perspective of particle resistance, this is advantageous. ROF The value is more preferably 1.4 or higher, even more preferably 1.6 or higher, and particularly preferably 1.8 or higher.

[0109] When the rare earth element is, for example, yttrium (Y), the maximum peak of yttrium oxyfluoride (YOF(Y1O1F1)) in its rhombohedral crystal system is not particularly limited, and generally becomes a diffraction peak belonging to the (012) plane of the crystal lattice. This diffraction peak is usually detected at around 2θ = 28.7°. Similarly, the maximum peak of yttrium oxyfluoride (Y5O4F7) in its orthorhombic crystal system is not particularly limited, and generally becomes a diffraction peak belonging to the (151) plane of the crystal lattice. These diffraction peaks are usually detected at around 2θ = 28.1°.

[0110] There are no particular limitations on the method for forming the spray coating of the present invention, but atmospheric plasma spraying (APS) and atmospheric suspended plasma spraying (SPS) are preferred.

[0111] In atmospheric plasma spraying, the plasma gas used to form the plasma can be argon alone, nitrogen alone, or a mixture of two or more gases selected from argon, hydrogen, helium, and nitrogen, and there are no particular limitations. Furthermore, the spraying distance in atmospheric plasma spraying is preferably 150 mm or less. As the spraying distance decreases, the film formation rate of the sprayed film increases, and the hardness increases while the porosity decreases. A spraying distance of 140 mm or less is more preferred, and 130 mm or less is even more preferred. There are no particular limitations on the lower limit of the spraying distance, but 50 mm or more is preferred, 60 mm or more is more preferred, and 70 mm or more is even more preferred.

[0112] In suspended plasma spraying, the plasma gas used to form the plasma can be any mixture of two or more gases selected from argon, hydrogen, helium, and nitrogen, and more preferably a mixture of three gases (argon, hydrogen, and nitrogen) or a mixture of four gases (argon, hydrogen, helium, and nitrogen). There are no particular limitations. The spraying distance in suspended plasma spraying is preferably 100 mm or less. As the spraying distance decreases, the film formation rate of the sprayed film increases, and the hardness increases while the porosity decreases. A spraying distance of 90 mm or less is more preferred, and 80 mm or less is even more preferred. There are no particular limitations on the lower limit of the spraying distance, but 50 mm or more is preferred, more preferably 55 mm or more, and even more preferably 60 mm or more.

[0113] When forming a spray coating film on a substrate or a film (base film) formed on a substrate, it is preferable to perform the spraying while cooling the substrate, the film (base film) formed on the substrate, and the resulting spray coating film (surface film). Examples of cooling methods include air cooling and water cooling.

[0114] Specifically, the temperature of the substrate during spraying, or the substrate temperature of the film formed on the substrate, is preferably 200°C or lower. Lower temperatures better prevent heat-induced damage and deformation of the substrate, or the substrate temperature of the film formed on the substrate. Furthermore, lower temperatures better suppress the generation of thermal stress, preventing peeling between the substrate and the formed sprayed film, or between the film formed on the substrate (base film) and the formed sprayed film. The temperature of the substrate during spraying, or the substrate temperature of the substrate and the film formed on the substrate, is more preferably 180°C or lower, and even more preferably 150°C or lower. This temperature can be achieved by controlling the cooling capacity.

[0115] Preferably, the temperature of the substrate during spraying, or the substrate and the film formed on the substrate, is 50°C or higher. Higher temperatures enhance the bonding between the substrate and the formed sprayed film, or between the film formed on the substrate (base film) and the formed sprayed film (surface film), resulting in a denser sprayed film. More preferably, the temperature of the substrate during spraying, or the substrate and the film formed on the substrate, is 60°C or higher, and even more preferably 80°C or higher.

[0116] There are no particular limitations on other spraying conditions such as the supply rate of the film-forming material (film-forming slurry), the gas supply volume, and the applied power (current value, voltage value) in plasma spraying. Conventionally known conditions can be used, and can be appropriately set according to the substrate, the film-forming material (film-forming slurry), and the intended use of the resulting sprayed component. If the film-forming material or film-forming slurry of the present invention is used, the desired sprayed film can be obtained without excessive application of power.

[0117] In particular, when a spray coating is formed directly on a substrate, as described above, by pre-increasing the surface roughness Ra of the surface on which the spray coating is formed on the substrate, and then setting the substrate temperature to the aforementioned temperature, a spray coating that is more difficult to peel off, has higher hardness, and is denser can be formed. In this case, the surface roughness Ra of the formed spray coating tends to increase. Therefore, by surface processing such as mechanical grinding (surface grinding, inner cylinder machining, mirror finishing, etc.), sandblasting using micro-beads, or hand grinding using diamond pads, the surface roughness Ra can be reduced, resulting in a spray coating that is more difficult to peel off, has higher hardness, is denser, and has a low surface roughness Ra, and is lubricated.

[0118] Example

[0119] The following examples and comparative examples illustrate the invention in detail, but the invention is not limited to the following examples.

[0120] [Example 1]

[0121] [Manufacturing of Yttrium Fluoride Particles]

[0122] A 2 mol / L yttrium nitrate aqueous solution (equivalent to 2 moles of yttrium nitrate) was heated to 50°C. A 12 mol / L ammonium fluoride aqueous solution (equivalent to 7 moles of ammonium fluoride) was then added to the heated yttrium nitrate aqueous solution. The mixture was stirred for 1 hour while maintaining the temperature at 50°C. The resulting precipitate was filtered, washed, and dried at 70°C for 24 hours to obtain yttrium ammonium fluoride double salt. Next, the obtained yttrium ammonium fluoride double salt was calcined at 850°C for 4 hours in a tubular furnace under a nitrogen atmosphere, followed by pulverization using a jet mill to obtain yttrium fluoride particles.

[0123] [Physical Property Evaluation of Yttrium Fluoride Particles]

[0124] 0.1 g of the obtained yttrium fluoride particles were mixed into 30 mL of pure water in a glass beaker with a maximum graduated volume of 30 mL, and ultrasonically dispersed at 40 W for 1 minute. The average particle size D50 (F1), cumulative 90% diameter D90 (F1), and cumulative 10% diameter D10 (F1) in the volumetric particle size distribution were measured. Additionally, 0.1 g of the obtained yttrium fluoride particles were mixed into 30 mL of pure water in a glass beaker with a maximum graduated volume of 30 mL, and ultrasonically dispersed at 40 W for 3 minutes. The average particle size D50 (F3) in the volumetric particle size distribution was measured. From these results, the...

[0125] P D =((D90(F1)-D10(F1)) / D50(F1), and

[0126] P FA =D50(F1) / D50(F3)

[0127] The values ​​were also determined. Additionally, the BET specific surface area and loose bulk density were measured. The results are shown in Table 1. Further details of each measurement and analysis will be described later.

[0128] [Manufacturing of Composite Particles]

[0129] Five moles of yttrium oxide particles with a cumulative 50% diameter (median diameter) of 2 μm in the volume-based particle size distribution were added to pure water and stirred to prepare a slurry with a yttrium oxide particle concentration of 20% by mass. Twelve moles of acidic ammonium fluoride were added to the resulting slurry, and the mixture was aged at 50°C for 3 hours. The obtained particles were filtered, washed, and dried at 70°C to obtain composite particles containing yttrium oxide and ammonium fluoride yttrium double salt.

[0130] Manufacturing of film-forming materials

[0131] The yttrium fluoride particles and composite particles manufactured by the above method were mixed in a mass ratio of yttrium fluoride particles:composite particles = 40:60 to obtain a film-forming material.

[0132] [Evaluation of the physical properties of materials used for film formation]

[0133] For the obtained film-forming material, X-ray diffraction (XRD) using CuKα rays as the characteristic X-rays was employed. The crystal phase was identified by diffraction peaks detected within the diffraction angle range of 2θ = 10–70°. The crystal composition was analyzed, the maximum peak of each crystal phase was determined, and the integrated intensity values ​​I(RNF) of the maximum peak attributable to rare earth element ammonium fluoride complex salts, I(RF) of the maximum peak attributable to rare earth element fluorides, and I(RO) of the maximum peak attributable to rare earth element oxides were calculated. Furthermore, based on these results, the following calculations were performed:

[0134] X F0 =I(RNF) / (I(RF)+I(RO)),

[0135] X F =I(RNF) / I(RF), and

[0136] The value of X0 = I(RNF) / I(RO).

[0137] X-ray diffraction was performed using an X'Pert PRO / MPD X-ray diffractometer (Malvern Panalytical). HighScore Plus software (Malvern Panalytical) was used to identify the crystal phase and calculate the integrated intensity. The measurement conditions were set as follows: characteristic X-ray: CuKα (tube voltage: 45 kV, tube current: 40 mA), scanning range: 2θ = 5–70°, step size: 0.0167113°, step time: 13.970 s, scanning speed: 0.151921° / s.

[0138] The loss on heat under atmospheric conditions at 500°C for 2 hours was measured for the obtained film-forming material. The oxygen content was also measured. Furthermore, 0.1 g of the obtained film-forming material was mixed into 30 mL of pure water in a glass beaker with a maximum graduated volume of 30 mL, and ultrasonically dispersed at 40 W for 1 minute. The average particle size D50 (S1) in the volumetric particle size distribution was measured. Additionally, 0.1 g of the obtained film-forming material was mixed into 30 mL of pure water in a glass beaker with a maximum graduated volume of 30 mL, and ultrasonically dispersed at 40 W for 3 minutes. The average particle size D50 (S3) in the volumetric particle size distribution was measured. From these results, the ratio P between the two was calculated. SA =D50(S1) / D50(S3). The results are shown in Table 2. Additionally, scanning electron microscope images of the film-forming material obtained in Example 1 are shown in... Figure 1 The X-ray diffraction distribution is shown in Figure 2 Furthermore, the details of each measurement and analysis will be described later.

[0139] [Preparation of film-forming slurry]

[0140] The film-forming material manufactured by the above method was mixed with a dispersion medium and dispersed to obtain a film-forming slurry. The slurry concentration and the dispersion medium used are shown in Table 2.

[0141] [Evaluation of physical properties of film-forming slurries]

[0142] The viscosity and pH of the resulting slurry were measured. The results are shown in Table 3. Further details regarding the viscosity determination will be described later.

[0143] [Example 2]

[0144] [Manufacturing of Yttrium Fluoride Particles]

[0145] Except for calcining the obtained yttrium ammonium fluoride double salt at 800°C for 2 hours, yttrium fluoride particles were obtained in the same manner as in Example 1.

[0146] [Physical Property Evaluation of Yttrium Fluoride Particles]

[0147] The procedure was carried out in the same manner as in Example 1. The results are shown in Table 1.

[0148] [Manufacturing of Composite Particles]

[0149] In addition to using yttrium oxide particles with a cumulative 50% diameter (median diameter) of 1 μm in the volume-based particle size distribution as yttrium oxide particles, composite particles were obtained in the same manner as in Example 1.

[0150] Manufacturing of film-forming materials

[0151] The yttrium fluoride particles and composite particles manufactured by the above method were mixed in a mass ratio of yttrium fluoride particles: composite particles = 45:55 to obtain a film-forming material.

[0152] [Evaluation of the physical properties of materials used for film formation]

[0153] The procedure was performed in the same manner as in Example 1. The results are shown in Table 2.

[0154] [Preparation of film-forming slurry]

[0155] Implemented in the same manner as in Example 1.

[0156] [Evaluation of physical properties of film-forming slurries]

[0157] The procedure was performed in the same manner as in Example 1. The results are shown in Table 3.

[0158] [Example 3]

[0159] [Manufacturing of Yttrium Fluoride Particles]

[0160] Except for calcining the obtained yttrium ammonium fluoride double salt at 440°C for 2 hours and crushing it using a hammer mill, yttrium fluoride particles were obtained in the same manner as in Example 1.

[0161] [Physical Property Evaluation of Yttrium Fluoride Particles]

[0162] The procedure was carried out in the same manner as in Example 1. The results are shown in Table 1.

[0163] [Manufacturing of Composite Particles]

[0164] The composite particles were obtained in the same manner as in Example 1, except that the amount of acidic ammonium fluoride was 7 moles.

[0165] Manufacturing of film-forming materials

[0166] The yttrium fluoride particles and composite particles manufactured by the above method are dispersed in water in a mass ratio of yttrium fluoride particles:composite particles = 50:50, mixed, and carboxymethyl cellulose is added as a binder to make a slurry. The resulting slurry is granulated using a spray dryer to obtain a granular film-forming material.

[0167] [Evaluation of the physical properties of materials used for film formation]

[0168] The determination of average particle size D50(S1) and average particle size D50(S3) and P were replaced. SA The value of was calculated by determining the average particle size D50 (S0) in the volumetric particle size distribution without ultrasonic dispersion treatment. Otherwise, the procedure was performed in the same manner as in Example 1. The results are shown in Table 2.

[0169] [Example 4]

[0170] [Manufacturing of Yttrium Fluoride Particles]

[0171] Except for calcining the obtained yttrium ammonium fluoride double salt at 950°C for 2 hours, yttrium fluoride particles were obtained in the same manner as in Example 1.

[0172] [Physical Property Evaluation of Yttrium Fluoride Particles]

[0173] The procedure was carried out in the same manner as in Example 1. The results are shown in Table 1.

[0174] [Manufacturing of Composite Particles]

[0175] The composite particles were obtained in the same manner as in Example 1, except that the amount of acidic ammonium fluoride was 7 moles.

[0176] Manufacturing of film-forming materials

[0177] The yttrium fluoride particles and composite particles manufactured by the above method were mixed in a mass ratio of 60:40 to obtain a film-forming material.

[0178] [Evaluation of the physical properties of materials used for film formation]

[0179] The procedure was performed in the same manner as in Example 1. The results are shown in Table 2.

[0180] [Preparation of film-forming slurry]

[0181] Implemented in the same manner as in Example 1.

[0182] [Evaluation of physical properties of film-forming slurries]

[0183] The procedure was performed in the same manner as in Example 1. The results are shown in Table 3.

[0184] [Example 5]

[0185] [Manufacturing of ytterbium fluoride particles]

[0186] A 2 mol / L aqueous solution of ytterbium nitrate (equivalent to 2 moles) was heated to 50°C. A 12 mol / L aqueous solution of ammonium fluoride (equivalent to 7 moles) was then added to the heated ytterbium nitrate solution. The mixture was stirred for 1 hour while maintaining the temperature at 50°C. The resulting precipitate was filtered, washed, and dried at 70°C for 24 hours to obtain ammonium ytterbium fluoride double salt. Next, the obtained ammonium ytterbium fluoride double salt was calcined at 900°C for 2 hours in a tubular furnace under a nitrogen atmosphere, followed by pulverization using a jet mill to obtain ytterbium fluoride particles.

[0187] [Physical Property Evaluation of Ytterbium Fluoride Particles]

[0188] The property evaluation of the yttrium fluoride particles in Example 1 was performed in the same manner. The results are shown in Table 1.

[0189] [Manufacturing of Composite Particles]

[0190] Five moles of ytterbium oxide particles with a cumulative 50% diameter (median diameter) of 1 μm in the volumetric particle size distribution were added to pure water and stirred to prepare a slurry with a ytterbium oxide particle concentration of 20% by mass. Ten moles of acidic ammonium fluoride were added to the resulting slurry, and the mixture was matured at 50°C for 3 hours. The obtained particles were filtered, washed, and dried at 70°C to obtain composite particles containing ytterbium oxide and ammonium fluoride ytterbium double salt.

[0191] Manufacturing of film-forming materials

[0192] Ytterbium fluoride particles and composite particles manufactured using the above method were mixed in a mass ratio of 65:35 to obtain a film-forming material.

[0193] [Evaluation of the physical properties of materials used for film formation]

[0194] The procedure was performed in the same manner as in Example 1. The results are shown in Table 2.

[0195] [Preparation of film-forming slurry]

[0196] Implemented in the same manner as in Example 1.

[0197] [Evaluation of physical properties of film-forming slurries]

[0198] The procedure was performed in the same manner as in Example 1. The results are shown in Table 3.

[0199] [Example 6]

[0200] [Manufacturing of scandium fluoride particles]

[0201] A 2 mol / L scandium nitrate aqueous solution (equivalent to 2 moles of scandium nitrate) was heated to 50°C. A 12 mol / L ammonium fluoride aqueous solution (equivalent to 7 moles of ammonium fluoride) was then added to the heated scandium nitrate aqueous solution. The mixture was stirred for 1 hour while maintaining the temperature at 50°C. The resulting precipitate was filtered, washed, and dried at 70°C for 24 hours to obtain scandium ammonium fluoride double salt. Next, the obtained scandium ammonium fluoride double salt was calcined in a tubular furnace under a nitrogen atmosphere at 850°C for 2 hours, followed by pulverization using a jet mill to obtain scandium fluoride particles.

[0202] [Physical Property Evaluation of Scandium Fluoride Particles]

[0203] The property evaluation of the yttrium fluoride particles in Example 1 was performed in the same manner. The results are shown in Table 1.

[0204] [Manufacturing of Composite Particles]

[0205] Five moles of scandium oxide particles with a cumulative 50% diameter (median diameter) of 1 μm in the volumetric particle size distribution were added to pure water and stirred to prepare a slurry with a scandium oxide particle concentration of 20% by mass. Nine moles of acidic ammonium fluoride were added to the resulting slurry, and the mixture was matured at 50°C for 3 hours. The obtained particles were filtered, washed, and dried at 70°C to obtain composite particles containing scandium oxide and ammonium fluoride scandium double salt.

[0206] Manufacturing of film-forming materials

[0207] Scandium fluoride particles and composite particles manufactured using the above method were mixed in a mass ratio of 40:60 (scandium fluoride particles: composite particles) to obtain a film-forming material.

[0208] [Evaluation of the physical properties of materials used for film formation]

[0209] The procedure was performed in the same manner as in Example 1. The results are shown in Table 2.

[0210] [Preparation of film-forming slurry]

[0211] Implemented in the same manner as in Example 1.

[0212] [Evaluation of physical properties of film-forming slurries]

[0213] The procedure was performed in the same manner as in Example 1. The results are shown in Table 3.

[0214] [Example 7]

[0215] [Manufacturing of Erbium Fluoride Particles]

[0216] A 2 mol / L erbium nitrate aqueous solution (equivalent to 2 moles of erbium nitrate) was heated to 50°C. A 12 mol / L ammonium fluoride aqueous solution (equivalent to 7 moles of ammonium fluoride) was then added to the heated erbium nitrate aqueous solution. The mixture was stirred for 1 hour while maintaining the temperature at 50°C. The resulting precipitate was filtered, washed, and dried at 70°C for 24 hours to obtain erbium ammonium fluoride double salt. Next, the obtained erbium ammonium fluoride double salt was calcined at 900°C for 3 hours in a tubular furnace under a nitrogen atmosphere, followed by pulverization using a jet mill to obtain erbium fluoride particles.

[0217] [Physical Property Evaluation of Erbium Fluoride Particles]

[0218] The property evaluation of the yttrium fluoride particles in Example 1 was performed in the same manner. The results are shown in Table 1.

[0219] [Manufacturing of Composite Particles]

[0220] Five moles of erbium oxide particles with a cumulative 50% diameter (median diameter) of 2 μm in the volumetric particle size distribution were added to pure water and stirred to prepare a slurry with an erbium oxide particle concentration of 20% by mass. Ten moles of acidic ammonium fluoride were added to the resulting slurry, and the mixture was matured at 50°C for 3 hours. The obtained particles were filtered, washed, and dried at 70°C to obtain composite particles containing erbium oxide and ammonium fluoride erbium double salt.

[0221] Manufacturing of film-forming materials

[0222] Erbium fluoride particles and composite particles manufactured using the above method were mixed in a mass ratio of 55:45 (erbium fluoride particles: composite particles) to obtain a film-forming material.

[0223] [Evaluation of the physical properties of materials used for film formation]

[0224] The procedure was performed in the same manner as in Example 1. The results are shown in Table 2.

[0225] [Preparation of film-forming slurry]

[0226] Implemented in the same manner as in Example 1.

[0227] [Evaluation of physical properties of film-forming slurries]

[0228] The procedure was performed in the same manner as in Example 1. The results are shown in Table 3.

[0229] [Comparative Example 1]

[0230] [Manufacturing of composite particles and film-forming materials]

[0231] Composite particles were obtained using the same method as in Example 2 and used as a film-forming material.

[0232] [Evaluation of the physical properties of materials used for film formation]

[0233] The procedure was performed in the same manner as in Example 1. The results are shown in Table 2.

[0234] [Preparation of film-forming slurry]

[0235] Implemented in the same manner as in Example 1.

[0236] [Evaluation of physical properties of film-forming slurries]

[0237] The procedure was performed in the same manner as in Example 1. The results are shown in Table 3.

[0238] [Comparative Example 2]

[0239] [Manufacturing of composite particles and film-forming materials]

[0240] Composite particles were obtained using the same method as in Example 1. The obtained composite particles were calcined in an atmospheric furnace at 900°C for 5 hours, and then pulverized using a jet mill to obtain particles containing yttrium oxyfluoride crystalline phase and yttrium fluoride crystalline phase, which were used as film-forming materials.

[0241] [Evaluation of the physical properties of materials used for film formation]

[0242] The procedure was performed in the same manner as in Example 1. The results are shown in Table 2.

[0243] [Preparation of film-forming slurry]

[0244] Implemented in the same manner as in Example 1.

[0245] [Evaluation of physical properties of film-forming slurries]

[0246] The procedure was performed in the same manner as in Example 1. The results are shown in Table 3.

[0247] [Comparative Example 3]

[0248] [Manufacturing of Yttrium Fluoride Particles]

[0249] A 2 mol / L yttrium nitrate aqueous solution (equivalent to 2 moles of yttrium nitrate) was heated to 50°C. A 12 mol / L ammonium fluoride aqueous solution (equivalent to 7 moles of ammonium fluoride) was then added to the heated yttrium nitrate aqueous solution. The mixture was stirred for 1 hour while maintaining the temperature at 50°C. The resulting precipitate was filtered, washed, and dried at 70°C for 24 hours to obtain yttrium ammonium fluoride double salt. Next, the obtained yttrium ammonium fluoride double salt was calcined at 650°C for 2 hours in a tubular furnace under a nitrogen atmosphere, followed by pulverization using a jet mill to obtain yttrium fluoride particles.

[0250] [Physical Property Evaluation of Yttrium Fluoride Particles]

[0251] The procedure was carried out in the same manner as in Example 1. The results are shown in Table 1.

[0252] Manufacturing of film-forming materials

[0253] Yttrium fluoride particles manufactured using the above method and yttrium oxide particles with a cumulative diameter (median diameter) of 2 μm in the volume-based particle size distribution were mixed in a mass ratio of yttrium fluoride particles: yttrium oxide particles = 75:25 to obtain a film-forming material.

[0254] [Evaluation of the physical properties of materials used for film formation]

[0255] The procedure was performed in the same manner as in Example 1. The results are shown in Table 2.

[0256] [Preparation of film-forming slurry]

[0257] Implemented in the same manner as in Example 1.

[0258] [Evaluation of physical properties of film-forming slurries]

[0259] The procedure was performed in the same manner as in Example 1. The results are shown in Table 3.

[0260] [Table 1]

[0261]

[0262] [Table 2]

[0263]

[0264] [Table 3]

[0265]

[0266] [Example 8]

[0267] The surface of a 100mm × 100mm × 5mm A5052 aluminum alloy substrate was degreased with acetone. For one side of the substrate, sandblasting with a corundum abrasive of grit #150 was performed to roughen the surface. Using the film-forming slurry obtained in Example 1, atmospheric suspension plasma spraying (SPS) was employed to directly form a sprayed film on the substrate, resulting in a sprayed component. Atmospheric suspension plasma spraying was performed using a plasma spraying machine 100HE (manufactured by Progressive Surface) and a spray material supply device LiquidfeederHE (manufactured by Progressive Surface), under the spraying conditions shown in Table 4, in an atmospheric atmosphere at normal pressure (the same applies to atmospheric suspension plasma spraying below).

[0268] The obtained sprayed film was identified by X-ray diffraction (XRD) using the same method as in Example 1. The crystal structure was analyzed, the maximum peak of each crystal phase was determined, and the rare earth element oxyfluorides (ROF(R1O1F1), R4O3F6, R5O4F7, R6O5F8, R7O6F9, R...) were calculated. 17 O 14 F 23 The integral intensity values ​​I(ROF) of the maximum peak of diffraction peaks of rare earth elements (such as Sc and Y), I(RF) of the maximum peak of diffraction peaks attributable to rare earth element fluorides, and I(RO) of the maximum peak of diffraction peaks attributable to rare earth element oxides were calculated. Furthermore, from these results, the integral intensity values ​​I(ROF) of the maximum peak of diffraction peaks attributable to rare earth element fluorides were calculated.

[0269] X ROF =I(ROF) / (I(RF)+I(RO))

[0270] The values ​​were also determined. Additionally, oxygen content, film thickness, surface roughness (Ra), and R particle quantity were measured. Further details of each measurement, analysis, and evaluation will be described later.

[0271] [Example 9]

[0272] Except for using the film-forming slurry obtained in Example 2, a spray coating was formed on the substrate in the same manner as in Example 8, resulting in a sprayed component. The obtained spray coating was subjected to the same measurements, analyses, and evaluations as in Example 8. The results are shown in Table 5.

[0273] [Example 10]

[0274] The surface of a 100mm × 100mm × 5mm A5052 aluminum alloy substrate was degreased with acetone. For the substrate's surface, it was roughened by sandblasting with a corundum abrasive of grit size #150. Using the granular film-forming material obtained in Example 3, atmospheric plasma spraying (APS) was employed to directly form a sprayed film on the substrate, resulting in a sprayed component. For atmospheric plasma spraying, an F4 plasma spraying machine (manufactured by Ericometco Corporation) and a TWIN-10 spraying material supply device (Ericometco Corporation) were used, and the process was carried out under the spraying conditions shown in Table 4, in an atmospheric atmosphere, and at normal pressure. The resulting sprayed film underwent the same measurements, analyses, and evaluations as in Example 8. The results are shown in Table 5.

[0275] [Example 11]

[0276] Except for using the film-forming slurry obtained in Example 4, a spray coating was formed on the substrate in the same manner as in Example 8, resulting in a sprayed component. The obtained spray coating was subjected to the same measurements, analyses, and evaluations as in Example 8. The results are shown in Table 5.

[0277] [Example 12]

[0278] Except for using the film-forming slurry obtained in Example 5, a spray coating was formed on the substrate in the same manner as in Example 8, resulting in a sprayed component. The obtained spray coating was subjected to the same measurements, analyses, and evaluations as in Example 8. The results are shown in Table 5.

[0279] [Example 13]

[0280] Except for using the film-forming slurry obtained in Example 6, a spray coating was formed on the substrate in the same manner as in Example 8, resulting in a sprayed component. The obtained spray coating was subjected to the same measurements, analyses, and evaluations as in Example 8. The results are shown in Table 5.

[0281] [Example 14]

[0282] Except for using the film-forming slurry obtained in Example 7, a spray coating was formed on the substrate in the same manner as in Example 8, resulting in a sprayed component. The obtained spray coating was subjected to the same measurements, analyses, and evaluations as in Example 8. The results are shown in Table 5.

[0283] [Comparative Example 4]

[0284] Except for using the film-forming slurry obtained in Comparative Example 1, a spray coating was formed on a substrate in the same manner as in Example 8, resulting in a sprayed component. The obtained spray coating was subjected to the same measurements, analyses, and evaluations as in Example 8. The results are shown in Table 5.

[0285] [Comparative Example 5]

[0286] Except for using the film-forming slurry obtained in Comparative Example 2, a spray coating was formed on a substrate in the same manner as in Example 8, resulting in a sprayed component. The obtained spray coating was subjected to the same measurements, analyses, and evaluations as in Example 8. The results are shown in Table 5.

[0287] [Comparative Example 6]

[0288] Except for using the film-forming slurry obtained in Comparative Example 3, a spray coating was formed on a substrate in the same manner as in Example 8, resulting in a sprayed component. The obtained spray coating was subjected to the same measurements, analyses, and evaluations as in Example 8. The results are shown in Table 5.

[0289] [Table 4]

[0290]

[0291] [Table 5]

[0292]

[0293] In the sprayed coatings obtained in Examples 8-14, the X-ray diffraction (XRD) is calculated from the integrated intensity value of the largest peak of the diffraction peaks belonging to rare earth element oxyfluorides (in cases where there are two or more compounds, it is the sum of the integrated intensity values ​​of the largest peaks of each diffraction peak of the two or more compounds) I(ROF), the integrated intensity value of the largest peak of the diffraction peaks belonging to rare earth element fluorides I(RF), and the integrated intensity value of the largest peak of the diffraction peaks belonging to rare earth element oxides I(RO). ROF The values ​​are all above 1.2. It can be seen that under these conditions, a spray coating film with rare earth element fluorides as the main crystalline phase and a low ratio of rare earth element fluorides to rare earth element oxides was obtained.

[0294] Furthermore, the film-forming materials obtained in Examples 1-7 are composed of particles containing crystalline phases of rare earth element fluorides and composite particles (particles containing crystalline phases of rare earth element oxides and particles containing crystalline phases of rare earth element ammonium fluoride complex salts, or particles containing crystalline phases of rare earth element oxides and crystalline phases of rare earth element ammonium fluoride complex salts). The X-ray diffraction (XRD) is calculated from the integrated intensity value I(RNF) of the largest peak of the diffraction peak belonging to the rare earth element ammonium fluoride complex salt, the integrated intensity value I(RF) of the largest peak of the diffraction peak belonging to the rare earth element fluoride, and the integrated intensity value I(RO) of the largest peak of the diffraction peak belonging to the rare earth element oxide. F0 X FBoth X and X0 values ​​are above 0.01. It can be seen that by including composite particles in the film-forming material, the reactivity in the spraying process is improved, and excessive spraying heat is not required. This allows for the production of sprayed films with a high proportion of rare earth element oxyfluorides and a low proportion of rare earth element fluorides and rare earth element oxides.

[0295] On the other hand, regarding the sprayed film obtained in Comparative Example 4, since the film-forming material of Comparative Example 1 does not contain particles of a crystalline phase containing rare earth element fluorides, the main phase of the sprayed film is rare earth element oxides. Furthermore, regarding the sprayed film obtained in Comparative Example 5, since the film-forming material of Comparative Example 2 does not contain particles of a crystalline phase containing rare earth element oxides, in the reaction between rare earth element fluorides and rare earth element oxyfluorides, the rare earth element fluorides were not completely consumed, and the formation of rare earth oxides was not suppressed. Therefore, as the crystalline phase of the sprayed film, a large amount of unreacted rare earth element fluorides remained, and rare earth element oxides were produced as byproducts. In particular, in the film-forming material of Comparative Example 2 used in Comparative Example 5, in order to make the main phase of the sprayed film a rare earth element oxyfluoride, it is necessary to increase the power of the spraying conditions. Furthermore, regarding the spray coating obtained in Comparative Example 6, since the film-forming material in Comparative Example 3 does not contain particles containing the crystalline phase of rare earth element ammonium fluoride double salt, the reaction between rare earth element fluoride and rare earth element oxide is not fully carried out during the short time of the spraying process. As the crystalline phase of the spray coating, a large amount of unreacted rare earth element fluoride and rare earth element oxide remain.

[0296] [Determination of Particle Size Distribution]

[0297] Particle size distribution was determined using laser diffraction. A Microtrac MT3300EX II laser diffraction-scattering particle size distribution measuring device (manufactured by MicrotracBELL Co., Ltd.) was used in the determination. The sample was added or dripped into the circulation system of the measuring device to achieve a concentration index (DV) suitable for use with the device, ranging from 0.01 to 0.09, before measurement.

[0298] [Determination of BET specific surface area]

[0299] The surface area was measured using a fully automated Macsorb HM model-1208 (manufactured by Macsorb Corporation).

[0300] [Determination of loose bulk density]

[0301] The powder was tested using a PT-X powder tester (manufactured by Hosokawa Micron Co., Ltd.).

[0302] [Determination of Loss of Heat Due to Intense Heat]

[0303] The sample of the film-forming material was placed in a platinum crucible and heated in an electric furnace at 500°C for 2 hours in the atmosphere. The thermal loss was calculated from the mass of the sample before and after heating.

[0304] [Determination of Oxygen Content]

[0305] The determination was performed using the inert gas melting infrared absorption method.

[0306] [Determination of slurry viscosity]

[0307] The measurement was performed using a TVB-10 viscometer (manufactured by Toki Sangyo Co., Ltd.), with the rotation speed set to 60 rpm and the rotation time set to 1 minute.

[0308] [Film thickness measurement]

[0309] The measurements were performed using an eddy current film thickness gauge LH-300J (manufactured by Ketsuto Scientific Research Institute Co., Ltd.).

[0310] [Determination of surface roughness (Ra)]

[0311] The surface roughness was measured using a HANDYSURF E-35A surface roughness measuring instrument (Tokyo Precision Co., Ltd.).

[0312] [Particle Evaluation Experiment (R Particle Quantity)]

[0313] For a 20mm×20mm (4cm) 2 Test pieces of sprayed components with a sprayed coating were subjected to ultrasonic cleaning (output power: 200W, irradiation time: 30 minutes) in ultrapure water with the sprayed coating side facing the water surface to remove contaminants after spraying. Next, after drying, the test pieces were immersed in 20ml of ultrapure water in a 100ml polyethylene bottle with the sprayed coating side facing the bottom of the bottle, and then subjected to ultrasonic treatment (output power: 200W, irradiation time: 15 minutes). After ultrasonic treatment, the test pieces were removed, and 2ml of 5.3N nitric acid aqueous solution was added to the treatment solution to dissolve the R particles (rare earth element compound particles) contained in the treatment solution. The amount of rare earth elements (R amount) contained in the treatment solution was determined by ICP-N (inductively coupled plasma) spectroscopy, and this amount was used as the unit surface area (per 4cm²) of the sprayed coating on the test piece. 2 The quality of the coating is evaluated by its R-value. The smaller the value, the fewer R-particles are on the surface of the coating.

Claims

1. A film-forming material, characterized in that, contain: Particles containing rare earth element fluorides in crystalline phases, Particles containing rare earth element oxides in crystalline phases, and Particles containing the crystalline phase of rare earth element ammonium fluoride double salt. The rare earth element is selected from one or more of yttrium, scandium, erbium, and ytterbium.

2. The film-forming material according to claim 1, characterized in that, The particles of the crystal phase containing rare earth element oxides and the particles of the crystal phase containing rare earth element ammonium fluoride double salts form mutually dispersed composite particles.

3. The film-forming material according to claim 1, characterized in that, The particles of the crystal phase containing rare earth element oxides are rare earth element oxide particles, and the particles of the crystal phase containing rare earth element ammonium fluoride double salts are rare earth element ammonium fluoride double salt particles.

4. A film-forming material, characterized in that, contain: Particles containing crystalline phases of rare earth element fluorides, and Particles containing crystalline phases of rare earth element oxides and crystalline phases of rare earth element ammonium fluoride double salts. The rare earth element is selected from one or more of yttrium, scandium, erbium, and ytterbium.

5. The film-forming material according to claim 4, characterized in that, The particles containing rare earth element oxides and rare earth element ammonium fluoride double salt crystal phases are formed by using the particles containing rare earth element oxides as a matrix, forming particles containing rare earth element ammonium fluoride double salt crystal phases or composite particles dispersed on the surface and / or inside the particles containing rare earth element oxides crystal phases.

6. The film-forming material according to claim 4, characterized in that, The particles of the crystal phase containing rare earth element oxides are rare earth element oxide particles, and the particles or layers of the crystal phase containing rare earth element ammonium fluoride double salts are rare earth element ammonium fluoride double salt particles or layers.

7. The film-forming material according to claim 1 or 4, characterized in that, The particles of the crystal phase containing rare earth element fluorides are rare earth element fluoride particles.

8. The film-forming material according to claim 1 or 4, characterized in that, The film-forming material does not contain rare earth element oxyfluoride crystal phases.

9. The film-forming material according to claim 1 or 4, characterized in that, The rare earth element ammonium fluoride complex salt contains elements selected from (NH4)3R. 3 F6, NH4R 3 F4, NH4R 3 2F7 and (NH4)3R 3 One or more of 2F9, where R 3 Each element is selected from one or more rare earth elements containing Sc and Y.

10. The film-forming material according to claim 1 or 4, characterized in that, The oxygen content is 0.3–10% by mass.

11. The film-forming material according to claim 1 or 4, characterized in that, In X-ray diffraction using CuKα rays as characteristic X-rays, among the diffraction peaks of the crystalline phase detected in the diffraction angle range of 2θ = 10–70°, the X-rays can be calculated according to the following formula. F0 The value is above 0.

01. X F0 =I(RNF) / (I(RF)+I(RO)) In the formula, I(RNF) is the integrated intensity value of the largest peak of the diffraction peak belonging to the rare earth element ammonium fluoride double salt, I(RF) is the integrated intensity value of the largest peak of the diffraction peak belonging to the rare earth element fluoride, and I(RO) is the integrated intensity value of the largest peak of the diffraction peak belonging to the rare earth element oxide.

12. The film-forming material according to claim 1 or 4, characterized in that, The average particle size D50 (F1) of the crystalline phase containing rare earth element fluorides is 0.5 to 10 μm. The average particle size D50 (F1) is the cumulative 50% diameter (median diameter) of the volume-based particle size distribution, which is determined by ultrasonic dispersion treatment at 40 W for 1 minute after mixing in 30 mL of pure water.

13. The film-forming material according to claim 1 or 4, characterized in that, In the particle size distribution of the crystalline phase containing rare earth element fluorides, P is calculated according to the following formula. D The value is below 4. P D =((D90(F1)-D10(F1)) / D50(F1) In the formula, D90(F1) is the cumulative 90% diameter of the particle size distribution of the volume reference, which is determined by ultrasonic dispersion treatment under conditions of 40W and 1 minute after mixing in 30mL of pure water; D10(F1) is the cumulative 10% diameter of the particle size distribution of the volume reference, which is determined by ultrasonic dispersion treatment under conditions of 40W and 1 minute after mixing in 30mL of pure water; and D50(F1) is the cumulative 50% diameter (median diameter) of the particle size distribution of the volume reference, which is determined by ultrasonic dispersion treatment under conditions of 40W and 1 minute after mixing in 30mL of pure water.

14. The film-forming material according to claim 1 or 4, characterized in that, The BET specific surface area of ​​the particles containing rare earth element fluorides is 10 m². 2 / g or less.

15. The film-forming material according to claim 1 or 4, characterized in that, The loose packing density of the particles containing the rare earth element fluoride crystalline phase is 0.6 g / cm³. 3 above.

16. The film-forming material according to claim 1 or 4, characterized in that, The film-forming material is in powder or granular form.

17. The film-forming material according to claim 16, characterized in that, The cumulative 50% diameter (median diameter), i.e., the average particle size D50 (S0), in the volumetric particle size distribution is 10–100 μm.

18. A film-forming slurry, characterized in that, It includes a film-forming material and a dispersion medium according to any one of claims 1 to 15.

19. The film-forming slurry according to claim 18, characterized in that, The slurry concentration is 10-70% by mass.

20. The film-forming slurry according to claim 18, characterized in that, The dispersion medium contains a non-aqueous solvent.

21. The film-forming slurry according to claim 18, characterized in that, The average particle size D50 (S1) of the volumetric standard particle size distribution, which is determined by ultrasonic dispersion treatment at 40W for 1 minute after mixing in 30 mL of pure water, is 1–10 μm.

22. The film-forming slurry according to claim 18, characterized in that, Based on the average particle size D50(S1) and average particle size D50(S3), P is calculated using the following formula. SA The value is above 1.

04. P SA =D50(S1) / D50(S3) Wherein, D50(S1) is the cumulative 50% diameter (median diameter) of the particle size distribution of the volume reference, which is determined by ultrasonic dispersion treatment at 40W for 1 minute after mixing in 30 mL of pure water, and D50(S3) is the cumulative 50% diameter (median diameter) of the particle size distribution of the volume reference, which is determined by ultrasonic dispersion treatment at 40W for 3 minutes after mixing in 30 mL of pure water.

23. The film-forming slurry according to claim 18, characterized in that, The film-forming material exhibits a thermal loss of more than 0.5% by mass under atmospheric conditions at 500°C for 2 hours.

24. The film-forming material according to claim 1 or 4, characterized in that, The film-forming material is a spraying material.

25. The film-forming slurry according to claim 18, characterized in that, The film-forming slurry is a spray coating slurry.

26. A spray-coated film, characterized in that, It is obtained by spraying the film-forming material according to claim 24 or the film-forming slurry according to claim 25.

27. A spray-painted component, characterized in that, The sprayed component has a sprayed coating as described in claim 26 on a substrate.

28. The spray-painted component according to claim 27, characterized in that, The sprayed component is a component used in semiconductor manufacturing equipment.

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