TWI688675B - Thermal spray material, thermal spray coating and thermal spray coated article - Google Patents

Abstract

The present invention provides a material for melt-spraying that can form a melt-spraying film having excellent characteristics such as porosity and hardness in addition to plasma corrosion resistance.

According to the technology disclosed in the present invention, a material for spraying is provided. The material for spraying contains a rare earth element oxyhalide (RE-OX) containing rare earth elements (RE), oxygen (O), and halogen elements (X) as constituent elements. And the characteristic is that the sum of the peak intensity I _B of the main peak of the rare earth element oxide in the X-ray diffraction pattern of the material for melting and the peak intensity I _C of the main peak of the rare earth element halide is relative to that of the rare earth element The peak intensity I _A of the main peak of the elemental oxygen halide has an intensity ratio [(I _B +I _C )/I _A ] of less than 0.02.

Description

Material for spraying, spray coating and member with spray coating

The present invention relates to a material for spraying, a film for spraying formed using the material for spraying, and a member with a film for spraying.

This application claims priority based on Japanese Patent Application No. 2015-095516 filed on May 8, 2015 and Japanese Patent No. 2016-043940 filed on March 7, 2016, the contents of which are incorporated by reference In this manual.

The technology that the surface of the substrate is coated with various materials to impart new functionality has been used in various fields since the past. As one of the surface coating technologies, for example, it is known to melt-spray particles made of materials such as ceramics on the surface of a substrate by blowing or blowing them into a softened or molten state by burning or electrical energy to form a melt made of the materials. Shot blasting method of film.

In the manufacturing field of semiconductor devices and the like, plasmas of halogen-based gases such as fluorine, chlorine, and bromine are generally used to perform fine processing on the surface of a semiconductor substrate by dry etching. Also, after dry etching, take The semiconductor substrate is patterned using oxygen plasma inside the chamber (vacuum container). At this time, components exposed to highly reactive oxygen plasma or halogen gas plasma in the chamber may be corroded. Therefore, when the erosion portion is detached from the member in the form of particles, the particles will adhere to the semiconductor substrate and may become foreign substances that may cause circuit defects (hereinafter referred to as foreign particles).

Therefore, in the past, in the semiconductor device manufacturing apparatus, for the purpose of reducing the generation of particles, a spray coating of a ceramic having a plasma corrosion resistance was provided on a member exposed to plasma of oxygen or halogen gas. For example, Patent Document 1 discloses that by using at least a part of particles containing yttrium oxyfluoride as a material for spraying, a spraying film with high corrosion resistance to plasma can be formed.

[Prior Technical Literature]

[Patent Literature]

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

However, with the increase in the integration of semiconductor devices, more precise management is required for the pollution caused by particles. Furthermore, regarding the ceramic spray coating provided in the semiconductor device manufacturing apparatus, further improvement in plasma corrosion resistance is required. In addition, when the characteristics of porosity and hardness of the spray coating are good, it is better to obtain a spray coating excellent in durability, etc. good.

In view of these circumstances, an object of the present invention is to provide a material for spraying that can form a spray coating that further improves plasma corrosion resistance, has a low porosity, and has excellent characteristics such as hardness. And another object is to provide a spray coating formed by using the material for spray coating and a member with a spray coating.

In the present invention, as a solution to the above-mentioned problems, a material for spraying having the following characteristics is provided. That is, the material for spraying disclosed herein is a material for spraying containing a rare earth element oxyhalide (RE-OX) containing rare earth elements (RE), oxygen (O) and halogen elements (X) as constituent elements , And is characterized by the sum of the peak intensity I _B of the main peak of the rare earth element oxide and the peak intensity I _C of the main peak of the rare earth element halide in the X-ray diffraction pattern of the material for spraying The intensity ratio of the peak intensity I _A of the main peak of the rare earth element oxyhalide [(I _B +I _C )/I _A ] is less than 0.02.

Based on the review by the inventors, the materials for spraying containing rare earth oxyhalides can be formed into halogen plasmas as compared with the materials for spraying containing rare earth element oxides or rare earth element halides. A spray coating that is more resistant to plasma corrosion. Rare earth element oxides and rare earth element halides are materials that are generally used to make the raw material of the rare earth element oxyhalides, and may remain as unreacted materials in the material for spraying, for example. For example, when the material for molten spray contains rare-earth element oxides and rare-earth element halides, by suppressing its total amount to satisfy the condition of the above strength ratio, it is possible to form a plasma spray coating having excellent plasma corrosion resistance A spray coating with excellent characteristics such as porosity and hardness.

The "main peak" here means a peak with the highest peak height (that is, the highest diffraction intensity) in the diffraction peak group derived from any compound detected in the X-ray diffraction pattern.

In addition, Patent Document 1 discloses a material for spraying that contains yttrium oxyfluoride (YOF) at a relatively high ratio (refer to Examples 9 to 11). However, regarding the results of X-ray diffraction analysis of these molten materials, the content of YOF calculated from the oxygen content is 77% by mass or more, and the material that does not contain yttrium oxide (Y ₂ O ₃ ) is not disclosed. That is, the material for spraying disclosed herein can be said to be a novel material for spraying that can form a spray coating that is excellent in plasma corrosion resistance and that has excellent characteristics such as porosity and hardness of the spray coating.

The preferred state of the material for spraying disclosed herein may be a form substantially free of the above-mentioned rare earth element halide. Furthermore, it may be in a form that does not substantially contain the aforementioned rare earth element oxide.

According to this configuration, as described above, the plasma corrosion resistance of the formed spray coating can be more reliably improved, the porosity of the spray coating can be reduced, and the hardness can be increased higher.

The preferred homomorphism of the material for spraying disclosed here is characterized in that the rare earth element oxyhalide has a molar ratio (X/RE) of the halogen element to the rare earth element of 1.1 or more. The molar ratio (X/RE) is preferably 1.3 or more and 1.38 or less. It is also preferable that the molar ratio (O/RE) of the oxygen to the rare earth element is 0.9 or less.

It is preferable to increase the ratio of the halogen element of the rare earth element oxyhalide in the material for spraying, because the resistance to halogen-based plasma can be further improved. In addition, by reducing the oxygen ratio of the rare earth element oxyhalide in the material for spraying, it is preferable because it is difficult to form a rare earth element oxide in the spray coating. Moreover, by adjusting these in a well-balanced manner, a spray coating with a low porosity and a high Vickers hardness can be obtained, which is preferable.

The preferred homomorphism of the material for spraying disclosed herein is characterized in that the rare earth element is yttrium, the halogen element is fluorine, and the rare earth element oxyhalide is yttrium oxyfluoride. With this configuration, it is possible to provide a material for melt-spraying that can form a melt-spraying film excellent in corrosion resistance to, for example, fluorine plasma.

In other aspects, the present invention provides a spray coating of a spray of the material for spraying described in any of the above. The oxide component of the rare earth element in the spray coating will embrittle the spray coating and degrade the plasma resistance. The spray coating disclosed here is formed by spraying the material for spraying described in any one of the above, and the oxide content of the rare earth element is reduced, so it can be provided as a sure improvement of plasma etching resistance .

The feature of the spray coating provided by the present invention is that the rare earth element oxyhalide (RE-OX) containing rare earth elements (RE), oxygen (O) and halogen elements (X) as constituent elements is the main component, The peak intensity of the main peak of the rare earth element oxide I _CB and the peak intensity of the main peak of the rare earth element halide I _CC are relative to the peak intensity of the main peak of the rare earth element oxyhalide I _CA [(I _CB +I _CC )/I _CA ] is 0.45 or less.

With this configuration, since the content ratio of the rare earth element oxide and the rare earth element halide in the spray coating is reduced, it is possible to provide a reliable increase Those who are resistant to plasma corrosion, reduce the porosity of the spray coating, and increase the hardness higher.

The feature of the preferred homomorphism of the spray coating disclosed herein is that it does not substantially contain the oxides of the above rare earth elements. When the spray coating does not substantially contain oxides of rare earth elements, it is more preferable to improve plasma corrosion resistance.

The preferred homomorphism of the material for spraying disclosed herein is characterized in that the rare earth element is yttrium, the halogen element is fluorine, and the rare earth oxyhalide is yttrium oxyfluoride. With this configuration, it is possible to surely constitute a spray coating film having excellent corrosion resistance to fluorine plasma and improved porosity and hardness of the spray coating film.

In addition, the feature of the member with a spray coating provided by the technology disclosed herein is that the surface of the base material has the spray coating described in any of the above. With this configuration, a member with a spray coating excellent in plasma corrosion resistance is provided.

FIG. 1 is a diagram showing X-ray diffraction patterns obtained by the materials for spraying of (a) No. 5 and (b) No. 8 of Embodiment 2. FIG.

Hereinafter, preferred embodiments of the present invention will be described. In addition, circumstances other than those specifically mentioned in this specification and necessary for the implementation of the present invention can be grasped as design matters of those skilled in the art based on prior art in the field. The present invention can be based on the content disclosed in the present invention book and the Implemented in the field of technical common sense.

[Materials for spraying]

The material for spraying disclosed herein is a rare earth element oxyhalide (RE-OX) containing rare earth elements (RE), oxygen (O), and halogen elements (X) as constituent elements. Furthermore, in the X-ray diffraction pattern of the material for spraying, the sum of the peak intensity I _B of the main peak of the rare earth element oxide and the peak intensity I _C of the main peak of the rare earth element halide is relative to the aforementioned rare earth The intensity ratio of the peak intensity I _A of the main peak of the element-like oxyhalide [(I _B +I _C )/I _A ] is less than 0.02.

In the technique disclosed here, the rare earth element (RE) is not particularly limited, and can be appropriately selected from scandium, yttrium, and lanthanide elements. Specifically, scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), palladium (Pr), rubidium (Nd), yttrium (Pm), samarium (Sm), europium (Eu), gallium ( Any one or a combination of two or more of Gd), Tb (Tb), Dysprosium (Dy), Y (Ho), Er (Er), Y (Tm), Yb (Yb), and Lu (Lu). From the viewpoint of improving plasma corrosion resistance, price, etc., preferred examples are Y, La, Gd, Tb, Eu, Yb, Dy, Ce, etc. The rare earth elements may include any one of these alone or may include a combination of two or more.

In addition, the halogen element (X) is not particularly limited as long as it belongs to any element of Group 17 of the periodic table. Specifically, it may be any one of halogen elements such as fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and astatine (At) alone or may include a combination of two or more. Preferably it is F, Cl, Br. The halogen element can be used alone or any combination of the two the above. As these rare earth element oxyhalides, representative examples include oxyfluoride, oxychloride, and oxybromide of various rare earth elements.

Here, the plasma corrosion resistance of the rare earth element oxyhalide is superior to yttrium oxide (Y ₂ O ₃ ) known as a material with high plasma corrosion resistance. By containing a larger amount of such rare earth element oxyhalide, it is preferable because it can show extremely good plasma resistance.

The rare-earth element oxide contained in the material for spraying can be directly present as the rare-earth element oxide in the spray coating by spraying. For example, the yttrium oxide contained in the material for spraying can exist as yttrium oxide directly in the spraying film by spraying. The plasma resistance of the rare earth element oxide (for example, yttrium oxide) is lower than that of the rare earth element oxyhalide. Therefore, when the portion containing the rare-earth element oxide is exposed to the plasma environment, a brittle metamorphic layer is likely to occur, and the metamorphic layer easily becomes fine particles and detaches. Furthermore, the fine particles may accumulate as particles on the semiconductor substrate. Therefore, the content of rare earth element oxides, which may become a source of particles, is relatively low.

In addition, the fluoride of the rare earth element contained in the material for spraying is oxidized by spraying to form a rare earth element oxide in the spray coating. For example, yttrium fluoride contained in the material for spraying may be oxidized by spraying to form yttrium oxide in the film for spraying. Since the oxides of these rare earth elements may become a source of particles as described above, it is better to have less content.

Based on the above point of view, in the technology disclosed herein, the rare earth element oxyhalide is specified in the X-ray diffraction pattern of the material for spraying, and the above intensity ratio [(I _B +I _C )/I _A ] is not Up to 0.02. In addition, when the material for spraying contains a complex composition of rare earth element oxyhalides, the total peak intensity of the main peak of each composition can be set to I _A. In addition, when the material for spraying includes a rare-earth element oxide in a plural composition, the total peak intensity of the main peak of each composition can be set to I _B. Furthermore, when the rare-earth element halide of plural compositions is contained in the material for spraying, the total peak intensity of the main peak of each composition can be set to I _C.

The aforementioned strength ratio [(I _B +I _C )/I _A ] is preferably 0.01 or less, more preferably 0.005 or less. These structures are better realized by, for example, a form in which the material for spraying does not substantially contain a halide of rare earth elements. Alternatively, it is better realized by, for example, a form in which the material for spraying does not substantially contain oxides of rare earth elements. Furthermore, the intensity ratio [(I _B +I _C )/I _A ] is substantially 0 (zero), which is particularly preferable. In other words, it is particularly desirable for the material for spraying to consist essentially of the rare earth element oxyhalide.

In addition, X-ray diffraction analysis of rare earth element oxyhalides, rare earth element oxides, and rare earth element halides can be preferably performed based on, for example, the following conditions. That is, specifically, an X-ray diffraction analyzer (Ultima IV manufactured by RIGAKU Corporation) is used, CuKα line is used as the X-ray source (voltage 20kV, current 10mA), and the scanning range is 2θ=10°~70°, The scanning speed is 10°/min, and the sampling width is 0.01°. In addition, at this time, it is preferable to adjust the divergence slit to 1°, the divergence longitudinal limit slit to 10 mm, the scattering slit to 1/6°, the light-receiving slit to 0.15 mm, and the compensation angle to 0°. With this analysis, for example, the main peaks of the representative rare earth element oxyhalides, rare earth element oxides, and rare earth element halides are detected roughly at the positions described below. With this, the peak intensity of the main peak of each compound can be obtained more accurately.

<Composition: main wave peak detection angle (θ/2θ)>

Y ₂ O ₃ 29.157°

YF ₃ 27.881°

YOF 28.064°

Y ₅ O ₄ F ₇ 28.114°

Y ₆ O ₅ F ₈ 28.139°

Y ₇ O ₆ F ₉ 28.137°

In addition, "substantially free" in this specification means that the content ratio of this component (here, oxide of rare earth element or halide of rare earth element) is 5 mass% or less, preferably 3 mass% or less, For example, 1 mass% or less. This configuration can also be grasped, for example, when X-ray diffraction analysis is performed on the material for spraying, and the diffraction peak based on the component is not detected. In addition, in this specification, what is essentially composed only of rare earth element oxyhalides can also be detected by X-ray diffraction analysis using the material for spraying, for example. Master the diffraction peak of the compound.

In the technology disclosed here, the halogen-based plasma is typically a plasma generated by generating a gas using a plasma containing a halogen-based gas (halogen compound gas). For example, SF ₆ , CF ₄ , CHF ₃ , ClF ₃ , HF and other fluorine-based gases used in the dry etching step during the manufacture of semiconductor substrates, or chlorine-based gases such as Cl ₂ , BCl ₃ and HCl, and bromine-based HBr and other gases Plasma generated by using one kind of gas alone or a mixture of two or more kinds is exemplified as a typical one. These gases can also be used as a mixed gas with inert gas such as argon (Ar).

The ratio of rare earth elements (RE) to oxygen (O) and halogen elements (X) constituting the rare earth element oxyhalide is not particularly limited.

For example, the halogen element does not specifically limit the mole ratio (X/RE) of rare earth elements. As a preferred example, the molar ratio (X/RE) may be, for example, 1, preferably greater than 1. Specifically, it is preferably 1.1 or more, for example, 1.2 or more, and further 1.3 or more. The upper limit of the molar ratio (X/RE) is not particularly limited, and can be set to, for example, 3 or less. Among them, the molar ratio of the halogen element to the rare earth element (X/RE) is preferably 2 or less, and further preferably 1.4 or less (less than 1.4). An example of a better molar ratio (X/RE) can be exemplified as 1.3 or more and 1.39 or less (for example, 1.32 or more and 1.36 or less). In this way, by increasing the ratio of the halogen element to the rare earth element, it is possible to provide resistance to halogen-based plasma, so it is preferable.

In addition, the oxygen element is not particularly limited to the molar ratio (O/RE) of rare earth elements. As a preferred example, the molar ratio (O/RE) may be, for example, 1, preferably less than 1. Specifically, it is preferably 0.9 or less, for example, 0.88 or less, and further preferably 0.86 or less. The lower limit of the molar ratio (O/RE) is not particularly limited, and can be set to, for example, 0.1 or more. Among them, as an example of a better molar ratio of oxygen to rare earth elements (O/RE), it is preferably more than 0.8 and not more than 0.85 (preferably 0.81 or more and 0.84 or less). In this way, by reducing the ratio of the oxygen element to the rare earth element, it is possible to suppress the formation of the oxide of the rare earth element (for example, Y ₂ O ₃ ) in the spray coating due to the oxidation during the spray.

That is, the rare earth element oxyhalide is preferably a compound having an arbitrary ratio of RE to O and X expressed by the general formula RE ₁ O _m1 X _m2 (eg 0.1≦m1≦1.2, 0.1≦m2≦3). As a preferable form, the case where the rare earth element is yttrium (Y), the halogen element is fluorine (F), and the rare earth element oxyhalide is yttrium oxyfluoride (YOF) will be described. The yttrium oxyfluoride is preferably, for example, a compound represented by YOF with a chemical composition of thermodynamic stability and a chemical composition of yttrium to oxygen to halogen of 1:1:1. Moreover, it is preferable that Y ₅ O ₄ F ₇ and Y ₆ O ₅ F _{8 be} expressed by the general formula Y ₁ O _1-n F _1+2n (where n is, for example, satisfying 0.12≦n≦0.22). , Y ₇ O ₆ F ₉ , Y ₁₇ O ₁₄ F _23, etc. In particular, Y ₆ O ₅ F ₈ and Y ₁₇ O ₁₄ F _{23 with} molar ratios (O/RE) and (X/RE) in the above-mentioned better ranges can form denser and higher hardness due to excellent plasma corrosion resistance The spray coating is preferred.

In addition, in the above example of yttrium oxyfluoride, since the same or similar crystal structure can be obtained, part or all of yttrium (Y) can be replaced with any rare earth element, and part or all of fluorine (F) can be replaced with Any halogen element.

The rare earth element oxyhalide may be composed of any one of the single phases mentioned above, or may be composed of any one or a mixture of mixed phases, solid melts, and compounds formed by combining two or more phases.

In addition, when the material for spraying includes a rare-earth element oxyhalide composed of a complex number (for example, a; when set to a natural number, a≧2), the above molar ratio (X/RE) and molar ratio ( O/RE), the molar ratio (Xa/REa) and the molar ratio (Oa/REa) are calculated for each composition, and the existence ratio of the composition is multiplied by the molar ratio (Xa/REa) and The molar ratio (Oa/REa) is added together to obtain the molar ratio (X/RE) and molar ratio of the entire rare earth element oxyhalide Ear ratio (O/RE).

The molar ratio (X/RE) and molar ratio (O/RE) of the above rare earth element oxyhalide can be calculated based on the composition of the rare earth element oxyhalide identified by X-ray diffraction analysis, for example.

The content ratio of the rare earth element oxyhalide contained in the material for spraying can be specifically calculated by measuring by the following method. First, the crystal structure of the substance contained in the material for spraying is specified by X-ray diffraction analysis. At this time, the rare earth element oxyhalide system is specified to its valence (element ratio).

Therefore, for example, when a rare earth element oxyhalide exists in the material for spraying and the remainder is YF ₃ , the oxygen content of the material for spraying can be determined by, for example, oxygen. nitrogen. A hydrogen analyzer (for example, ONH836 manufactured by LECO Corporation) measures and quantifies the content of rare earth element oxyhalide from the obtained oxygen concentration.

When there are two or more rare earth element oxyhalides or a mixture of oxygen-containing compounds such as yttrium oxide, for example, the ratio of each compound can be quantified by a calibration curve method. Specifically, prepare samples of varying content ratios of several types of compounds, perform X-ray diffraction analysis on each sample, and create a calibration line showing the relationship between the main peak intensity and the content of each compound, and then use the calibration line as a reference , The quantitative content of the main peak intensity of the rare earth element oxyhalide of the XRD of the material for spraying measured.

The aforementioned materials for spraying are typically provided in powder form. The powder may be composed of granulated particles obtained by granulating finer primary particles, or may be a powder mainly composed of a collection of primary particles (including aggregated forms). From the viewpoint of spraying efficiency, for example, if the average particle size is There is no particular limitation for the thickness below about 30 μm, and the lower limit for the average particle diameter is also not particularly limited. The average particle diameter of the material for spraying can be, for example, 50 μm or less, preferably 40 μm or less, and more preferably 35 μm or less. The lower limit of the average particle diameter is also not particularly limited. When considering the fluidity of the material for spraying, it may be, for example, 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and for example, 20 μm or more.

[Melting Film]

By spraying the above materials for spraying, a spray coating can be formed. Since the spray coating is provided on the surface of the base material, it is provided as a member with a spray coating and the like. Hereinafter, the member with the spray coating and the spray coating will be described.

(Substrate)

In the member with a spray coating disclosed herein, the base material for forming the spray coating is not particularly limited. For example, if the base material is made of a material having the desired resistance to the melt-spraying material, the material, shape, etc. are not particularly limited. Examples of the material constituting the base material include, for example, metal materials containing various metals, semi-metals, and alloys thereof, and various inorganic materials. Specifically, examples of the metal material include metal materials such as aluminum, aluminum alloy, iron, iron steel, copper, copper alloy, nickel, nickel alloy, gold, silver, bismuth, manganese, zinc, and zinc alloy; silicon (Si ), group IV semiconductors such as germanium (Ge), group II-VI compound semiconductors such as zinc selenide (ZnSe), cadmium sulfide (CdS), zinc oxide (ZnO), gallium arsenic (GaAs), indium phosphide (InP) ), Group III-V compound semiconductors such as gallium nitride (GaN), Group IV compound semiconductors such as silicon carbide (SiC), silicon germanium (SiGe), copper. indium. Chalcopyrite such as selenium (CuInSe ₂ ) is a semi-metallic material such as semiconductor; etc. Examples of inorganic materials include substrate materials of calcium fluoride (CaF) and quartz (SiO ₂ ), oxide ceramics such as aluminum oxide (Al ₂ O ₃ ) and zirconia (ZrO ₂ ), and silicon nitride (Si ₃ N ₄ ), boron nitride (BN), titanium nitride (TiN) and other nitride ceramics, silicon carbide (SiC), tungsten carbide (WC) and other carbide-based ceramics. Any one of these materials may constitute a substrate, or two or more types may be combined to constitute a substrate. Among them, as a preferred example, various SUS materials (which may be so-called stainless steel) with a large thermal expansion coefficient among widely used metal materials are represented by steel, heat-resistant alloys represented by Inconel, etc., Low expansion alloys represented by invar, kovar, etc., corrosion-resistant alloys represented by Hastelloy, etc., and 1000 series to 7000 series useful as lightweight structural materials Aluminum alloy is the base material made of representative aluminum alloy. The base material may be, for example, a member constituting a semiconductor device manufacturing apparatus, and a member exposed to an oxygen plasma or halogen gas plasma with high reactivity. In addition, for example, the above-mentioned silicon carbide (SiC) and the like can also be conveniently classified into different categories such as compound semiconductors or inorganic materials, but the same materials.

(Melting film)

The spray coating disclosed herein is formed by spraying the material for spray on the surface of an arbitrary substrate, for example. Therefore, the spray coating system is constituted to contain rare earth elements (RE), oxygen (O) and halogen elements (X) as constituent elements Rare earth element oxygen halide (RE-O-X) as the main component of the coating.

Here, the "main component" means the component with the largest content among the components constituting the spray coating. Specifically, it means, for example, that the component accounts for 50% by mass or more of the entire spray coating film, preferably 75% by mass or more, for example, 80% by mass or more. Since the rare-earth element oxyhalide is the same as the above-mentioned material for spraying, detailed description is omitted.

Although the detailed mechanism is unclear, the rare earth element oxyhalide has excellent plasma corrosion resistance, especially for halogen-based plasmas. Therefore, the spray coating containing the rare earth element oxyhalide as the main component can be extremely excellent in plasma corrosion resistance.

Moreover, the spray coating is not necessarily limited to this, but it is characterized by the peak intensity of the main peak of the rare earth element oxide in the X-ray diffraction pattern I _CB and the peak of the main peak of the rare earth element halide The intensity ratio of the total intensity I _CC relative to the peak intensity I _CA of the main peak of the rare earth element oxyhalide [(I _CB +I _CC )/I _CA ] is 0.45 or less. The peak intensities I _CA , I _CB and I _CC can be considered to be the same as the peak intensities I _A , I _B and I _{C of the} material for spraying. The X-ray diffraction intensity ratio [(I _CB +I _CC )/I _CA ] of the melt-sprayed film is preferably 0.3 or less, more preferably 0.1 or less, and still more preferably 0.05 or less, for example, it is particularly desirable that it is substantially 0( zero). In other words, it is particularly desirable that the spray coating is substantially composed of rare earth element oxyhalides.

In addition, the spray coating is provided as a better aspect, and is also provided as a material that does not substantially contain the above-mentioned rare earth element oxide. The rare-earth element oxide contained in the melt-spraying film is typically considered to have the rare-earth element oxide contained in the melt-spraying material directly contained in the melt-spraying film, and the material contained in the melt-spraying material Rare earth element halides are oxidized to rare earth element oxides by spraying. Since the rare-earth element oxide is not substantially contained in the melt-sprayed film, the material for the melt-spraying material used to form the melt-sprayed film is also substantially free of rare-earth element oxide and rare-earth element halide. Furthermore, although the rare earth element oxide is relatively hard, it is brittle, so particles may occur when exposed to the plasma environment. Therefore, since the spray coating disclosed here does not substantially contain the rare earth element oxide, it can be more excellent in plasma corrosion resistance.

In addition, dry etching devices used for manufacturing semiconductor devices are required to have low particle size. As a cause of the occurrence of the particles, in addition to the peeling of the reaction product adhering to the vacuum chamber, for example, the chamber is deteriorated due to the use of halogen gas plasma or oxygen plasma. The larger the particle size of the particle system becomes, the more problematic it becomes. In the past few years, the precision of processing precision has been strict, and it is necessary to strictly limit the occurrence of particles with a particle size of 0.2 μm or less (less than 0.2 μm, such as 0.1 μm or less). Based on the discussion by the present inventors, it was confirmed that the number or size of particles generated from the spray coating under a dry etching environment has a large influence on the composition of the spray coating. For example, according to the conventional spray coating, particles of 0.2 μm or more may occur. However, when the materials disclosed herein are used for proper spraying, a spray coating excellent in plasma corrosion resistance can be obtained. Typically, for example, according to the spray coating disclosed herein, under the current dry etching environment, coarse particles of about 0.2 μm or more will not be formed as the cause of the modified layer. This is because when the melt-spraying film disclosed here is corroded in a dry etching environment, the generated particles are composed of a particle-like modified layer with a size of about 0.2 μm or less (typically 0.1 μm or less). Therefore, the spray coating disclosed here can be suppressed to, for example, about 0.2 μm or less (eg, 0.1 μm or less, typical The upper limit is 0.06 μm or less, preferably 19 nm or less, and more preferably 5 nm or less, and most preferably 1 nm or less). For example, the number of occurrences of these particles is substantially suppressed to zero.

The plasma corrosion resistance of the spray coating can be evaluated by, for example, the number of particles that occur when the spray coating is exposed to a specific plasma environment. In dry etching, an etching gas is introduced into a vacuum container (chamber), and the etching gas is excited by high frequency or microwave to generate plasma and generate free radicals and ions. The free radicals and ions generated by the plasma react with the object to be etched (wafer), and the reaction product is exhausted as a volatile gas from the vacuum exhaust system to the outside, and the object to be etched can be finely processed. For example, in an actual parallel plate type RIE (reactive ion etching) device, a pair of parallel plate electrodes are provided in an etching chamber (chamber). Next, a high frequency is applied to an electrode to generate plasma, and a wafer is placed on the electrode for etching. Plasma is generated in the pressure band around 10mTorr to 200mTorr. As the etching gas system as described above, various halogen gases, oxygen, and inert gases can be considered. When evaluating the plasma corrosion resistance of the spray coating, it is preferable to use a mixed gas containing halogen gas and oxygen (for example, a mixed gas containing argon, carbon tetrafluoride, and oxygen at a specific volume ratio) as the etching gas. The flow rate of the etching gas is preferably about 0.1 L/min or more and 2 L/min or less, for example.

Therefore, by measuring the number of particles that occur after placing the spray film in this plasma environment for a specific time (such as the time for processing 2000 semiconductor substrates (silicon wafers, etc.)), the spray film can be better evaluated Resistance to plasma corrosion. Here, in order to achieve a high level of quality control, particles having a diameter of, for example, 0.06 μm or more may be used as the measurement target, but may be appropriately changed according to the required quality. Therefore, for example, it can be calculated how many particles of this size are accumulated per unit area of the semiconductor substrate, and the number of particles generated (pieces/cm ² ), etc. can be obtained to evaluate the plasma corrosion resistance.

The preferred state of the spray coating disclosed herein can be identified as the number of particles suppressed to about 4 particles/cm ² or less. For example, the number of particles generated under the conditions specified below can be set to 4 particles/cm ² or less. With such a configuration, it is preferable to realize a spray coating that is surely improved in plasma corrosion resistance.

[Conditions for counting particles]

A 70 mm x 50 mm spray coating is provided on the upper electrode of the parallel flat plate plasma etching device. And the plasma processing target substrate with a diameter of 300mm is set on the platform. Next, in order to simulate the long-term use state of the spray coating, 2,000 substrates (silicon wafers) were subjected to plasma dry etching treatment, and a virtual operation was performed for an extended 100 hours. The plasma generation conditions are pressure: 13.3 Pa (100 mTorr), etching gas: a mixed gas of argon, carbon tetrafluoride, and oxygen, and applied voltage: 13.56 MHz, 4000 W. Subsequently, a substrate (silicon wafer) for measurement and monitoring was placed on the platform, and plasma was generated for 30 seconds under the same conditions as above. In addition, before and after the plasma treatment, the number of particles with a diameter of 0.06 μm or more deposited on the substrate for measurement monitoring was calculated. At this time, the number of particles counted divided by the area of the substrate was used as the number of particles generated (number/cm ² ) for evaluation. In this case, the etching gas is a mixed gas containing argon, carbon tetrafluoride, and oxygen. In addition, the flow rate of the etching gas is set to 1 L/min, for example.

(Coating method)

Moreover, the above-mentioned spray coating can be formed by supplying the material for spraying disclosed herein to a spraying device based on a conventional spraying method. The spraying method suitable for spraying the material for spraying is not particularly limited. For example, it is preferably exemplified by a plasma spray method, a high-speed flame spray method, a flame spray method, a burst spray method, an aerosol deposition method, and the like. The characteristics of the spray coating may depend to some extent on the spray method and its spray conditions. However, when using any of the spraying methods and spraying conditions, by using the materials for spraying disclosed herein, it is possible to form a spray coating with more excellent plasma corrosion resistance than when using other spraying materials .

Hereinafter, several embodiments of the present invention will be described, but the present invention is not intended to be limited to those shown in the embodiments.

[Embodiment 1]

A powder of yttrium oxide, which is generally used as a protective film of a member in a semiconductor device manufacturing apparatus, is prepared as a material for No. 1 spray. Furthermore, yttrium fluoride powder of rare earth element halide was prepared as the material for No. 2 spraying. Next, powdery yttrium-containing compounds and fluorine-containing compounds are appropriately mixed and fired to obtain powdery materials for powder spraying No. 3 to 8. The physical properties of these spray shot materials were investigated and shown in Table 1 below. In addition, in Table 1, for reference, the information of the material for spraying disclosed in Patent Document 1 also contains information about the material for spraying (Examples 10 and 11 of Patent Document 1) in which the proportion of YOF is large. As reference examples A and B.

[Table 1]

The column of “XRD detection phase of melt-sprayed material” in Table 1 is the result of X-ray diffraction analysis of each material for melt-spraying, and represents the detected crystal phase. In the same column, "Y2O3" means that a phase made of yttrium oxide is detected, "YF3" means that a phase made of yttrium fluoride is detected, and "Y5O4F7" means that the chemical composition is detected, which is represented by Y ₅ O ₄ F ₇ The phase formed by yttrium oxyfluoride, "Y6O5F8" indicates that the chemical composition is detected by the yttrium oxyfluoride expressed by Y ₆ O ₅ F ₈ , and the "Y7O6F9" indicates that the chemical composition is detected by Y ₇ O ₆ F ₉ represents a phase formed by yttrium oxyfluoride, and “YOF” represents a phase formed by detecting a yttrium oxyfluoride represented by YOF (Y ₁ O ₁ F ₁ ).

In this analysis, an X-ray diffraction analyzer (Ultima IV manufactured by RIGAKU Corporation) was used, and CuKα line was used as the X-ray source (voltage 20kV, current 10mA), scanning range was 2θ=10°~70°, scanning speed 10°/min, sampling width 0.01°. In addition, the divergence slit is adjusted to 1°, the divergence longitudinal limit slit is 10 mm, the scattering slit is 1/6°, the light-receiving slit is 0.15 mm, and the compensation angle is 0°. For reference, the X-ray diffraction patterns obtained for the materials for No. 5 and No. 8 are shown in FIG. 1 (a) and (b) in sequence.

The column "Relative intensity of X-ray diffraction main peak" in Table 1 is based on the main peaks of each crystal phase detected in the diffraction pattern obtained from the above powder X-ray diffraction analysis results of each material for spraying And the relative value when the highest main peak intensity is set to 100.

The column of "Intensity ratio [(I _B +I _C )/I _A ]" in Table 1 represents the relative intensity of the main peak of each crystal phase detected above, and the peak intensity of the main peak of the rare earth element oxide The result of the calculation of the ratio of the peak intensity I _C of the main peak of I _B and the rare earth element halide to the peak intensity I _A of the main peak of the rare earth element oxyhalide.

The columns of "Oxygen" and "Fluorine" in Table 1 show the results of measuring the amount of oxygen and the amount of fluorine contained in each material for spraying, respectively. The oxygen content uses oxygen. nitrogen. The value measured by a hydrogen analyzer (ONCO 836 manufactured by LECO Corporation), and the amount of fluorine are measured using an automatic fluoride ion analyzer (manufactured by HORIBA, model FLIA-101).

The column of "Ratio of each crystal phase" in Table 1 indicates that the ratio of each crystal phase when the total amount of the four crystal phases detected in each material for spraying is set to 100% by mass is determined by X-ray diffraction. The result of the calculation of the relative intensity of the peak and the amount of oxygen and nitrogen.

The column of "average particle diameter" in Table 1 shows the average particle diameter of each material for spraying. The average particle size is the value of D50% of the volume basis measured using a laser diffraction/scattering particle size distribution measuring device (manufactured by HORIBA, LA-300).

(Evaluation)

As understood from the results of XRD analysis, it can be seen that as No. 5 to 8 materials for spraying, a single phase of yttrium oxyfluoride is obtained. From the results of the intensity ratio in Table 1, it was confirmed that the materials for spraying disclosed herein were obtained as the materials for spraying of Nos. 5 to 8.

As also shown in the ratio of the crystal phases in Table 1, it can be seen that the above-mentioned molten material whose intensity ratio is less than 0.02 is substantially in the XRD pattern, and only the rare earth element oxyhalide is detected.

[Embodiment 2]

These No. 1~8 materials for spraying are sprayed by the plasma spraying method, and a member with melt spraying provided with the No. 1~8 spray coatings is produced. The spray conditions are as follows.

That is, first prepare a plate (70mm×50mm×2.3mm) made of aluminum alloy (A16061) as the base material of the material to be sprayed, and apply the spray treatment with the brown alumina grinding material (A#40) use. For plasma spraying, a commercially available plasma spraying device (Praxair Surface Technologies, SG-100) was used. The plasma generation conditions are to use argon gas 50 psi (0.34 MPa) and helium gas 50 psi (0.34 MPa) as the plasma actuating gas, and generate plasma at a voltage of 37.0 V and a current of 900 A. In addition, the material for spraying is supplied to the spraying device by using a powder feeder (model 1264 manufactured by Praxair Surface Technologies) at a speed of 20 g/min to the spraying device to form a spray coating with a thickness of 200 μm. . In addition, the moving speed of the melt-spraying gun is 24m/min, and the melt-spraying distance is 90mm.

The physical properties of the resulting spray coating were investigated and shown in Table 2 below. In addition, the number of particles generated when the spray film was exposed to halogen-based plasma was investigated by the following three different methods. These results are shown in Table 2. In addition, the data item column shown in Table 2 that is common to Table 1 indicates the result of investigating the same content as Table 1 for the spray coating.

[Table 2]

In addition, the column of "Crystal Phase of Spray Material" in Table 2 is based on the ratio of each crystal phase calculated in Embodiment 1 and the XRD analysis results. Said.

The column of "XRD detection phase of the melt-sprayed film" in Table 2 is the result of X-ray diffraction analysis of each melt-sprayed film, and represents the detected crystal phase.

The column of "Intensity ratio [(I _CB +I _CC )/I _CA ]" in Table 2 shows the relative intensity of the main peak of each crystal phase detected above, and the peak intensity of the main peak of the rare earth element oxide The peak intensity of the main peak of I _CB and the rare earth element halide I _CC is calculated relative to the ratio of the peak intensity of the main peak of the rare earth element oxyhalide I _CA.

The column of "Porosity" in Table 2 shows the measurement results of the porosity of each spray coating. The porosity is measured as follows. That is, the melt-spraying film was cut at a plane orthogonal to the surface of the substrate, and the obtained cross-section was embedded in a resin and polished, and then a cross-sectional image was taken using a digital microscope (manufactured by OMRON Corporation, VC-7700). Next, the image is analyzed using image analysis software (manufactured by Japan ROPER Co., Ltd., Image Pro), and the area of the stomatal part in the cross-sectional image is specified. By calculating the area of the stomatal part in all the cross-sections Calculate the proportion.

The "Vicat hardness" column in Table 2 shows the measurement results of the Vicat hardness of each spray coating. Vicat hardness is measured in accordance with JIS R1610: 2003, using a hard and micro hardness tester (Shimadzu Corporation, HMV-1), with a sapphire load of 136° opposite angle Vicat hardness (Hv0.2) determined at a test force of 1.96N.

The column of "number of particles [1]" in Table 2 shows the results of evaluating the number of particles that occurred when each spray coating was exposed to plasma under the following conditions. That is, first, the surface of the fused film of the member with the fused film produced above was mirror-polished using colloidal silica with an average particle diameter of 0.06 μm. Next, the member with the spray film was placed on the member serving as the upper electrode in the chamber of the parallel flat-type semiconductor device manufacturing device with the polished surface exposed. Next, a silicon wafer with a diameter of 300 mm was set on the platform in the chamber, and 2,000 silicon wafers were subjected to plasma dry etching for 100 hours of virtual operation. The plasma in the etching process keeps the pressure in the chamber at 13.3Pa, while supplying an etching gas containing argon gas, carbon tetrafluoride and oxygen in a specific ratio at a flow rate of 1L/min, and applying a high frequency of 4000W at 13.56MHz Electricity. Subsequently, a silicon wafer with a diameter of 300 mm for particle counting is set on the platform in the chamber, and when the plasma is generated under the same conditions as above for 30 seconds, it is calculated from the spray film to be deposited on the silicon wafer for particle counting The number of particles. The number of particles was measured using a particle counter (wafer surface inspection device, Surfscan SP2) manufactured by KLA-Tencor, and the total number of particles with a diameter of 0.06 μm (60 nm) or more was measured. When counting the total number of particles, count the number of particles on the silicon wafer before and after plasma etching in 30 seconds, and set the difference to the particles that are deposited on the silicon wafer from the self-spraying film after durability (after virtual operation) Number (total). In addition, the evaluation of the number of particles generated is calculated by calculating the relative value when the total number of particles of the No. 1 spray coating made of 100% yttrium is 100 (reference).

"A" in the number of particles [1] indicates the number of particles (phase Contrasting value) When it is less than 1, "B" means that the number of particles is more than 1 and less than 5, "C" means that the number of particles is more than 5 and less than 15, "D" means the number of particles When it is 15 or more and less than 100, "E" indicates that the number of particles is more than 100.

In addition, the number of particles of the spray coating obtained from the materials referenced A and B refers to the value measured by particles having a particle diameter of about 0.2 μm or more attached to the surface of the silicon wafer under the plasma etching conditions described in Patent Document 1. .

The column of "number of particles [2]" in Table 2 indicates the number of particles generated when plasma etching is performed on each spray coating under the same conditions as above. The wafer surface inspection device made by KLA-Tencor is used to replace Surfscan SP2 with Surfscan SP5 Evaluation results at the time of measurement. Surfscan SP5 can detect particles with a diameter of more than 19nm. The number of particles [2] indicates the result when finer particles are deposited on a silicon wafer as the measurement object. When counting the total number of particles, count the number of particles on the silicon wafer before and after plasma etching in 30 seconds, and set the difference to the number of particles accumulated on the silicon wafer from the sputtered film after durability (total number) . In addition, the evaluation of the number of particles generated is calculated by calculating the relative value when the total number of particles of the No. 1 spray coating made of 100% yttrium is 100 (reference).

"A" in the number of particles [2] column indicates the number of particles (relative value) is less than 1, "B" indicates that the number of particles is more than 1 and less than 5, "C" indicates the number of particles When it is 5 or more and less than 15, "D" indicates that the number of particles is 15 or more and less than 100, and "E" indicates that the number of particles is 100 or more.

The column of "number of particles [3]" in Table 2 indicates that the measurement After the plasma is irradiated with plasma under the following conditions and then ultrasonic waves are applied, the result is the number of particles when the particles are actively free from the spray coating.

Specifically, in this example, after the mirror surface of the prepared member with a spray coating is mirror-polished, four corners of the spray coating are marked with a marking tape to prepare a test piece that exposes a 10 mm×10 mm spray coating. Next, the test piece was set on the upper electrode of the semiconductor device manufacturing device, and while maintaining the pressure in the chamber at 13.3 Pa, an etching gas containing carbon tetrafluoride and oxygen at a specific ratio was supplied at a flow rate of 1 L/min at 13.56. A high-frequency power of 700W applied at MHz was applied for a total of 1 hour, and the test piece was exposed to the plasma. Subsequently, air was supplied into the chamber, and ultrasonic waves of 22 Hz and 400 W were applied to the spray film of the test piece after plasma exposure for 30 seconds to escape the particles from the spray film, and the particles in the air were measured by a counter. For the measurement of particles, a particle counter (manufactured by PMS, LASAIR) was used to measure the total number of particles with a diameter of 100 nm or more. The result was calculated and evaluated based on the relative value when the total number of particles of the No. 1 spray coating made of 100% yttrium was 100 (reference).

"A" in the number of particles [3] column means that the number of particles (relative value) is less than 10, "B" means that the number of particles is more than 10 and less than 25, and "C" means the number of particles When it is 25 or more and less than 50, "D" means that the number of particles is more than 50 and less than 90, and "E" means that the number of particles is more than 90.

(Evaluation)

It is understood from the results of No. 1 in Table 2 that it can be seen that the spray film formed by spraying the material for spraying made only of Y ₂ O ₃ is essentially composed of Y ₂ O ₃ only, and no melting is seen. Further oxidative decomposition of Y ₂ O ₃ hit.

And from the results of Nos. 2~5, it can be seen that the spray film formed by the spray material containing only YF ₃ , or only YOF, or the mixed phase containing these, part of YF ₃ or YOF is oxidized to Y ₂ O ₃ , but contains Y ₂ O ₃ . Especially from the results of No. 3 and No. 4, it can be seen that all 10% by mass of YF ₃ contained in the spray material is oxidized to Y ₂ O _{3. When} YF ₃ and YOF are mixed in the spray material, the YOF ₃ The oxidation stability is high and there is a tendency for YF _{3 to} preferentially oxidize.

Next, from the results of Nos. 5 to 8, it can be seen that the content of oxygen in the yttrium oxyfluoride in the material for spraying is less than YOF’s Y ₇ O ₆ F ₉ , Y ₆ O ₅ F ₈ and Y ₅ O ₄ F ₇ is oxidized by spraying, and it first changes to a more stable YOF phase, and Y ₂ O _{3 is} not directly formed. Moreover, if it is such materials for No. 6 to 8 for spraying, it can be seen that Y ₂ O ₃ is not formed in the spray coating in the general atmospheric piezoelectric paste spraying method as in this embodiment. That is, it can be confirmed that by using yttrium oxyfluoride with an oxygen content ratio less than YOF as the material for spraying, the formation of Y ₂ O ₃ in the spray coating can be suppressed.

About the number of particles [1]

Regarding the characteristics of the spray coating, in the No. 1 spray coating consisting only of Y ₂ O ₃ , the number of particles generated in the plasma environment is (E)100 (reference), per unit area on the silicon wafer The number of particles is approximately 500 to 1000 per tablet. In general, it is known that the yttrium oxide-based spray coating has better plasma corrosion resistance than alumina-based spray coatings, etc. However, in this embodiment, the number of particles of the spray coating system formed only by Y ₂ O ₃ is the largest , The result of the poorest plasma resistance among all spray coatings.

In addition, regarding the No. 2 spray coating, the number of particles generated in the plasma environment is (D) 15 or more and less than 100. The No. 2 spray coating is formed by oxidizing YF ₃ in the spray material The proportion of Y ₂ O ₃ is more. Therefore, when exposed to fluorine plasma, it is likely to cause deterioration and form a brittlely modified layer. Therefore, due to the following dry etching, when it is exposed to the plasma environment, it peels off into particles and tends to accumulate on the semiconductor substrate. Therefore, it can be confirmed that the spray coating film contains Y ₂ O ₃ , which reduces the plasma corrosion resistance.

In addition, about 90% or more of the measured particles are extremely fine particles that have not been managed so far with a diameter of 0.06 μm or more and less than 0.2 μm.

On the other hand, the spray coatings of Nos. 3 to 5 do not contain YF ₃ and are composed of YOF and Y ₂ O ₃ . The number of particles generated by these spray coatings in the plasma environment is the same as that of No. 3 and No. 2, but the amount of Y ₂ O ₃ of No. 4 and No. 5 is reduced and reduced to (C) less than 15 . From this, it is considered that YOF present in the spray coating is extremely stable to the plasma, and YOF exerts the effect of suppressing the peeling of the Y ₂ O ₃ modified layer due to the plasma.

In addition, the spray coating obtained by spraying the materials for spray of Reference Examples A and B presumably contains both YOF and Y ₂ O ₃ . Moreover, from the comparison of the number of particles in Reference Examples A and B, it can be understood that even if only a small amount of Y ₂ O ₃ is increased in the spray coating, the plasma corrosion resistance is greatly impaired.

Moreover, as shown in Nos. 6 to 8, it can be confirmed that the spray coating film which is substantially free of YF _{3 and} Y ₂ O ₃ and is substantially composed of yttrium oxyfluoride only has particles (A) to (B) Less than 5, and suppressed to a very small amount. These spray coatings show good values of porosity and Vicat hardness being well-balanced, which can be said to form good quality spray coatings. Regarding these particles, it can be confirmed that almost all of them are extremely small with a diameter of 0.06 μm or more and less than 0.2 μm.

In addition, it can be seen that the No. 9 and 10 spray coatings formed by using Y ₇ O ₆ F ₉ and Y ₆ O ₅ F ₈ as materials for spraying have a particle count of (A) less than 1, which is higher than using Y ₅ O ₄ F ₇ No.11 formed of it as a material for spraying with spray coating, plasma resistance, and thus more excellent corrosion properties. From the viewpoint of porosity, the coating film for spraying No. 11 is even better.

In addition, regarding the spray coatings Nos. 1, 3 to 5, the main peak intensity of Y ₂ O _{3 was} confirmed, and as the ratio of Y ₂ O ₃ decreased, the porosity became higher and the Vicat hardness tended to decrease. However, regarding the No. 5 spray coating, the values of porosity and Vicat hardness were significantly improved. This is considered to be influenced not only by the composition of the crystal phase constituting the spray coating, but also by the crystal phase constituting the material for spray coating.

Therefore, after reviewing the crystal phase constituting the material for spraying, the following was found. That is, yttrium oxide contained in the material for spraying is directly contained in the film for spraying, so it is not good to contain yttrium oxide in the material for spraying (refer to No. 1). In addition, if the material for spraying contains yttrium fluoride, the number of particles generated in the plasma environment becomes larger than that of yttrium oxyfluoride, which is undesirable (refer to Nos. 2 to 4). In terms of yttrium oxide and yttrium fluoride, yttrium oxide is less suitable for materials for spraying (refer to Nos. 1 and 2 above, and Reference Examples A and B). On the other hand, when the yttrium oxyfluoride is included in the material for spraying, in addition to the physical properties such as the porosity and Vicat hardness of the spray coating, the plasma corrosion resistance is also good (refer to No. 3~8) .

As can be seen from the above, among the materials for spraying, the rare earth element oxide (in this case, yttrium oxide) and the rare earth element fluoride (in this case, yttrium fluoride) relative to the rare earth element oxyhalide (in this case, yttrium oxide) If the proportion of fluoride is relatively small, in addition to the plasma corrosion resistance, a spray coating with good porosity and Vicat hardness can be formed. The relative intensity ratio of these crystalline phases, that is, the intensity ratio [(I _B +I _C )/I _A ] is preferably suppressed to less than 0.02, for example. In addition, the intensity ratio [(I _CB +I _CC )/I _CA ] of the spray coating formed by using such a material for spray coating is preferably, for example, 0.45 or less.

About the number of particles [2]

As shown in Table 2, it can be seen that the evaluation result of the number of particles [2] is sufficiently consistent with the evaluation result of the number of particles [1]. As can be seen from this, the number of particles formed by spraying the material for spraying disclosed here is relatively reduced compared to the spraying film of No. 1 made of Y ₂ O ₃ alone, especially Even the occurrence of fine particles of 19 to 60 nm is suppressed to a small amount. The so-called particles above 19nm are the smallest particle size that can be measured at this stage, and it can be said that these fine particles are almost zero. As a result, the spray coating of the spray of the material for spraying disclosed herein confirmed that even if the accuracy of the lower detection limit of the particles is improved, it still exhibits high plasma corrosion resistance.

About the number of particles [3]

As shown in Table 2, it can be seen that the evaluation result of the number of particles [3] is sufficiently consistent with the evaluation result of the number of particles [1] [2]. However, the particles detected in the number of particles [3] are relatively coarse particles above 100 nm, which can be distinguished as the critical value of A~D and become an evaluation approaching E. That is, if according to the number of particles [3], it can be detected that more and bigger particles occur due to ultrasonic shock. Therefore, according to the number of particles [3], in addition to the particles directly generated by the irradiation of the halogen-based plasma, it is also possible to evaluate the particle generation source that did not actually occur but may subsequently become particles. The so-called particle generation source is considered to be a melt-sprayed film (modified layer) that is deteriorated by the irradiation of halogen-based plasma, and may become part of the particles due to subsequent plasma etching. Thus, by irradiating ultrasonic waves to the spray film exposed to the halogen-based plasma, the plasma corrosion resistance of the spray film can be more accurately evaluated. Moreover, according to the number of particles [3], it is possible to predict the occurrence of particles originating from the spray coating when a large number of wafers are processed for more than 2000 wafers, for example. Furthermore, from the results in Table 2, it can be confirmed that, for example, the spray coating of N0.6 to 8 can more highly suppress the generation of particles when exposed to halogen-based plasma.

Although the specific examples of the present invention have been described in detail above, these are only examples and do not limit the scope of patent application. The technology described in the patent application scope includes various changes and modifications to the specific examples illustrated above.

Claims (9)

A material for spraying, which is a material for spraying containing a rare earth element oxyhalide (RE-OX) containing rare earth elements (RE), oxygen (O), and halogen elements (X) as constituent elements, and the In the X-ray diffraction pattern of the material for spraying, the sum of the peak intensity I _B of the main peak of the rare earth element oxide and the peak intensity I _C of the main peak of the rare earth element halide is relative to the above-mentioned rare earth element oxyhalogenation The intensity ratio of the peak intensity I _A of the main peak of the substance [(I _B +I _C )/I _A ] is less than 0.02, and among the aforementioned rare earth element oxyhalides, the halogen element has a molar ratio to the aforementioned rare earth element. The ratio (X/RE) is 1.1 or more, and the molar ratio (O/RE) of the oxygen to the rare earth element is 0.9 or less. The material for spray shot according to claim 1, which is substantially free of the aforementioned rare earth element halide. The material for spraying as claimed in claim 2, which is substantially free of the aforementioned rare earth element oxide. The material for spray shot according to any one of claims 1 to 3, wherein the molar ratio (X/RE) of the halogen element to the rare earth element in the rare earth element oxyhalide is 1.3 or more and 1.39 or less. The material for spray shot according to any one of claims 1 to 3, wherein the rare earth element is yttrium, the halogen element is fluorine, and the rare earth oxyhalide is yttrium oxyfluoride. A spray coating, which is a spray of the material for spraying according to any one of claims 1 to 5. A melt-spraying film, which is composed of a rare earth element oxyhalide (RE-OX) containing rare earth elements (RE), oxygen (O) and halogen elements (X) as constituent elements, and the X-ray In the radiographic pattern, the peak intensity I of the main peak of the rare earth element oxide I _CB and the peak intensity I of the main peak of the rare earth element halide I _CC are relative to the peak intensity I of the main peak of the rare earth element oxyhalide The intensity ratio of _CA [(I _CB +I _CC )/I _CA ] is 0.45 or less. The spray coating according to claim 6 or 7, which substantially does not contain the aforementioned rare earth element oxide. A member with a spray coating is provided with the spray coating according to any one of claims 6 to 8 on the surface of a base material.

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