TW201639978A - Thermal spray material, thermal spray coating and thermal spray coated article - Google Patents

Abstract

This invention provides a thermal spray material capable of forming a thermal spray coating excellent in plasma erosion resistance as well as in properties such as porosity and hardness. The thermal spray material comprises a rare earth element oxyhalide (RE-O-X) which comprises a rare earth element (RE), oxygen (O) and a halogen atom (X) as its elemental constituents. The thermal spray material has an X-ray diffraction pattern that shows a main peak intensity IA corresponding to the rare earth element oxyhalide, a main peak intensity IB corresponding to a rare earth element oxide and a main peak intensity IC corresponding to a rare earth element halide, satisfying a relationship [(IB+IC)/IA]<0.02.

Description

a material for spraying, a spray film, and a member with a spray film

The present invention relates to a material for a spray, a sprayed film formed using the material for spray, and a member to which a sprayed film is attached.

The present application claims priority on the basis of Japanese Patent Application No. 2015-095516, filed on May 8, 2015, the entire disclosure of In this manual.

The technique of imparting new functionality to the surface of a substrate by coating various materials has been utilized in various fields since the past. As one of the surface coating techniques, it is known that, for example, a molten particle formed of a material such as ceramic is blown on the surface of a substrate by burning or electric energy into a softened or molten state to form a melt formed by the material. The film is sprayed.

Further, in the field of manufacturing semiconductor devices and the like, a plasma of a halogen-based gas such as fluorine, chlorine or bromine is generally subjected to microfabrication on the surface of a semiconductor substrate by dry etching. Again, after dry etching, take The semiconductor substrate is patterned inside the chamber (vacuum container) using oxygen plasma. At this time, the components exposed to the highly reactive oxygen plasma or the halogen gas plasma in the chamber are corroded. Therefore, when the erosion portion is detached from the member in the form of particles, the particles may adhere to the semiconductor substrate and may become a foreign matter causing a circuit defect (hereinafter, the foreign matter is referred to as a particle).

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

[Previous Technical Literature]

[Patent Literature]

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

However, as the degree of integration of semiconductor devices increases, the contamination caused by particles requires more precise management. Further, regarding the spray coating of the ceramic provided in the semiconductor device manufacturing apparatus, further improvement in plasma corrosion resistance is required. When the characteristics of the porosity, hardness, and the like of the sprayed film are good, for example, a spray film excellent in durability and the like is obtained. good.

In view of the above circumstances, an object of the present invention is to provide a material for spraying which can form a spray coating having improved plasma corrosion resistance and a low porosity and excellent properties such as hardness. Other objects are to provide a spray coating formed of the material for spray coating and a member to which a spray coating is attached.

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

According to the review by the inventors of the present invention, the molten material containing a rare earth oxyhalide can be formed into a halogen-based plasma as compared with a molten material containing a rare earth element oxide or a rare earth element halide. A spray coating that is more resistant to plasma corrosion. The rare earth element oxide and the rare earth element halide are materials which are generally used for producing a raw material of the rare earth element oxyhalide, and may remain as a material for the deposition, for example, as an unreacted material. For example, when a material for a molten material contains a rare earth element oxide and a rare earth element halide, by suppressing the total amount thereof to satisfy the above-described strength ratio, it is possible to form a plasma film having excellent corrosion resistance and a spray film. A spray coating having excellent characteristics such as porosity and hardness.

Here, the "main peak" means a peak having the highest peak height (i.e., the highest diffraction intensity) in the diffraction peak group derived from any compound detected in the X-ray diffraction pattern.

Further, Patent Document 1 discloses a material for spraying which contains a neodymium fluoride fluoride (YOF) in a relatively high ratio (Reference Examples 9 to 11). However, as a result of the X-ray diffraction analysis of the above-mentioned molten materials, the content ratio of YOF calculated from the oxygen content was 77% by mass or more of the total, and the material containing no yttrium oxide (Y ₂ O ₃ ) was not disclosed. In other words, the material for the spray disclosed herein can be said to be a novel spray material which can form a spray coating having excellent plasma corrosion resistance and excellent properties such as porosity and hardness of the sprayed film.

The preferred state of the material for spraying disclosed herein may be a form substantially free of the above-mentioned rare earth element halide. Further, it may be in a form substantially free of the aforementioned rare earth element oxide.

According to this configuration, as described above, the plasma corrosion resistance of the formed sprayed film can be more surely improved, the porosity of the sprayed film can be lowered, and the hardness can be increased.

Preferably, the material for the melt disclosed herein 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. Further, it is 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 resistance to the halogen-based plasma by increasing the ratio of the halogen element of the rare earth element oxyhalide in the material for the spray. Further, by reducing the ratio of the oxygen of the rare earth element oxyhalide in the material for the melt, it is preferable that the rare earth element oxide is hardly formed in the sprayed film. Further, by adjusting these in a well-balanced manner, it is preferable to obtain a sprayed film having a low porosity and a high Vickers hardness.

The preferred material of the material for spraying disclosed herein is characterized in that the rare earth element is lanthanum, the halogen element is fluorine, and the rare earth element oxyhalide is lanthanum oxyfluoride. According to this configuration, it is possible to provide a material for spraying which can form a spray coating excellent in corrosion resistance to, for example, fluorine plasma.

In other aspects, the present invention provides a spray coating of a melt of a material for spraying described in any of the above. The oxide component of the rare earth element in the sprayed film causes the sprayed film to be embrittled to deteriorate the plasma resistance. The melted film disclosed herein is formed by spraying the above-described molten material, and the oxide content of the rare earth element is reduced. Therefore, it can be provided as a person who reliably improves plasma etching resistance. .

Further, the spray film provided by the present invention is characterized in that a rare earth element oxyhalide (RE-OX) containing a rare earth element (RE), oxygen (O), and a halogen element (X) as a constituent element is used as a main component. And the intensity ratio of the peak intensity I _CB of the main peak of the rare earth element oxide to the peak intensity I _CC of the main peak of the rare earth element halide relative to the peak intensity I _CA of the main peak of the rare earth element oxygen halide [(I _CB + I _CC ) / I _CA ] is 0.45 or less.

According to this configuration, since the content ratio of the rare earth element oxide and the rare earth element halide in the sprayed film is reduced, it is possible to provide a positive improvement. It is resistant to plasma corrosion and reduces the porosity of the sprayed film and increases the hardness.

The preferred state of the sprayed film disclosed herein is characterized by being substantially free of oxides of the above rare earth elements. When the molten film is substantially free of rare earth element oxide, it is preferable to further improve plasma corrosion resistance.

The preferred material of the material for spraying disclosed herein is characterized in that the rare earth element is cerium, the halogen element is fluorine, and the rare earth oxyhalide is cerium oxyfluoride. According to this configuration, it is possible to reliably form a sprayed film which is excellent in corrosion resistance to, for example, fluorine plasma, and has improved porosity, hardness, and the like of the sprayed film.

Further, the member of the sprayed film provided by the technique disclosed herein is characterized in that the surface of the substrate is provided with the sprayed film described in any of the above. According to this configuration, the member with the spray coating excellent in plasma corrosion resistance is provided.

Fig. 1 is a view showing an X-ray diffraction pattern obtained by the materials for spraying of (a) No. 5 and (b) No. 8 of the second embodiment.

Hereinafter, preferred embodiments of the present invention will be described. Further, the case other than those specifically mentioned in the present specification and the case necessary for the implementation of the present invention can be grasped based on the prior art in the field as a design matter of the present inventors. The present invention can be based on the content disclosed in the present invention and Implemented in the field of technical common sense.

[Material for spraying]

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

Among the techniques disclosed herein, the rare earth element (RE) is not particularly limited and may be appropriately selected from the elements of lanthanum, cerium and lanthanide. Specifically, 钪 (Sc), 钇 (Y), 镧 (La), 铈 (Ce), 鐠 (Pr), 铷 (Nd), 鉕 (Pm), 钐 (Sm), 铕 (Eu), gallium ( Any one or a combination of two or more of Gd), Tb, Dy, Ho, Er, Tm, Yb, and Lu. From the viewpoint of improving plasma corrosion resistance, price, and the like, Y, La, Gd, Tb, Eu, Yb, Dy, Ce, and the like are preferable. The rare earth elements may comprise any one of these or may comprise a combination of two or more.

Further, the halogen element (X) is not particularly limited as long as it belongs to any of the elements 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 ruthenium (At), or may be a combination of two or more types. It is preferably F, Cl or Br. The halogen element may be used alone or in combination of two or more the above. As such a rare earth element oxyhalide, oxyfluoride, oxychloride, and oxybromide of various rare earth elements are exemplified as representative examples.

Here, the plasmon corrosion resistance of the rare earth element oxyhalide is more excellent than that of yttrium oxide (Y ₂ O ₃ ) which is known as a material having high plasma corrosion resistance. It is preferred to contain a relatively large amount of such a rare earth element oxyhalide because it exhibits extremely good plasma resistance.

The rare earth element oxide contained in the material for spraying can be directly deposited as a rare earth element oxide in the spray film by spraying. For example, cerium oxide contained in the material for spraying can be directly deposited as cerium oxide in the molten film by spraying. The rare earth element oxide (e.g., cerium oxide) has lower plasma resistance than 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 be generated, and the altered layer is likely to become fine particles and be separated. Further, the fine particles are deposited on the semiconductor substrate as particles. Therefore, the content of the rare earth element oxide which may become a source of particles is less preferable.

Further, the fluoride of the rare earth element contained in the material for the spray is oxidized by the spray to form a rare earth element oxide in the sprayed film. For example, barium fluoride contained in the material for spraying may be oxidized by melting to form cerium oxide in the spray film. Since the oxides of these rare earth elements may become a source of particles as described above, the content is less preferred.

Based on the above, in the technique disclosed herein, the rare earth element oxyhalide is defined as an X-ray diffraction pattern of the material for spraying, and the intensity ratio [(I _B + I _C ) / I _A ] is not Up to 0.02. Further, when the molten material contains a plurality of rare earth element oxyhalides, the peak intensity of the main peak of each of the compositions may be I _A . When the molten material contains a rare earth element oxide having a plurality of compositions, the total peak intensity of the main peak of each composition may be I _B . Further, when the material for the spray contains a rare earth element halide having a plurality of compositions, the total peak intensity of the main peak of each of the compositions may be I _C .

The above strength ratio [(I _B + I _C ) / I _A ] is preferably 0.01 or less, more preferably 0.005 or less. Such a configuration is better achieved by, for example, a form in which the material for the spray is substantially free of a rare earth element halide. Alternatively, it can be better realized by, for example, a form in which the material for the spray is substantially free of the rare earth element oxide. Further, the above-described intensity ratio [(I _B + I _C ) / I _A ] is particularly preferably 0 (zero). In other words, the material for the spray is particularly desirably composed only of the rare earth element oxyhalide.

Further, the X-ray diffraction analysis of the rare earth element oxyhalide, the rare earth element oxide, and the rare earth element halide can be preferably carried out based on, for example, the following conditions. Specifically, an X-ray diffraction analysis apparatus (Ultima IV, manufactured by RIGAKU Co., Ltd.) is used, and a CuKα line is used as an X-ray source (voltage: 20 kV, current: 10 mA), and the scanning range is 2θ=10° to 70°. The measurement was carried out at a scanning speed of 10°/min and a sampling width of 0.01°. Further, in this case, it is preferable to adjust the divergence slit to be 1°, the divergence vertical restriction slit to be 10 mm, the scattering slit to be 1/6°, the light receiving slit to be 0.15 mm, and the compensation angle to be 0°. By this analysis, for example, the main peaks of representative rare earth element oxyhalides, rare earth element oxides, and rare earth element halides are detected at substantially the following positions. Thereby, the peak intensity of the main peak of each compound can be obtained more accurately.

<Composition: main 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, the term "substantially free" in the present specification means that the content of the component (here, the rare earth element oxide or the rare earth element halide) is 5% by mass or less, preferably 3% by mass or less. For example, it is 1 mass% or less. In this configuration, for example, when the X-ray diffraction analysis is performed on the material for spraying, it is not possible to grasp the diffraction peak based on the component. In addition, in the present specification, substantially only the rare earth element oxyhalide is used, and when the X-ray diffraction analysis is performed by, for example, the material for spraying, no rare earth element oxyhalide is detected. Master the diffraction peaks of the compound.

Further, in the technique disclosed herein, the halogen-based plasma is typically a plasma generated by using a plasma-generating gas containing a halogen-based gas (halogen compound gas). For example, it is specifically a fluorine-based gas such as SF ₆ , CF ₄ , CHF ₃ , ClF ₃ or HF used in a dry etching step, or a chlorine-based gas such as Cl ₂ , BCl ₃ or HCl, or a bromine system such as HBr. A plasma produced by using one type of gas alone or in combination of two or more kinds is exemplified as a typical one. These gases can also be used as a mixed gas with an inert gas such as argon (Ar).

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

For example, the molar ratio (X/RE) of the halogen element to the rare earth element is not particularly limited. As a preferred example, the molar ratio (X/RE) may be, for example, 1, preferably greater than 1. Specifically, it is more preferably 1.1 or more, and is desirably, 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 may be, 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 more preferably 1.4 or less (less than 1.4). A more preferable example of the molar ratio (X/RE) is exemplified as 1.3 or more and 1.39 or less (for example, 1.32 or more and 1.36 or less). Thus, by increasing the ratio of the halogen element to the rare earth element, it is preferable to provide resistance to the halogen-based plasma.

Further, the molar ratio (O/RE) of the oxygen element to the rare earth element is not particularly limited. As a preferred example, the molar ratio (O/RE) may be, for example, 1, preferably less than 1. Specifically, it is more preferably 0.9 or less, and is desirably, 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 may be, for example, 0.1 or more. Among them, a more preferable example of the molar ratio (O/RE) of the rare earth element to the oxygen element is preferably more than 0.8 and less than 0.85 (preferably 0.81 or more and 0.84 or less). As described above, by reducing the ratio of the oxygen element to the rare earth element, it is preferable to suppress the formation of an oxide (for example, Y ₂ O ₃ ) of the rare earth element in the spray film by oxidation in the spray.

That is, the rare earth element oxyhalide is preferably a compound having a ratio of RE to O and X expressed by, for example, the formula: RE ₁ O _m1 X _m2 (for example, 0.1 ≦m1 ≦ 1.2, 0.1 ≦ m 2 ≦ 3). In a preferred embodiment, the case where the rare earth element is yttrium (Y), the halogen element is fluorine (F), and the rare earth element oxyhalide is fluorinated oxyfluoride (YOF) will be described. The fluorenyl fluoride is preferably a compound represented by YOF which is, for example, thermodynamically stable and has a chemical composition of 1:1 and oxygen to a halogen element of 1:1:1. Further, it is preferably a thermodynamically stable Y ₅ O ₄ F ₇ , Y ₆ O ₅ F ₈ represented by the general formula Y ₁ O _1-n F _1+2n (where n is, for example, 0.12≦n≦0.22). , Y ₇ O ₆ F ₉ , Y ₁₇ O ₁₄ F ₂₃ and the like. In particular, Y ₆ O ₅ F ₈ and Y ₁₇ O ₁₄ F _{23 having} a molar ratio of O/RE and (X/RE) in the above-mentioned better range can be formed into a denser and higher hardness due to excellent plasma corrosion resistance. The spray film is preferred.

Further, in the above-described example of the fluorinated fluorinated substance, 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.

Such a rare earth element oxyhalide may be composed of any of the above-described single phases, or may be composed of a mixed phase, a solid solution, a compound, or a mixture of any two or more of them.

Further, when the molten material contains a rare earth element oxyhalide having a composition of a plurality (for example, a; a natural number, a ≧ 2), the above-described 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 Moer than (Oa/REa) and totaling, the molar ratio (X/RE) of the rare earth element oxyhalide can be obtained and Mo Ear ratio (O/RE).

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

The content ratio of the rare earth element oxyhalide contained in the material for spraying can be specifically calculated 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 is specified to its valence (element ratio).

Therefore, for example, when a rare earth element oxyhalide is present in the material for spraying and the remainder is YF ₃ , the oxygen content of the material for spraying can be by, for example, oxygen. nitrogen. A hydrogen analyzer (for example, ONH836, manufactured by LECO Co., Ltd.) was measured, and the content of the rare earth element oxyhalide was quantified from the obtained oxygen concentration.

When two or more rare earth element oxyhalides are present in an oxygen-containing compound such as cerium oxide, for example, the ratio of each compound can be quantified by a calibration line method. Specifically, a sample in which the ratio of the content of each of the plurality of compounds is changed is prepared, and X-ray diffraction analysis is performed on each sample to prepare a correction line showing the relationship between the intensity of the main peak and the content of each compound, and then based on the correction line. The main peak intensity quantitative content of the rare earth element oxyhalide of XRD determined from the material for the melt to be measured.

The above-mentioned materials for spraying are typically provided in the form of a powder. 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 agglomerated form). Based on the viewpoint of the efficiency of the spray, for example, if the average particle diameter is The temperature of about 30 μm or less is not particularly limited, and the lower limit of the average particle diameter is 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, more preferably 35 μm or less. The lower limit of the average particle diameter is not particularly limited, and 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, in consideration of the fluidity of the material for the spray.

[Molded film]

A molten film can be formed by spraying the above-mentioned material for spraying. The film is provided on the surface of the substrate as a member to which a film is attached, and the like. Hereinafter, the member to which the sprayed film is attached and the sprayed film will be described.

(substrate)

Among the members to which the sprayed film is attached, the substrate for forming the sprayed film is not particularly limited. For example, the material, shape, and the like are not particularly limited as long as it is a substrate made of a material having a desired resistance to the melting of the material for spraying. The material constituting the substrate is exemplified by, for example, a metal material containing various metals, semimetals, and alloys thereof, or various inorganic materials. Specifically, the metal material is exemplified by a metal material such as aluminum, aluminum alloy, iron, iron steel, copper, copper alloy, nickel, nickel alloy, gold, silver, lanthanum, manganese, zinc, zinc alloy, or the like; Group II semiconductors such as germanium (Ge), group II-VI compound semiconductors such as zinc selenide (ZnSe), cadmium sulfide (CdS), and zinc oxide (ZnO), gallium arsenide (GaAs), and indium phosphide (InP) ), a group III-V compound semiconductor such as gallium nitride (GaN), a group IV compound semiconductor such as tantalum carbide (SiC) or germanium (SiGe), copper. indium. Chalcopyrite such as selenium (CuInSe ₂ ) is a semi-metal material such as a semiconductor; Examples of the inorganic material include a substrate material of calcium fluoride (CaF) and quartz (SiO ₂ ), an oxide ceramic such as alumina (Al ₂ O ₃ ) or zirconium oxide (ZrO ₂ ), and tantalum nitride (Si ₃ N). ₄ ), a nitride ceramic such as boron nitride (BN) or titanium nitride (TiN), a carbide-based ceramic such as tantalum carbide (SiC) or tungsten carbide (WC). These materials may be used to form a substrate, or two or more types may be combined to form a substrate. In the above, a steel material represented by various types of SUS materials (which may be so-called stainless steel) having a large thermal expansion coefficient and a heat resistant alloy typified by Inconel or the like is used as a preferred example. A low-expansion alloy represented by invar, kovar, a corrosion-resistant alloy represented by Hastelloy, etc., 1000 series to 7000 series useful as a lightweight structural material A base material such as an aluminum alloy represented by an aluminum alloy or the like. The substrate may be, for example, a member constituting a semiconductor device manufacturing apparatus, and is a member exposed to a highly reactive oxygen plasma or a halogen gas plasma. Further, for example, the above-described niobium carbide (SiC) or the like may be classified into a different type of compound semiconductor or inorganic material, but is the same material.

(spray film)

The spray coating disclosed herein is formed by spraying the above-mentioned material for spraying onto, for example, the surface of an arbitrary substrate. Therefore, the spray coating is configured to contain a rare earth element (RE), oxygen (O), and a halogen element (X) as constituent elements. A rare earth element oxyhalide (RE-O-X) is used as a film of a main component.

The term "main component" as used herein means the component having the largest content among the constituent components constituting the spray coating film. Specifically, it means that the component accounts for 50% by mass or more, preferably 75% by mass or more, and for example, 80% by mass or more of the entire melted film. Since the rare earth element oxyhalide is the same as that of the above-mentioned material for spraying, detailed description thereof will be omitted.

Although the detailed mechanism is not clear, the plasma corrosion resistance of the rare earth element oxyhalide is excellent in corrosion resistance to the halogen plasma. Therefore, the spray coating film containing a rare earth element oxyhalide as a main component can be excellent in plasma corrosion resistance.

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

Further, the sprayed film is preferably provided as a material which does not substantially contain the above-mentioned rare earth element oxide. The rare earth element oxide contained in the sprayed film is typically considered to be directly contained in the spray film by the rare earth element oxide contained in the spray material, and is contained in the spray material. A rare earth element halide is oxidized to a rare earth element oxide by melting. Since the rare earth element oxide is substantially not contained in the sprayed film, it is considered that the molten material for forming the sprayed film substantially does not contain the rare earth element oxide and the rare earth element halide. Moreover, although the rare earth element oxide is relatively hard, it is brittle, so particles may be generated when exposed to the plasma environment. Therefore, since the sprayed film disclosed herein does not substantially contain the rare earth element oxide, it can be more excellent in plasma corrosion resistance.

Further, the dry etching apparatus for manufacturing a semiconductor device requires low granulation. As the cause of the particle generation, in addition to the peeling of the reaction product attached to the vacuum chamber, the chamber is deteriorated by using a halogen gas plasma or an oxygen plasma. The larger the particle size of the particle system is, the more serious the processing precision is. In recent years, it has been necessary to strictly limit the occurrence of particles having a particle diameter of 0.2 μm or less (less than 0.2 μm, for example, 0.1 μm or less). According to the investigation by the inventors of the present invention, it was confirmed that the number or size of particles generated by the sprayed film in the dry etching environment greatly affects the composition of the sprayed film. For example, particles of 0.2 μm or more may be generated depending on the conventional film to be sprayed, but a spray film excellent in plasma corrosion resistance can be obtained by appropriately spraying the material for spraying disclosed herein. Typically, for example, according to the melted film disclosed herein, in the present dry etching environment, coarse particles having a size of about 0.2 μm or more are not formed as a deteriorated layer. When the sprayed film disclosed herein is etched in a dry etching environment, the particles which are generated are composed of a particulate modified layer having a size of about 0.2 μm or less (typically 0.1 μm or less). Therefore, the spray coating disclosed herein can suppress, for example, about 0.2 μm or less (for example, 0.1 μm or less, typical). Particles having a diameter of 0.06 μm or less, preferably 19 nm or less, more preferably 5 nm or less, and most preferably 1 nm or less occur. For example, the number of occurrences of such particles is substantially suppressed to zero.

The plasma corrosion resistance of the sprayed film can be evaluated by, for example, the number of particles which occur when the sprayed film is exposed to a specific plasma environment. In the dry etching, an etching gas is introduced into a vacuum vessel (chamber), and the etching gas is excited by a high frequency or a microwave to generate a plasma, and generates radicals and ions. The 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, electrodes of a pair of parallel flat plates are provided in an etching chamber (chamber). A high frequency is applied to one of the electrodes to generate a plasma, and a wafer is placed on the electrode for etching. The plasma is produced in a pressure zone of about 10 mTorr or more and 200 mTorr or less. As the etching gas system, as described above, various halogen gases or oxygen gas and inert gas can be considered. When the plasma corrosion resistance of the sprayed film is evaluated, it is preferred to use a mixed gas containing a halogen gas and oxygen (for example, a mixed gas containing argon and carbon tetrafluoride and oxygen in a specific volume ratio) as an etching gas. The flow rate of the etching gas is preferably, for example, about 0.1 L/min or more and 2 L/min or less.

Therefore, by measuring the number of particles which occur after the molten film is placed in such a plasma environment for a certain period of time (for example, the time of processing 2000 semiconductor substrates (such as wafers), the film can be better evaluated. Resistance to plasma corrosion. Here, in order to achieve high quality management, the particles may be measured, for example, at a diameter of 0.06 μm or more, but may be appropriately changed according to the required quality. Therefore, for example, it is calculated how much particles of such a size are deposited per unit area of the semiconductor substrate, and the number of particles generated (cm/cm ² ) is determined, and the plasma corrosion resistance can be evaluated.

The preferred state of the sprayed film disclosed herein can be recognized as the number of occurrences of the particles being suppressed to about 4/cm ² or less. For example, the number of particles generated by the conditions specified below can be set to 4 pieces/cm ² or less. According to this configuration, it is preferable to realize a spray coating which is improved in plasma corrosion resistance.

[Particle count count condition]

A 70 mm × 50 mm spray film was placed on the upper electrode of the parallel plate type plasma etching apparatus. And a substrate of a plasma processing target having a diameter of 300 mm is provided on the platform. Next, first, in order to simulate the long-term use state of the sprayed film, a plasma dry etching process was performed on 2000 substrates (the wafer), and a virtual operation was performed for 100 hours. The plasma generation conditions were 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 for measurement and monitoring (a wafer) was placed on the stage, and plasma was generated for 30 seconds under the same conditions as described above. Further, before and after the above plasma treatment, the number of particles having 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. Further, at this time, the etching gas is a mixed gas containing argon, carbon tetrafluoride, and oxygen. Further, the flow rate of the etching gas is set to, for example, 1 L/min.

(film formation method)

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

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

[Embodiment 1]

A powder of cerium oxide generally used as a protective film for a member in a semiconductor device manufacturing apparatus is prepared as a material for spraying No. 1. Further, a cerium fluoride powder of a rare earth element halide was prepared as a material for spraying No. 2. Then, the powdery compound containing ruthenium and the fluorine-containing compound are appropriately mixed and fired to obtain a powdery spray material No. 3 to 8. The physical properties of the materials for the above-mentioned materials were examined and shown in Table 1 below. In addition, in Table 1, the information of the material for the spray which is contained in the patent document 1 and which has a large proportion of the material for the spray of the YOF (Examples 10 and 11 of Patent Document 1) is also shown. As Reference Examples A and B.

[Table 1]

The column of "XRD detecting phase of the molten material" in Table 1 indicates the crystal phase to be detected as a result of X-ray diffraction analysis of each of the materials for spraying. In the same column, "Y2O3" means that the phase formed by cerium oxide is detected, "YF3" means that the phase formed by cesium fluoride is detected, and "Y5O4F7" means that the chemical composition is detected by Y ₅ O ₄ F ₇ The phase formed by the oxyfluoride, "Y6O5F8" indicates that the chemical composition is detected by the 钇 oxyfluoride represented by Y ₆ O ₅ F ₈ , and "Y7O6F9" indicates that the chemical composition is detected by Y ₇ O ₆ F ₉ represents the phase formed by the fluorinated fluoride, and "YOF" represents the phase in which the chemical composition is detected by the fluorinated fluorinated fluoride represented by YOF (Y ₁ O ₁ F ₁ ).

Further, in this analysis, an X-ray diffraction analysis apparatus (Ultima IV, manufactured by RIGAKU Co., Ltd.) was used, and a CuKα line was used as an X-ray source (voltage: 20 kV, current: 10 mA), and the scanning range was 2θ=10° to 70°, and the scanning speed was used. The condition was 10°/min and the sampling width was 0.01°. Further, the divergence slit was adjusted to 1°, the divergence vertical restriction slit was 10 mm, the scattering slit was 1/6°, the light receiving slit was 0.15 mm, and the compensation angle was 0°. For reference, the X-ray diffraction patterns obtained for the materials for spraying No. 5 and No. 8 are sequentially shown in Figs. 1 (a) and (b).

The column "relative intensity of X-ray diffraction main peaks" in Table 1 is the main peak of each crystal phase detected in the diffraction pattern obtained by the above-mentioned powder X-ray diffraction analysis of each of the materials for spraying. The intensity is the result of 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 indicates the peak intensity of the main peak of the rare earth element oxide based on the relative intensity of the main peak of each crystal phase detected above. The result of calculating 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 indicate the results of measuring the amount of oxygen and the amount of fluorine contained in each of the materials for spraying. The oxygen is oxygen. nitrogen. The value measured by a hydrogen analyzer (ONH836, manufactured by LECO Co., Ltd.), and the amount of fluorine was a value measured using an automatic fluoride ion measuring device (manufactured by HORIBA, FLIA-101 type).

The column of "the ratio of each crystal phase" in Table 1 indicates that the ratio of each crystal phase when the total amount of the four kinds of crystal phases detected in each of the materials for spraying is 100% by mass is X-ray diffraction. The calculated relative peak intensity and the amount of oxygen and nitrogen.

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

(Evaluation)

As is understood from the results of the XRD analysis, it was found that a single phase of the fluorinated fluorinated material was obtained as the material for the spraying of Nos. 5 to 8. Further, from the results of the strength ratios in Table 1, it was confirmed that the materials for the spray disclosed herein were obtained as the materials for the spray of Nos. 5 to 8.

Further, as shown by the ratio of each crystal phase in Table 1, it is understood that the above-described strength ratio of the molten material which is less than 0.02 is substantially in the XRD pattern, and only the material of the rare earth element oxyhalide is detected.

[Embodiment 2]

The materials for the spraying of Nos. 1 to 8 were sprayed by a plasma spray method to produce a member having a spray coating of Nos. 1 to 8. The spraying conditions are as follows.

That is, first, a plate made of an aluminum alloy (A16061) (70 mm × 50 mm × 2.3 mm) is prepared as a base material of the material to be fused, and a brown alumina ground material (A#40) is subjected to a spray treatment. use. In the plasma spray, a commercially available plasma spray device (SG-100, manufactured by Praxair Surface Technologies Co., Ltd.) was used. The plasma generation conditions were 50 psi (0.34 MPa) of argon gas and 50 psi (0.34 MPa) of helium gas as a plasma actuating gas, and plasma was generated at a voltage of 37.0 V and a current of 900 A. In addition, the material for the spray was supplied to the spray device by using a powder feeder (Model 1264, manufactured by Praxair Surface Technologies Co., Ltd.) to supply the spray material to the spray device at a speed of 20 g/min to form a spray film having a thickness of 200 μm. . Further, the moving speed of the spray gun was 24 m/min, and the spray distance was 90 mm.

The physical properties of the obtained sprayed film were examined and shown in Table 2 below. Further, the number of particles generated when the sprayed film was exposed to the halogen-based plasma was investigated by the following three different methods, and the results are shown in Table 2. In the data item column shown in Table 2, the same as Table 1 indicates the result of the same content as that of Table 1 in the investigation of the spray film.

[Table 2]

In addition, in the column of "the crystal phase of the molten material" in Table 2, based on the ratio of each crystal phase calculated in the first embodiment and the XRD analysis result, the crystal phase constituting each of the materials for the melt and the approximate ratio thereof are given. Said.

The column of "XRD detection phase of the sprayed film" in Table 2 is a result of performing X-ray diffraction analysis on each of the sprayed coatings, and indicates the detected crystal phase.

The column of "intensity ratio [(I _CB + I _CC ) / I _CA ]" in Table 2 indicates the peak intensity of the main peak of the rare earth element oxide based on the relative intensity of the main peak of each crystal phase detected above. total peak intensity of the main peak of the I _CB halides of rare earth elements and I _CC of the results relative to the peak intensity of the main peak of the rare earth element oxyhalide I _CA calculates the ratio.

Further, the column of "porosity" in Table 2 indicates the results of measurement of the porosity of each of the sprayed films. The measurement of the porosity was carried out as follows. In other words, the sprayed film was cut on a surface 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 (VC-7700, manufactured by OMRON Co., Ltd.). Then, the image was analyzed using an image analysis software (Image Pro, manufactured by Japan ROPER Co., Ltd.), and the area of the pore portion in the cross-sectional image was specified, and the area of the pore portion was calculated in the entire section. Calculated by the proportion.

The column of "Vicat hardness" in Table 2 indicates the measurement results of the Vicker hardness of each of the spray coatings. The measurement of the Vicat hardness is based on JIS R1610:2003, using a hard micro hardness tester (HMV-1, manufactured by Shimadzu Corporation), with a sapphire pressure load of 136° to the face angle The Vicat hardness (Hv0.2) obtained at a test force of 1.96 N.

The column of "number of particles [1]" in Table 2 indicates the result of evaluating the number of particles which occurred when the respective spray coatings were exposed to the plasma by the following conditions. That is, first, the surface of the sprayed film of the member to which the sprayed film was produced was mirror-polished using colloidal cerium oxide having an average particle diameter of 0.06 μm. Then, the member to which the film is attached is placed on the member as the upper electrode in the chamber of the parallel-plate type semiconductor device manufacturing apparatus so that the polishing surface is exposed. Next, a 300 mm diameter germanium wafer was placed on the platform in the chamber, and a plasma dry etching was performed on 2000 wafers for 100 hours of virtual operation. The plasma in the etching process maintains the pressure in the chamber at 13.3 Pa, and supplies argon gas and carbon tetrafluoride and oxygen etching gas at a flow rate of 1 L/min in a specific ratio, and applies a high frequency of 4000 W at 13.56 MHz. Electricity happens. Then, on the platform in the chamber, a silicon wafer having a diameter of 300 mm for particle counting is set, and when plasma is generated for 30 seconds under the same conditions as above, the film is deposited from the spray film and deposited on the 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 Co., Ltd., and the total number of particles having a diameter of 0.06 μm (60 nm) or more was measured. When the total number of particles is counted, the number of particles on the germanium wafer before and after the plasma etching is counted in 30 seconds, and the difference is made into a particle which is generated on the germanium wafer after the self-drilling film is generated after the endurance (after the virtual operation). Number (total). In addition, the evaluation of the number of occurrences of the particles was carried out by calculating the relative value when the total number of particles of the sprayed film of No. 1 made of 100% bismuth was set to 100 (reference).

The number "A" in the column of the number of particles [1] indicates the number of particles (phase When the value is less than 1, "B" indicates that the number of particles is 1 or more and does not reach 5, and "C" indicates that the number of particles is 5 or more and 15 or less, and "D" indicates the number of particles. In the case of 15 or more and less than 100, "E" indicates a case where the number of particles is 100 or more.

In addition, the number of particles of the spray coating obtained from the materials of the reference A and B is the value measured by the particles having a particle diameter of about 0.2 μm or more attached to the surface of the tantalum wafer by 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 each of the sprayed films was plasma-etched under the same conditions as above. The surface inspection apparatus made of KLA-Tencor was used to replace Surfscan SP5 with Surfscan SP5. Evaluation results at the time of measurement. Surfscan SP5 can detect particles with a diameter of 19 nm or more, and the number of particles [2] indicates the result of depositing on the germanium wafer with finer particles as the measurement target. When counting the total number of particles, count the number of particles on the germanium wafer before and after plasma etching for 30 seconds, and set the difference to the number of particles (total) deposited on the germanium wafer after the self-solation film is formed after endurance. . In addition, the evaluation of the number of occurrences of the particles was carried out by calculating the relative value when the total number of particles of the sprayed film of No. 1 made of 100% bismuth was set to 100 (reference).

"A" in the column of the number of particles [2] indicates that the number of particles (relative value) is less than 1, and "B" indicates that the number of particles is 1 or more and less than 5, and "C" indicates the number of particles. In the case of 5 or more and less than 15, "D" indicates that the number of particles is 15 or more and does not reach 100, and "E" indicates a case where the number of particles is 100 or more.

The column of "number of particles [3]" in Table 2 indicates the measurement for each melting The film is irradiated with the following conditions to apply ultrasonic waves, and the number of particles when the particles are actively released from the film is actively released.

Specifically, in the present example, the surface of the film to be coated with the member to be sprayed is mirror-polished, and then the four corners of the sprayed film are marked with a mark tape to prepare a test piece for exposing a spray film of 10 mm × 10 mm. Next, the test piece was placed on the upper electrode of the semiconductor device manufacturing apparatus, while the pressure in the chamber was maintained at 13.3 Pa, and the etching gas containing carbon tetrafluoride and oxygen in a specific ratio was supplied at a flow rate of 1 L/min to 13.56. A high frequency power of 700 W was applied at MHz for a total of 1 hour, and the test piece was exposed to the plasma. Subsequently, air was supplied to the chamber, and a frequency of 22 Hz was applied to the spray film of the test piece after the plasma exposure, and an ultrasonic wave of 400 W was output for 30 seconds to escape the particles from the spray film, and the particles in the air were measured by a counter. The measurement of the particles was carried out by using a particle counter (manufactured by PMS Co., Ltd., LASAIR) to measure the total number of particles having a diameter of 100 nm or more. As a result, the relative value when the total number of particles of the spray coating of No. 1 made of 100% bismuth was set to 100 (reference) was calculated and evaluated.

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

(Evaluation)

Understood from the results of Table 2 No.1, the apparent cause of the Y ₂ O ₃ formed by thermal spraying of spray material formed only by the nature of the spray film consists only of Y ₂ O _3, did not see the melting Further oxidative decomposition of Y ₂ O ₃ in the shot.

Further, as a result of Nos. 2 to 5, it is understood that YF ₃ or YOF is partially oxidized to Y ₂ O, which is formed of a molten film containing only YF ₃ or only a YOF or a mixed material containing the mixed phases. ₃ , but contains Y ₂ O ₃ . In particular, as a result of No. 3 and No. 4, it is understood that 10% by mass of YF ₃ contained in the molten material is oxidized to Y ₂ O ₃ , and when YF ₃ and YOF are mixed in the material for spraying, YOF is Oxidation stability is high and there is a tendency for YF _{3 to} preferentially oxidize.

Next, if the result of No.5 ~ 8, it is found that spraying of the material with yttrium oxyfluoride oxygen content of less than YOF of _{Y 7 O 6 F 9, Y} 6 O 5 F 8 and Y ₅ O ₄ F ₇ or the like is oxidized by the melt, and firstly changed to a more stable YOF phase, and Y ₂ O _{3 is} not directly formed. Further, in the case of the materials for the spraying of No. 6 to 8, it is understood that Y ₂ O ₃ is not formed in the molten film in the general atmospheric piezoelectric slurry spraying method of the present embodiment. In other words, it has been confirmed that the formation of Y ₂ O ₃ in the sprayed film can be suppressed by using a fluorinated fluorinated product having a ratio of oxygen containing less than YOF as a material for spraying.

About the number of particles [1]

Regarding the characteristics of the sprayed film, when the sprayed film consisting of only Y ₂ O _{3 is} No. 1, the number of particles generated in the plasma environment is (E) 100 (reference), and the area per unit area on the wafer The number of particles is approximately 500 to 1000 pieces/piece. In general, it is known that the oxidized coating of the yttrium oxide-based film is superior to the alumina-based spray coating, but in the present embodiment, the number of particles of the spray coating formed only by Y ₂ O ₃ is the largest. It is the worst result of plasma resistance in all sprayed films.

Further, in the case of the spray film of No. 2, the number of particles generated in the plasma environment is (D) 15 or more and less than 100, and the spray film of No. 2 is oxidized by YF ₃ in the spray material. The ratio of Y ₂ O ₃ is relatively large. Therefore, when it is exposed to the fluorine plasma, it is liable to cause deterioration and a brittle metamorphic layer is formed. Therefore, when it is exposed to the plasma environment by dry etching as follows, it is peeled off into particles and is easily deposited on the semiconductor substrate. Therefore, it was confirmed that the plasma corrosion resistance was lowered due to the inclusion of Y ₂ O ₃ in the sprayed film.

Further, about 90% or more of the particles to be measured are extremely fine particles which have hitherto been unmanageable in the range of 0.06 μm or more in diameter and less than 0.2 μm.

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

Further, the spray coating obtained by spraying the materials for spraying of Reference Examples A and B is presumed to contain both YOF and Y ₂ O ₃ . Further, from the comparison of the number of particles of Reference Examples A and B, it is understood that the Y ₂ O ₃ in the sprayed film greatly impairs the plasma corrosion resistance even if it is only increased in a small amount.

Further, as shown in Nos. 6 to 8, it is confirmed that the spray film is formed of only yttrium oxyfluoride without YF _{3 and} Y ₂ O _{3 ,} and the number of particles is (A) to (B). Less than 5, and suppressed to a very small amount. These sprayed films show a good value in which the porosity and the Vicat hardness are well balanced, and it can be said that a good melted film can be formed. Regarding these particles, it was confirmed that almost all of them were extremely small in diameter of 0.06 μm or more and less than 0.2 μm.

Further, it is known that the spray coatings of Nos. 9 and 10 formed by using Y ₇ O ₆ F ₉ and Y ₆ O ₅ F ₈ as the materials for spraying have a particle number of (A) of less than 1, and use of 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 the porosity, the coating film of No. 11 is further preferably further.

Further, regarding the spray coatings of Nos. 1 and 3 to 5, the main peak intensity of Y ₂ O _{3 was} confirmed, and as the ratio of Y ₂ O ₃ was decreased, the porosity was high and the Vicker hardness was lowered. However, regarding the spray film of No. 5, the values of the porosity and the Vicat hardness were remarkably improved. This is considered to be affected not only by the constitution of the crystal phase constituting the spray coating but also by the crystal phase constituting the material for the melt.

Therefore, after reviewing the crystal phase constituting the material for the melt, the following was found. That is, the cerium oxide contained in the material for spraying is directly contained in the molten film, so that the cerium oxide contained in the material for spraying is not preferable (refer to No. 1). Further, if the material for the spray contains barium fluoride, the number of particles generated in the plasma environment is more than that of the barium fluoride fluoride (refer to Nos. 2 to 4). In the case of cerium oxide and cerium fluoride, cerium oxide is less suitable for materials for spraying (refer to Nos. 1 to 2 and Reference Examples A and B above). On the other hand, when the fluorinated fluorinated material is contained in the material for the spray, it is preferable because the plasma corrosion resistance is good, in addition to the physical properties such as the porosity and the Vicat hardness of the sprayed film (refer to No. 3 to 8). .

From the above, it can be seen that the rare earth element oxide (in this case, cerium oxide) and the rare earth element fluoride (in this case, cesium fluoride) are relative to the rare earth element oxyhalide (in this case, bismuth oxide). In the case where the proportion of the fluoride is small, a spray coating having a good porosity and a Vicat hardness in addition to the plasma corrosion resistance can be formed. The relative intensity ratio of the crystal phases, that is, the intensity ratio [(I _B + I _C ) / I _A ] is preferably suppressed to less than, for example, 0.02. Further, the intensity ratio [(I _CB + I _CC ) / I _CA ] of the spray coating formed using such a material for spraying is preferably 0.45 or less.

About the number of particles [2]

As shown in Table 2, it was found that the evaluation result of the number of particles [2] was sufficiently consistent with the evaluation result of the number of particles [1]. Thus, it can be seen that the number of particles relatively reduced, in particular, by the spray film formed by spraying the material for spraying disclosed herein, compared with the spray film of No. 1 formed only of Y ₂ O ₃ Even if fine particles of 19 to 60 nm occur, they are suppressed to a small amount. The so-called particle size of 19 nm or more is the smallest particle size that can be measured at this stage, and it can be said that the fine particles slightly approach zero. Thereby, the spray film of the melted material of the material for spray disclosed herein exhibits high plasma corrosion resistance even if the detection limit accuracy of the particles is improved.

About the number of particles [3]

As shown in Table 2, it was found that the evaluation result of the number of particles [3] was sufficiently consistent with the evaluation results of the number of particles [1] [2]. However, the comparatively coarse particles whose particles are detected at the number of particles [3] of 100 nm or more can be distinguished as the critical value of A to D and become closer to E. That is, according to the number of particles [3], it can detect more coarse particles 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 possible to evaluate the source of the particles which may not actually occur but which may become particles later. The particle generation source is considered to be a sprayed film (deteriorated layer) which is deteriorated by irradiation of a halogen-based plasma, and may be a part of particles due to subsequent plasma etching. Thus, when the ultrasonic film is exposed to the molten film exposed to the halogen-based plasma, the plasma corrosion resistance of the sprayed film can be more accurately evaluated. Further, according to the number of particles [3], it is possible to predict the occurrence of particles originating from the sprayed film at the time of a large amount of processing of, for example, more than 2,000 wafers. Further, from the results of Table 2, for example, it was confirmed that the spray film of N0.6 to 8 can suppress the occurrence of particles when exposed to the halogen-based plasma more highly.

The specific examples of the present invention have been described in detail above, but these are merely illustrative and are not intended to limit the scope of the claims. The technology described in the patent application scope includes various changes and modifications to the specific examples described above.

Claims (11)

A material for spraying, which is a material for spraying a rare earth element oxyhalide (RE-OX) containing a rare earth element (RE), oxygen (O), and a halogen element (X) as a constituent element, and In the X-ray diffraction pattern of the material for the molten material, 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 are combined with the above-mentioned rare earth element oxygen halogenation. The intensity ratio [(I _B +I _C )/I _A ] of the peak intensity I _A of the main peak of the object is less than 0.02. A material for spraying according to claim 1, which substantially does not contain the aforementioned rare earth element halide. A material for spraying according to claim 1 or 2, which substantially does not contain the aforementioned rare earth element oxide. The material for spraying according to any one of claims 1 to 3, wherein, in the rare earth element oxyhalide, a molar ratio (X/RE) of the halogen element to the rare earth element is 1.1 or more. The material for spraying according to claim 4, wherein in the rare earth element oxyhalide, the molar ratio (X/RE) of the halogen element to the rare earth element is 1.3 or more and 1.39 or less. The material for a spray according to any one of claims 1 to 5, wherein, in the rare earth element oxyhalide, the molar ratio (O/RE) of the oxygen to the rare earth element is 0.9 or less. The material for spraying according to any one of claims 1 to 6, wherein the rare earth element is cerium, the halogen element is fluorine, and the rare earth oxyhalide It is a fluorinated fluoride. A spray film which is a melt of a material for a spray according to any one of claims 1 to 7. A molten film comprising a rare earth element oxyhalide (RE-OX) containing a rare earth element (RE), oxygen (O), and a halogen element (X) as a constituent element as a main component, and the X-ray is wound In the pattern, the peak intensity I _CB of the main peak of the rare earth element oxide and the peak intensity I _CC of the main peak of the rare earth element halide 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 film of claim 8 or 9, which is substantially free of the foregoing rare earth element oxide. A member with a spray coating comprising a spray coating according to any one of claims 8 to 10 on a surface of a substrate.