KR20180052517A - Structure - Google Patents

Abstract

It is an object of the present invention to provide a structure containing yttrium oxyfluoride and capable of increasing plasma resistance. Provided is the structure having a polycrystalline body of yttrium oxyfluoride having a rhombohedral crystal structure as a main component and an average crystallite size in the polycrystalline body being less than 100 nm, wherein the peak intensity of the rhombohedral body detected at about the diffraction angle 2θ=13.8° by X-ray diffraction is represented as r1, the peak intensity of the rhombohedral peak detected at around the diffraction angle 2θ=36.1° is defined as r2, and when the ratio γ1 is γ1(%)=r2/r1x100, the ratio γ1 is not less than 0% and less than 100%.

Description

Structure {STRUCTURE}

Embodiments of the present invention generally relate to structures.

BACKGROUND ART A member used under a plasma irradiation environment such as a semiconductor manufacturing apparatus and having a coating film with high plasma resistance formed on its surface is used. As the film, for example, an oxide such as alumina (Al ₂ O ₃ ), yttria (Y ₂ O ₃ ), or a nitride such as aluminum nitride (AlN) is used.

On the other hand, in the oxide-based ceramics according to the fluoride by the reaction of a CF-based gas, the membrane by a volume expansion and the like cracks, as a result, by that connection to the generation of particles, originally it has been fluoride yttrium with fluoride (YF _3), etc. (Patent Document 1).

Although YF ₃ has a high resistance to the F-system plasma, the coating film or the sintered body of yttrium oxyfluoride (YOF) is used because of the insufficient resistance to the Cl-based plasma or the chemical stability of the fluoride or the like (Patent Documents 2 and 3).

So far, YF ₃ and YOF have been studied in the thermal sprayed coating and the bulk coating. However, in the case of a thermal sprayed film or a bulk body, the plasma resistance may be insufficient, and it is required to further increase the plasma resistance.

For example, it has been studied to form a sprayed film using oxyfluoride of a rare earth element as a raw material (Patent Document 4). However, in thermal spraying, oxidation occurs by the oxygen in the atmosphere during heating. For this reason, Y ₂ O ₃ is mixed in the obtained thermal sprayed film and it is sometimes difficult to control the composition. In addition, there is still a challenge to the dense nature of the dry film. In plasma etching, when the YF ₃ coated chamber is used by spraying or the like, the etching rate drifts and is not stabilized (Patent Document 5). Further, a method of forming a film containing Y ₂ O ₃ and then subjecting the film to annealing by annealing such as plasma treatment has been studied (Patent Document 6). However, in this method, since a film containing Y ₂ O ₃ formed once is subjected to fluorination, the volume of the film may change due to fluorination, resulting in a problem that the film is peeled off from the substrate or a crack enters the film . In addition, it may be difficult to control the composition of the entire film. Further, in the sprayed or sintered body, F ₂ gas is released by thermal decomposition of the fluoride raw material fine particles during heating, and there is a problem in safety.

On the other hand, Patent Document 7 discloses that Y ₂ O ₃ can form a plasma-resistant structure at room temperature by an aerosol deposition method. However, the aerosol deposition method using yttrium oxyfluoride has not been sufficiently studied.

Japanese Patent Application Laid-Open No. 2013-140950 Japanese Patent Application Laid-Open No. 2014-009361 Japanese Patent Application Laid-Open No. 2016-098143 Japanese Patent No. 5927656 U.S. Patent Application Publication No. 2015/0126036 U.S. Patent Application Publication No. 2016/273095 Japanese Patent Application Laid-Open No. 2005-217351

In the case of a structure containing yttrium oxyfluoride, there is a case where variation in plasma resistance occurs.

An object of the present invention is to provide a structure capable of increasing plasma resistance.

The first invention is a structure having as a main component a polycrystal of yttrium oxyfluoride having a rhombohedral crystal structure and an average crystallite size of less than 100 nanometers in the polycrystalline structure, wherein X-ray diffraction shows a diffraction angle 2? = 13.8 (%) = R 2 / r 1 100 (%), where r 1 is the ratios of the rhombohedral positive peak intensity detected in the vicinity of the diffraction angle 2θ = 36.1 ° and r 2 is the peak intensity of the rhombohedral peak detected near the diffraction angle 2θ = , The ratio? 1 is 0% or more and less than 100%.

The second invention is the structure according to the first invention, wherein the ratio? 1 is less than 80%.

The present inventors have found that there is a correlation between the predetermined peak intensity ratio (ratio? 1) of the rhombohedral definite yttrium oxyfluoride and the plasma plasma performance. When the ratio? 1 is 100% or more, the plasma plasma performance is found to be lowered. By setting the ratio gamma 1 to be not less than 0% and less than 100%, preferably less than 80%, practically excellent plasma plasma performance can be exhibited.

A third aspect of the present invention is the first or second invention, wherein the structure further comprises yttrium oxyfluoride which does not contain yttrium oxyfluoride having a tetragonal crystal structure, or yttrium oxyfluoride having a tetragonal crystal structure, and has a diffraction angle 2θ = 16.1 2 is 0% or more and less than 100% when the square-law positive peak intensity detected in the vicinity of the rhombohedral is o and the square definition ratio with respect to the rhombus body is γ2 (%) = o / r1 × 100 .

The present inventors have found that there is a correlation between the ratio of the compound or crystal phase in the structure (ratio? 2) and the plasma resistance. When the ratio? 2 is 100% or more, the plasma resistance is found to be low. By setting the ratio? 2 from 0% to less than 100%, plasma resistance can be enhanced.

The fourth aspect of the present invention is the structure according to any one of the first to third aspects, wherein the yttrium oxyfluoride having a rhombohedral definite crystal structure is YOF.

A fifth aspect of the present invention is the structure according to the third aspect, wherein the yttrium oxyfluoride having a four-way crystal structure is YOF of 1: 1: 2.

According to these structures, the plasma resistance can be enhanced.

The sixth invention is the structure according to the third invention, wherein the ratio? 2 is 85% or less.

The seventh aspect of the invention is the structure according to the third aspect, wherein the ratio? 2 is 70% or less.

The eighth invention is the structure according to the third invention, wherein the ratio? 2 is 30% or less.

According to these structures, the plasma resistance can be further increased.

The ninth invention is the structure according to any one of the first to eighth aspects, wherein the average crystallite size is less than 50 nm.

The tenth aspect of the present invention is the structure according to any one of the first to eighth aspects, wherein the average crystallite size is less than 30 nm.

The eleventh invention is the structure according to any one of the first to eighth aspects, wherein the average crystallite size is less than 20 nanometers.

According to these structures, since the average crystallite size is small, the particles generated from the structure by the plasma can be made small.

The twelfth aspect of the present invention is the method according to any one of the first to eleventh aspects, wherein, when the peak intensity detected at the diffraction angle 2? = 29.1 占 by X-ray diffraction is?, The ratio of? And the ratio of? To r2 is less than 1%.

According to this structure, since the Y ₂ O ₃ contained in the structure is minute, the fluorination due to the CF-based plasma can be suppressed and the plasma resistance can be further enhanced.

In a thirteenth aspect of the present invention, in any one of the first to eleventh inventions, when the peak intensity detected in the vicinity of the diffraction angle 2? = 29.1 占 by X-ray diffraction is?, The ratio of? And the ratio of? To r2 is 0%.

According to this structure, since Y ₂ O ₃ is not substantially contained, fluorination by the CF-based plasma is suppressed, and the plasma resistance can be further enhanced.

(Effects of the Invention)

According to an aspect of the present invention, there is provided a structure including yttrium oxyfluoride having a rhombohedral crystal structure and capable of enhancing plasma resistance.

1 is a cross-sectional view illustrating a member having a structure according to an embodiment.
Figure 2 is a table illustrating the raw materials of the structure.
3 is a table illustrating a sample of the structure.
Figs. 4 (a) and 4 (b) are graphs showing X-ray diffraction in a sample of a structure. Fig.
Fig. 5 is a graph showing X-ray diffraction in a sample of a structure. Fig.
6 is a cross-sectional view illustrating a member having another structure according to the embodiment;
7 is a photograph showing a structure according to the embodiment.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the drawings, the same constituent elements are denoted by the same reference numerals, and a detailed description thereof will be appropriately omitted.

1 is a cross-sectional view illustrating a member having a structure according to an embodiment.

As shown in Fig. 1, the member 10 is a composite structure having the base material 15 and the structure 20, for example.

The member 10 is, for example, a member for a semiconductor manufacturing apparatus having a chamber, and is provided inside the chamber. Since gas is introduced into the chamber to generate plasma, the member 10 is required to have plasma resistance. The member 10 (structure 20) may be used outside the chamber, and the semiconductor manufacturing apparatus includes any semiconductor manufacturing apparatus (semiconductor processing apparatus) that performs processes such as annealing, etching, sputtering, and CVD . Further, the member 10 (structure 20) may be used for members other than the semiconductor manufacturing apparatus.

The substrate 15 includes, for example, alumina. However, the material of the substrate 15 is not limited to ceramics such as alumina, and may be quartz, alumite, metal, glass, or the like. In this example, the member 10 having the base material 15 and the structure 20 is described. Only the structure 20 without the substrate 15 is included in the embodiment. The arithmetic mean roughness Ra (JIS B0601: 2001) of the surface of the base material 15 (surface on which the structure 20 is formed) is less than 5 micrometers (탆), preferably less than 1 탆, More preferably less than 0.5 mu m.

The structure 20 includes a polycrystalline body of yttrium oxyfluoride having a rhombohedral crystal structure. The main component of the structure 20 is a polycrystal of yttrium oxyfluoride (YOF) having a rhombohedral crystal structure.

In the present specification, the main component of the structure refers to a compound that is contained in a relatively larger amount than other compounds contained in the structure 20 by quantitative or semi-quantitative analysis by X-ray diffraction (XRD) of the structure . For example, the main component is a compound which is the most included in the structure, and the ratio of the main component in the structure is greater than 50% by volume or mass ratio. The ratio of the main component is more preferably greater than 70%, and more preferably greater than 90%. The ratio of the main component may be 100%.

The yttrium oxyfluoride is a compound of yttrium (Y), oxygen (O) and fluorine (F). Examples of the yttrium oxyfluoride include YOF (molar ratio Y: O: F = 1: 1: 1) having a weight ratio of Y: O: F = 1: : 2). The range of Y: O: F = 1: 1: 2 in the present specification is not limited to the composition of Y: O: F exactly 1: 1: 2, and the molar ratio of fluorine to yttrium (F / Y) is greater than 1 and less than 3 may be included. Y ₅ O ₄ F ₇ (molar ratio of Y: O: F = 5: 4: 7) and Y ₆ O ₅ F ₈ (molar ratio: Y ₂ O ₃ ) are used as yttrium oxyfluoride of Y: O: F = 1: the Y: O: F = 6: 5: 8), Y 7 O 6 F 9 ( molar ratio of Y: O: F = 7: 6: 9), Y 17 O 14 F 23 ( a molar ratio of Y: O: F = 17: 14: 23). In the present specification, "YOF" means Y: O: F = 1: 1: 1 and "1: 1: 2 YOF" means Y: O: F = 1: 1: 2. Further, a composition other than the above may be included in the range of yttrium oxyfluoride.

In the example of Fig. 1, the structure 20 has a single-layer structure, but the structure formed on the substrate 15 may have a multi-layer structure (see Fig. 6). For example, a separate layer 22 (for example, a layer containing Y ₂ O ₃ ) is formed between the substrate 15 and the layer 21 corresponding to the structure 20 in FIG. 1 . The layer 21 corresponding to the structure 20 forms the surface of the multi-layered structure 20a.

The structure 20 is formed by a raw material containing, for example, yttrium oxyfluoride. This raw material is produced, for example, by fluorinating yttria. By this manufacturing process, raw materials are roughly classified into two types, one having a high oxygen content and one having a low oxygen content. The oxygen content of the raw material is large, for example, YOF, 1: 1: 2 of YOF _{(e.g., Y 5 O 4 F 7,} Y 7 O 6 F 9 , etc.) and a. The raw material having a high oxygen content may include only YOF. The raw material having a low oxygen content includes, for example, YF ₃ in addition to Y ₅ O ₄ F ₇ and Y ₇ O ₆ F _9, and does not include YOF. In the case of sufficient fluorination treatment, the raw material contains only YF ₃ and may not contain yttrium oxyfluoride. In this embodiment, the structure includes rhombohedral yttrium oxyfluoride. The fact that the raw material or the structure contains rhombohedral positive yttrium oxyfluoride means that a peak is detected in at least one of the vicinity of the diffraction angle 2θ = 13.8 ° and the vicinity of the diffraction angle 2θ = 36.1 ° in X-ray diffraction.

YF ₃ , Y ₅ O ₄ F ₇ , Y ₇ O ₆ F _9, and the like may be oxidized and converted to YOF over a long period of time in a structure used for a semiconductor manufacturing apparatus or the like. It is also reported that YOF is superior in corrosion resistance to other compositions (Patent Document 3).

The present inventors have found that there is a correlation between the plasma resistance and the crystal structure of the structure in a structure containing yttrium oxyfluoride as a main component and that the plasma resistance can be increased by controlling the crystal structure. The plasma resistance can be improved by controlling the crystal structure of the yttrium oxyfluoride contained in the structure.

Specifically, the crystal structure of the structure 20 according to the embodiment is as follows.

The structure 20 includes a polycrystalline body of yttrium oxyfluoride having a rhombohedral crystal structure. In the X-ray diffraction of the structure 20, the ratio? 1 of the rhombohedral positive peak intensity is 0% or more and less than 100%, preferably 80% or less.

Here, the ratio? 1 is calculated by the following method.

X-ray diffraction is performed on the structure 20 containing yttrium oxyfluoride on the substrate by the? -2? Scan. The peak intensity of the rhomboid, which is detected near the diffraction angle 2? = 13.8 占 by the X-ray diffraction of the structure 20, is referred to as r1. The peak intensity of the rhomboid body detected at the diffraction angle 2? = 36.1 占 by the X-ray diffraction of the structure 20 is r2. At this time,? 1 (%) = r2 / r1 100. For example, the ratio? 1 indicates the degree of orientation of rhombohedral yttrium oxyfluoride.

It is considered that the peak near the diffraction angle 2? = 13.8 ° and the peak near the diffraction angle 2? = 36.1 ° are caused, for example, by the rhombohedral definition YOF.

For example, the vicinity of the diffraction angle 2? = 13.8 ° is about 13.8 ± 0.4 ° (13.4 ° to 14.2 °) and the diffraction angle 2θ = 36.1 ° is about 36.1 ° ± 0.4 ° ° or less).

In addition, the structure 20 includes yttrium oxyfluoride having a rhombohedral crystal structure, and does not include yttrium oxyfluoride having a tetragonal crystal structure.

Alternatively, the structure 20 includes yttrium oxyfluoride having a rhombohedral crystal structure and yttrium oxyfluoride having a tetragonal crystal structure, wherein a square definition ratio? 2 to a rhombohedral structure is 0% or more and less than 100%.

Here, the ratio? 2 is calculated by the following method.

X-ray diffraction (X-ray diffraction) is performed on the structure 20 containing yttrium oxyfluoride on the substrate by θ-2θ scan. The peak intensity of the rhomboid that is detected near the diffraction angle 2? = 13.8 占 by X-ray diffraction is referred to as r1. The omnidirectional peak intensity detected at the diffraction angle 2? = 16.1 deg. By X-ray diffraction is defined as o. At this time,? 2 (%) = o / r1 × 100.

Further, it is considered that the peak near the diffraction angle 2? = 16.1 is due to the YOF (for example, at least any of four-sided positive Y ₅ O ₄ F ₇ or Y ₇ O ₆ F ₉ ) do.

Further, the vicinity of the diffraction angle 2? = 16.1 ° is, for example, about 16.1 ± 0.4 ° (15.7 ° or more and 16.5 ° or less).

The square definition ratio? 2 to the rhombohedral shape is preferably 85% or less, more preferably 70% or less, still more preferably 30% or less, and most preferably 0%. In the present specification,? 2 = 0% means that the lower limit of detection in the measurement is not more than 10%, and does not include yttrium oxyfluoride having a four-sided crystal structure.

In the polycrystal of yttrium oxyfluoride contained in the structure, the average crystallite size is, for example, less than 100 nm, preferably less than 50 nm, more preferably less than 30 nm, and most preferably less than 20 nm. By reducing the average crystallite size, the particles generated by the plasma can be reduced.

X-ray diffraction can be used for the determination of crystallite size.

The crystallite size can be calculated by the following Scherr's equation as the average crystallite size.

D = K? / (? Cos?)

Here, D is the crystallite size,? Is the peak half width (radian),? Is the Bragg's angle (rad), and? Is the wavelength of the X-ray used in the measurement.

In the Scherr equation,? Is calculated by? = (? Obs-? Std). ? obs is the half width of the X-ray diffraction peak of the test sample, and? std is the half width of the X-ray diffraction peak of the standard sample. K is a Scherr constant.

The X-ray diffraction peak that can be used for calculating the crystallite size in the yttrium oxyfluoride is, for example, a peak due to the mirror surface 006 near the diffraction angle 2? = 28 占 and a peak due to the diffraction angle 2? A peak attributed to the mirror surface 018 near the diffraction angle 2? = 47 占 and a peak attributable to the mirror surface 110 near the diffraction angle 2? = 48 degrees, and the like.

Further, the crystallite size may be calculated from an image such as a TEM observation. For example, the average crystallite size may be an average of the circle equivalent diameters of crystallites.

Further, the interval between adjacent crystallites is preferably 0 nm or more and less than 10 nm. The interval between adjoining crystallizers is the interval between crystallizers closest to each other and does not include voids composed of a plurality of crystallizers. The interval between crystallites can be obtained from an image obtained by observation using a transmission electron microscope (TEM). Fig. 7 shows a TEM image of an example of the structure 20 according to the embodiment. The structure 20 includes a plurality of crystallites 20c (crystal grains).

Also, for example, the structure 20 does not substantially contain Y ₂ O ₃ . The peak intensity due to Y ₂ O ₃ detected at the diffraction angle 2? = 29.1 ° when the X-ray diffraction is performed on the structure 20 on the substrate by θ-2θ scan is referred to as ε. At this time, at least one of the ratio of? To r1 (? / R1) and the ratio of? To r2 (? / R2) is less than 1%, and more preferably 0%. The structure 20 does not contain Y ₂ O ₃ , or the Y ₂ O ₃ contained in the structure 20 is so fine that fluorination by the CF-based plasma is suppressed, and the plasma resistance can be further increased. Further, the vicinity of 2? = 29.1 ° is, for example, about 29.1 ± 0.4 ° (28.7 ° or more and 29.5 ° or less).

The structure 20 according to the embodiment can be formed, for example, by disposing fine particles such as a brittle material on the surface of the base material 15 and imparting a mechanical impact force to the fine particles. Here, as the method of "imparting a mechanical impact force", for example, a brush or a roller of high hardness that rotates at a high speed, a piston which moves up and down at high speed, or the like may be used, a compression force by a shock wave generated at the time of explosion may be used, Acting on ultrasound, or a combination of these.

It is also preferable that the structure 20 according to the embodiment is formed by, for example, an aerosol deposition method.

The "aerosol deposition method" is a method in which "aerosol" in which fine particles containing a brittle material are dispersed in a gas is jetted from a nozzle toward a substrate, and fine particles are collided against a substrate made of metal, glass, ceramics or plastic, (For example, a layered structure or a film-like structure) containing the constituent material of the fine particles is directly formed on the substrate by deforming or crushing the brittle material fine particles by the impact of the fine particles. According to this method, it is possible to obtain a structure having a mechanical strength equal to or higher than that of the sintered body, which can form a structure at room temperature without requiring a heating means or a cooling means. Further, it is possible to variously change the density, mechanical strength, electrical characteristics, and the like of the structure by controlling the conditions for colliding the fine particles and the shape and composition of the fine particles.

In the present specification, the term " polycrystal " refers to a structure in which crystal grains are bonded and integrated. The crystal grains constitute substantially one crystal. The diameter of the crystal grain is, for example, 5 nanometers (nm) or more. However, when the fine particles are introduced into the structure without being broken, the crystal grains are, for example, polycrystals.

In the present specification, the term " fine particles " refers to particles having an average particle size of 5 micrometers (탆) or less when measured by particle size distribution measurement or scanning electron microscope when primary particles are dense particles. And when the primary particles are porous particles that are susceptible to fracture by impact, the average particle diameter is 50 탆 or less.

The term " aerosol " in the present specification refers to a solid / gas mixture body in which the above-described fine particles are dispersed in a gas (carrier gas) such as helium, nitrogen, argon, oxygen, dry air or a mixed gas containing them Quot; aggregate ", but actually refers to a state in which the fine particles are dispersed singly. The gas pressure and temperature of the aerosol are arbitrary, but the concentration of the fine particles in the gas is in the range of 0.0003 mL / L to 5 mL / L at the time of spraying from the discharge port when the gas pressure is converted into 1 atmosphere and the temperature is changed to 20 degrees Celsius Which is preferable in the formation of the structure.

The process of aerosol deposition is usually characterized by the fact that it is carried out at room temperature and that the structure can be formed at a temperature sufficiently lower than the melting point of the particulate material, that is, below 100 degrees Celsius.

In the present specification, the " normal temperature " means a significantly lower temperature than the sintering temperature of the ceramics, and substantially refers to a room temperature environment of 0 to 100 캜.

In the present specification, the term " powder " refers to a state where the above-mentioned fine particles coagulate naturally.

Hereinafter, the examination by the present inventors will be described.

Figure 2 is a table illustrating the raw materials of the structure.

In this study, eight kinds of powders of raw materials F1 to F8 shown in Fig. 2 are used. These raw materials are powders of yttrium oxyfluoride, YOF, and 1: 1: 2 of YOF (for _{example, Y 5 O 4 F 7,} Y 7 O 6 F 9 , etc.) includes at least one of a. Further, each raw material does not substantially contain YF ₃ and Y ₂ O ₃ .

The fact that YF ₃ is not substantially contained means that the peak intensity due to YF ₃ in the vicinity of the diffraction angle 2? = 24.3 ° or around 25.7 ° in the X-ray diffraction is within the vicinity of the diffraction angle 2θ = 13.8 ° or around 36.1 ° Is less than 1% of the peak intensity attributable to YOF. Or, is not substantially free of YF _3, the peak intensity due to the diffraction angle 2θ = 24.3 ° or near 25.7 ° near the YF ₃ in the X-ray diffraction, the diffraction angle 2θ = 32.8 ° 1 in the vicinity of 1: 2 < / RTI > of YOF. In addition, the vicinity of 2? = 24.3 ° is, for example, about 24.3 ± 0.4 ° (23.9 ° or more and 24.7 ° or less). 2θ = 25.7 ° is, for example, about 25.7 ± 0.4 ° (25.3 ° to 26.1 °). 2? = 32.8? Is, for example, about 32.8 占 .4 占 (about 32.4 占 to about 33.2 占).

The fact that Y ₂ O ₃ is not substantially contained means that the peak intensity due to Y ₂ O ₃ in the vicinity of the diffraction angle 2θ = 29.1 ° in the X-ray diffraction is smaller than the diffraction angle 2θ around 13.8 ° or around 36.1 ° Is less than 1% of the peak intensity attributable to YOF. Or, Y ₂ it does not include the O ₃ substantially, the X-ray diffraction peak intensity due to the diffraction angle 2θ = 29.1 ° the vicinity of the Y ₂ O _3, the diffraction angle 2θ = 32.8 ° 1 in the vicinity of 1: 2 < / RTI > of YOF.

The raw materials F1 to F8 differ from each other in particle diameter, as in the median diameter (D50 (mu m)) shown in Fig. The median diameter is a diameter of 50% in the cumulative distribution of the particle diameters of the respective raw materials. The diameter of each particle is determined by the circular approximation.

Samples of a plurality of structures (layered structures) were produced by varying the combination of these raw materials and film forming conditions (kind of carrier gas and flow rate), and the plasma resistance was evaluated. In this example, the aerosol deposition method is used for producing the sample.

3 is a table illustrating a sample of the structure.

As shown in FIG. 3, nitrogen (N ₂ ) or helium (He) is used as the carrier gas. The aerosol is obtained by mixing the carrier gas and the raw material powder (raw material fine particles) in the aerosol generator. The obtained aerosol is jetted from a nozzle connected to the aerosol generator by a pressure difference toward a substrate disposed inside the film-forming chamber. At this time, the air in the film formation chamber is exhausted to the outside by a vacuum pump. The flow rate of the carrier gas is 5 (liters / min: L / min) to 10 (L / min) for nitrogen and 3 (L / min) to 5 (L / min) for helium.

Each of the structures of Samples 1 to 10 mainly contained a polycrystalline body of yttrium oxyfluoride, and the average crystallite size in the polycrystalline body was less than 100 nm.

X-ray diffraction was used to measure the crystallite size.

As the XRD device, " X'PertPRO / panical agent " was used. Tube voltage 45kV, tube current 40mA, step size 0.033 °, time per step 336 seconds or more.

As the average crystallite size, crystallite size based on the above-mentioned Scherr's equation was calculated. 0.94 was used as the value of K in the Scherr equation.

X-ray diffraction was used to measure the crystal phase main component of oxyfluoride of yttrium. As the XRD device, " X'PertPRO / panical agent " was used. X-ray Cu-K alpha (wavelength: 1.5418 A), tube voltage of 45 kV, tube current of 40 mA, step size of 0.033 °, and time per step of 100 seconds or more. The calculation of the main component was made using XRD analysis software "High Score Plus". (RIR = Reference Intensity Ratio) of the ICDD card based on the relative intensity ratio obtained when a peak search is performed on the diffraction peak. Further, in the measurement of the main component of the oxyfluoride of yttrium in the case of the laminated structure, it is preferable to use the measurement result of the depth region of less than 1 mu m from the outermost surface by thin film XRD.

Further, the crystal structure of the oxyfluoride of yttrium was evaluated using X-ray diffraction. As the XRD device, " X'PertPRO / panical agent " was used. X-ray Cu-K alpha (wavelength 1.5418 A), tube voltage 45 kV, tube current 40 mA, and step size 0.033 deg. In addition, in order to increase the measurement accuracy, the time per step is preferably 700 seconds or more.

The ratio γ1 of the oxyfluoride of yttrium in relation to the rhombohedral positive peak intensity is determined by the peak intensity r1 due to the rhyme of oxyfluoride of yttrium near the diffraction angle 2θ = 13.8 ° and the diffraction angle 2θ = 36.1 ° Is calculated by r2 / r1 100 (%) using the peak intensity r2 attributable to the rhombohedral configuration of the oxyfluoride of yttrium in the vicinity.

In the oxyfluoride of yttrium, X-ray diffraction was used as described above for the measurement of the square definition ratio? 2 with respect to the rhombus. As the XRD device, " X'PertPRO / panical agent " was used. X-ray Cu-K alpha (wavelength 1.5418 A), tube voltage 45 kV, tube current 40 mA, and step size 0.033 deg. In addition, in order to increase the measurement accuracy, the time per step is preferably 700 seconds or more.

The square definition ratio? 2 with respect to the rhombohedral is defined as the peak intensity r1 due to the rhombohedral definite mirror surface 003 including the YOF and the like near the diffraction angle 2? = 13.8 占 and the peak intensity r1 near the diffraction angle 2? = 16.1 (O) / rhombohedral definite peak intensity (r1) by using the peak intensity (o) attributable to the quadrilateral positive mirror surface (100) including ₇ O ₆ F ₉ or Y ₅ O ₄ F ₇ ) X 100 (%).

4 (a), 4 (b) and 5 are graphs showing X-ray diffraction in a sample of a structure.

In each of Figs. 4 (a), 4 (b) and 5, the horizontal axis represents the diffraction angle 2?, And the vertical axis represents the intensity. As shown in Fig. 4 (a) and Fig. 5, samples 1 to 10 each contain rhombohedral definite yttrium oxyfluoride (e.g., YOF polycrystal) and each sample has a peak Pr1 is detected. Further, as shown in Fig. 4 (b), in each of the samples 3, 4, and 6 to 10, the peak Pr2 is detected near the diffraction angle 2? = 36.1 deg. In Samples 1 and 2, no peak is detected near the diffraction angle 2? = 36.1 °.

4 (a) and FIG. 5, Samples 3 to 7 are samples of tetragonal yttrium oxyfluoride (for example, at least any one of Y ₅ O ₄ F ₇ or Y ₇ O ₆ F ₉ ) , And a peak Po is detected in the vicinity of the diffraction angle 2 &thetas; = 16.1 DEG. In Samples 1, 2, and 8 to 10, no peak is detected near the diffraction angle 2? = 16.1 deg.

With respect to each sample, the peak intensities (r1 and r2) were calculated except for the background intensity in the data shown in Figs. 4 (a) and 4 (b) Is obtained. Further, with respect to each sample, the peak intensities (r1 and o) described above are calculated with the exception of the background intensity in the data shown in Fig. 5, and the quadrature positive ratio? 2 with respect to the rhombus body is obtained. The obtained ratio? 1 and ratio? 2 are shown in Fig.

As shown in Fig. 3, the ratio? 1 largely changes depending on the combination of the raw material and film forming conditions. The inventors of the present invention have obtained new knowledge that the orientation of the rhombohedral definite yttrium oxyfluoride is changed by the combination of raw materials and film forming conditions.

Also, the ratio? 2 greatly changes depending on the combination of the raw material and film forming conditions. The inventors of the present invention have found for the first time that the ratio of the compound in the structure is changed according to the film forming conditions and the like. For example, in the raw powder having a large oxygen content such as the raw materials F1 to F5, the square definition ratio? 2 to the rhombohedral is 50% or more and 100% or less. On the other hand, by the film formation in the aerosol deposition method, the ratio? 2 becomes 0% in the samples 1 and 2, and exceeds 100% in the sample 7.

Incidentally, in all of the samples 1 to 10, no peak of intensity was detected near the diffraction angle 2? = 29.1 °. That is, ratio of peak intensity to the peak intensity ε r1, except the intensity of the background (ε / r1) is 0%, the samples 1 to 10 did not include Y ₂ O _3.

In addition, the samples 1 to 7 were evaluated for plasma resistance.

A plasma etching apparatus and a surface shape measuring instrument were used to evaluate the plasma of oxyfluoride of yttrium.

&Quot; Muc-21 Rv-Aps-Se / Sumitomo Seimitsu Co., Ltd. " was used for the plasma etching apparatus. The conditions of the plasma etching were 1500W of ICP output, 750W of bias output, and a mixed gas of CHF ₃ 100ccm and O ₂ 10ccm as a process gas, a pressure of 0.5Pa, and a plasma etching time of 1 hour as power output.

&Quot; Surfcom 1500DX / Tokyo Seimitsu " was used for the surface roughness meter. The arithmetic average roughness (Ra) was used as an index of the surface roughness. A standard value suitable for the arithmetic mean roughness (Ra) of the measurement results in accordance with JIS B0601 was used as the cut off and the evaluation length in the measurement of the arithmetic mean roughness (Ra).

The plasma resistance was evaluated by the surface roughness change amount (Ra ₁ -Ra ₀ ) by using the surface roughness (Ra ₀ ) before the plasma etching of the sample and the surface roughness (Ra ₁ ) after the plasma etching of the sample .

Fig. 3 shows the evaluation results of plasma resistance. &Quot; o " indicates that the plasma is higher than the sintered body of yttria. &Quot; " indicates that the plasma resistance is higher than " ", and that the plasma is equivalent to or higher than the yttria structure produced by the aerosol deposition method. Indicates that the plasma resistance is lower than that of "? &Quot;, and that the plasma is equivalent to that of the sintered body of yttria. &Quot; x " indicates that the plasma resistance is lower than " DELTA ".

As shown in Fig. 3, the inventors of the present invention have found that there is a correlation between the plasma resistance and the ratio? 1. That is, in samples 6 and 7 having a ratio? 1 of 100% or more, plasma resistance is low. By controlling the ratio? 1 to less than 100% depending on film formation conditions and the like, the plasma resistance can be increased, and sufficient plasma resistance can be obtained practically.

By setting the ratio? 1 to less than 80%, the plasma resistance as in Samples 3, 4, 9, and 10 can be made higher than that of the sintered body of yttria.

By setting the ratio? 1 to 0%, the plasma resistance as in Samples 1, 2 and 8 can be increased to be equal to or higher than that of the yttria structure produced by the aerosol deposition method.

Further, as shown in Fig. 3, the inventors of the present invention found that there is a correlation between the plasma resistance and the ratio? 2. That is, in the sample 7 having the ratio? 2 of 106% or more, the plasma resistance is low. In the structure 20 according to the embodiment, by adjusting the film forming conditions and the like, the ratio? 2 is controlled to be less than 100%, whereby the plasma resistance can be enhanced and practically sufficient plasma resistance can be obtained.

By setting the ratio? 2 to 85% or less, preferably 70% or less, the plasma resistance can be increased to the equivalent of the sintered body of yttria as in Samples 5 and 6. [

By setting the ratio? 2 to 30% or less, the plasma resistance as in the samples 3 and 4 can be increased to the same level as the yttria structure by the aerosol deposition method.

By setting the ratio [gamma] 2 to 0%, plasma resistance can be further increased as in Samples 1 and 2.

Generally, when a structure of an oxide such as Al ₂ O ₃ or Y ₂ O ₃ is formed by an aerosol deposition method, it is known that the structure has no crystal orientation.

On the other hand, since YF ₃ or yttrium oxyfluoride has wall characteristics, for example, the fine particles of the raw material tend to be cracked along the cleaved surface due to the application of mechanical impact. Therefore, it is considered that the fine particles are cracked along the cleavage plane at the time of film formation by the mechanical impact force, and the structure is oriented in a specific crystal direction.

Further, when the raw material has wall characteristics, if the structure is damaged by the plasma irradiation, cracks are generated along the cleavage plane, and there is a fear that particles are generated starting from this. Therefore, at the time of forming the structure, the fine particles are crushed in advance along the cleavage plane to adjust the orientation. More specifically, the ratios? 1 and? 2 are adjusted. Thus, it is considered that the plasma resistance can be improved.

The embodiments of the present invention have been described above. However, the present invention is not limited to these techniques. It is within the scope of the present invention as long as the features of the present invention are provided to those skilled in the art regarding the above-described embodiments with appropriate design changes. For example, shapes, dimensions, materials, arrangements and the like of structures, substrates, and the like are not limited to those illustrated, and can be appropriately changed.

In addition, each element included in each of the above-described embodiments can be combined as far as technically possible, and any combination thereof is included in the scope of the present invention as long as it includes the features of the present invention.

10: member 15: substrate
20, 20a: Structure 20c: Crystallizer
Po, Pr1, Pr2: peak

Claims (13)

A structure having a polycrystalline body of yttrium oxyfluoride having a rhombohedral crystal structure as a main component and an average crystallite size in the polycrystalline body being less than 100 nm,
Ratios of the ratios of the ratios of the ratios of the rhombohedral bodies detected at about the diffraction angle 2? = 13.8 ° by X-ray diffraction are represented by r1, the ratios of the peaks of the ridge pyramids detected at around the diffraction angle 2? ? 1 (%) = r2 / r1 100, the ratio? 1 is 0% or more and less than 100%. The method according to claim 1,
Wherein the ratio? 1 is less than 80%. The method according to claim 1,
The structure comprises:
Does not include yttrium oxyfluoride having a tetragonal crystal structure, or
Wherein the quadratic positive peak intensity detected by X-ray diffraction near the diffraction angle 2? = 16.1 is represented by o and the quadrilateral positive definite ratio against the rhombohedral is represented by? 2 ( %) = o / r1x100, the ratio? 2 is 0% or more and less than 100%. 4. The method according to any one of claims 1 to 3,
Wherein the yttrium oxyfluoride having a rhombohedral crystal structure is YOF. The method of claim 3,
Wherein the yttrium oxyfluoride having a tetragonal crystal structure is a YOF of 1: 1: 2. The method of claim 3,
Wherein the ratio? 2 is 85% or less. The method of claim 3,
Wherein the ratio? 2 is 70% or less. The method of claim 3,
Wherein the ratio? 2 is 30% or less. 4. The method according to any one of claims 1 to 3,
Wherein the average crystallite size is less than 50 nanometers. 4. The method according to any one of claims 1 to 3,
Wherein the average crystallite size is less than 30 nanometers. 4. The method according to any one of claims 1 to 3,
Wherein the average crystallite size is less than 20 nanometers. 4. The method according to any one of claims 1 to 3,
At least one of the ratio of? With respect to r1 and the ratio of? With respect to r2 is less than 1% when the peak intensity detected in the vicinity of the diffraction angle 2? = 29.1? structure. 4. The method according to any one of claims 1 to 3,
, And the ratio of? With respect to r1 and the ratio of? With respect to r2 is 0% when the peak intensity detected at around the diffraction angle 2? = 29.1? structure.

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