JP7115582B2 - COMPOSITE STRUCTURES AND SEMICONDUCTOR MANUFACTURING EQUIPMENT WITH COMPOSITE STRUCTURES - Google Patents

Description

The present invention relates to a composite structure excellent in low-particle generation resistance, which is preferably used as a member of a semiconductor manufacturing apparatus, and a semiconductor manufacturing apparatus having the same.

A technique of coating the surface of a base material with ceramics to impart a function to the base material is known. For example, as a member for a semiconductor manufacturing apparatus used in a plasma irradiation environment such as a semiconductor manufacturing apparatus, a member having a surface coated with a highly plasma-resistant film is used. The coating includes, for example, oxide-based ceramics such as alumina (Al ₂ O ₃ ) and yttria (Y ₂ O ₃ ), and fluoride-based ceramics such as yttrium fluoride (YF ₃ ) and yttrium oxyfluoride (YOF). Used.

Furthermore _, oxide ceramics include erbium oxide _{( Er2O3} ) or _{Er3Al5O12 ,} gadolinium oxide _{( Gd2O3} ) or _{Gd3Al5O12 ,} yttrium aluminum garnet ₍ YAG: _Y3 Al ₅ O ₁₂ ) or Y ₄ Al ₂ O ₉ has been proposed as a protective layer (Patent Document 1). With the miniaturization of semiconductors, a higher level of particle resistance is required for various members in semiconductor manufacturing equipment.

Japanese translation of PCT publication No. 2016-528380

The present inventors recently investigated the hardness of a structure containing yttrium and aluminum oxide Y ₃ Al ₅ O ₁₂ (hereinafter abbreviated as “YAG”) as a main component, and an index of particle contamination accompanying plasma corrosion. We found that there is a correlation with a certain particle resistance, and succeeded in creating a structure with excellent particle resistance.

Accordingly, it is an object of the present invention to provide a composite structure with excellent low-particle generation resistance. A further object of the present invention is to use this composite structure as a member for semiconductor manufacturing equipment and to provide a semiconductor manufacturing equipment using the composite structure.

A composite structure according to the present invention is a composite structure comprising a substrate and a structure provided on the substrate and having a surface, wherein the structure contains Y ₃ Al ₅ O ₁₂ as a main component. and characterized in that its indentation hardness is greater than 8.5 GPa.

Also, the composite structure according to the present invention is used in an environment where particle resistance is required.

Further, a semiconductor manufacturing apparatus according to the present invention includes the composite structure according to the present invention.

1 is a schematic cross-sectional view of a member having a structure according to the invention; FIG. 4 is a graph showing the relationship between the depth from the structure surface and the fluorine atom concentration after standard plasma test 1; 10 is a graph showing the relationship between the depth from the surface of the structure and the concentration of fluorine atoms after standard plasma test 2; 10 is a graph showing the relationship between the depth from the surface of the structure and the concentration of fluorine atoms after standard plasma test 3; SEM images of the surface of the structure after standard plasma tests 1-3.

Composite Structure The basic structure of the composite structure according to the present invention will be explained with reference to FIG. FIG. 1 is a schematic cross-sectional view of a composite structure 10 according to the invention. The composite structure 10 comprises a structure 20 provided on a substrate 15, the structure 20 having a surface 20a.

The structure 20 that the composite structure according to the invention comprises is a so-called ceramic coat. Various physical properties and characteristics can be imparted to the substrate 15 by applying the ceramic coat. In this specification, the terms "structure (or ceramic structure)" and "ceramic coat" are used synonymously unless otherwise specified.

The composite structure 10 is provided, for example, inside a chamber of a semiconductor manufacturing apparatus having a chamber. SF-based or CF-based fluorine-based gas or the like is introduced into the chamber to generate plasma, and the surface 20a of the structure 20 is exposed to the plasma atmosphere. Therefore, the structure 20 on the surface of the composite structure 10 is required to have particle resistance. Also, the composite structure according to the present invention may be used as a member mounted outside the chamber. In this specification, the semiconductor manufacturing equipment using the composite structure according to the present invention is used to include any semiconductor manufacturing equipment (semiconductor processing equipment) that performs processes such as annealing, etching, sputtering, and CVD.

Substrate In the present invention, the substrate 15 is not particularly limited as long as it is used for its purpose, and is composed of alumina, quartz, alumite, metal, glass, etc., preferably alumina. According to a preferred embodiment of the present invention, the arithmetic mean roughness Ra (JISB0601:2001) of the surface of the substrate 15 on which the structures 20 are formed is, for example, less than 5 micrometers (μm), preferably less than 1 μm, more preferably less than 1 μm. is less than 0.5 μm.

Structure In the present invention, the structure contains YAG as a main component. Also, according to one aspect of the invention, the YAG is polycrystalline.

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

In the present invention, the components that the structure may contain in addition to YAG include oxides such as yttrium oxide, scandium oxide, eurobium oxide, gadolinium oxide, erbium oxide, and ytterbium oxide, yttrium fluoride, and yttrium oxyfluoride. Fluorides such as and may include two or more of these.

In the present invention, the structure is not limited to a single-layer structure, and may be a multi-layer structure. A plurality of layers mainly composed of YAG with different compositions may be provided, and another layer such as a layer containing Y ₂ O ₃ may be provided between the substrate and the structure.

Indentation Hardness In the present invention, the structure containing YAG as a main component has an indentation hardness of more than 8.5 GPa. Thereby, particle resistance can be improved. According to a preferred embodiment of the invention, the indentation hardness is 10 GPa or higher, more preferably 13 GPa or higher. The upper limit of the indentation hardness is not particularly limited and may be determined according to the required properties, but is, for example, 20 GPa or less.

Here, the indentation hardness of the structure is measured by the following method. That is, the hardness measurement is performed by a micro indentation hardness test (nanoindentation) on the surface of the structure containing YAG as a main component on the base material. The indenter is a Berkovich indenter, the indentation depth is set to a fixed value of 200 nm, and the indentation hardness (indentation hardness) _HIT is measured. A surface that excludes scratches and dents is selected as the _HIT measurement point on the surface. More preferably, the surface is a polished smooth surface. The number of measurement points shall be at least 25 points. The average value of 25 or more measured _HITs is defined as the hardness in the present invention. Other test and analysis methods, procedures for verifying the performance of test equipment, and conditions required for standard reference samples conform to ISO14577.

2. Description of the Related Art In a semiconductor manufacturing apparatus, highly corrosive fluorine-based plasma using a CF-based gas, an SF-based gas, or the like is used. The structure containing YAG as a main component according to the present invention undergoes little change in crystal structure even when exposed to such fluorine-based plasma and fluorinated. Therefore, it is thought that it is possible to suppress changes in the crystal structure of the surface of the structure even during use in which it is exposed to corrosive plasma, and to realize even lower particles.

According to one aspect of the invention, when the YAG contained in the structure is polycrystalline, its average crystallite size is for example less than 100 nm, preferably less than 50 nm, more preferably less than 30 nm, most preferably 20 nm is less than A small average crystallite size can reduce particles generated by plasma.

As used herein, the term "polycrystalline" refers to a structure formed by joining and accumulating crystal grains. It is preferable that the crystal grain constitutes a crystal substantially alone. The diameter of the crystal grains is, for example, 5 nanometers (nm) or more.

In the present invention, the crystallite size is measured, for example, by X-ray diffraction. As the average crystallite size, the crystallite size can be calculated by the following Scherrer formula.
D=Kλ/(β cos θ)
Here, D is the crystallite size, β is the peak half width (unit: radian (rad)), θ is the Bragg angle (unit: rad), and λ is the wavelength of the characteristic X-ray used for XRD. is.

In Scherrer's formula, β is calculated by β=(βobs−βstd). βobs is the half width of the X-ray diffraction peak of the measurement sample, and βstd is the half width of the X-ray diffraction peak of the standard sample. K is the Scherrer constant.

In YAG, the X-ray diffraction peak that can be used to calculate the crystallite size is the peak near the diffraction angle 2θ = 17.9 ° attributed to the Miller index (hkl) = (211) in the YAG cubic crystal, A peak near the diffraction angle 2θ = 27.6° attributed to the Miller index (hkl) = (321), a peak near the diffraction angle 2θ = 29.5° attributed to the Miller index (hkl) = (400), The peak near the diffraction angle 2θ=33.1° attributed to the Miller index (hkl)=(420).

Also, the crystallite size may be calculated from an image obtained by observation using a transmission electron microscope (TEM). For example, as the average crystallite size, the average value of equivalent circle diameters of crystallites can be used.

In embodiments where the YAG is polycrystalline, the spacing between adjacent crystallites is preferably 0 nm or more and less than 10 nm. The interval between adjacent crystallites is the interval at which the crystallites are closest to each other, and does not include voids composed of a plurality of crystallites. The distance between crystallites can be obtained from an image obtained by observation using a TEM.

Penetration Depth of Fluorine According to a preferred aspect of the present invention, the structure provided in the composite structure according to the present invention has a predetermined fluorine atomic concentration at a predetermined depth from the surface when exposed to a specific fluorine-based plasma. A value less than that indicates favorable particle resistance. A composite structure according to this aspect of the invention, after being exposed to a fluorine-based plasma under the following three conditions, satisfies the following predetermined fluorine atomic concentrations at depths from the surface, respectively: . In the present invention, the tests of exposure to fluorine-based plasma under the three conditions are referred to as standard plasma tests 1 to 3, respectively.

Standard plasma tests 1 to 3 assume various conditions assumed in semiconductor manufacturing equipment. Standard plasma tests 1 and 2 are conditions in which bias power is applied, and the structure is used as a member such as a focus ring located around the silicon wafer inside the chamber, and is exposed to a corrosive environment due to radical and ion collision. These are assumed test conditions. Standard plasma test 1 evaluates performance against CHF ₃ plasma, and standard plasma test 2 evaluates performance against SF ₆ plasma. On the other hand, the standard plasma test 3 is a condition in which no bias is applied. These test conditions assume exposure to a corrosive environment mainly due to radicals. According to preferred embodiments of the present invention, composite structures according to the present invention meet predetermined values for fluorine concentration in at least one of these tests.

(1) Plasma exposure conditions The surface of a structure containing YAG as a main component on a substrate is exposed to a plasma atmosphere using an inductively coupled reactive ion etching (ICP-RIE) apparatus. The plasma atmosphere is formed under the following three conditions.

Standard plasma test 1:
A mixed gas of 100 sccm CHF ₃ and 10 sccm O ₂ is used as the process gas, and the power output is 1500 W for the coil output for ICP and 750 W for the bias output.

Standard plasma test 2:
The process gas is SF ₆ of 100 sccm, the power output is 1500 W for ICP coil output, and 750 W for bias output.

Standard plasma test 3:
The process gas is SF ₆ of 100 sccm, the power output is 1500 W for the ICP coil output, and the bias output is OFF (0 W). In other words, the high-frequency power for biasing the electrostatic chuck is not applied.

Common to standard plasma tests 1 to 3, the chamber pressure is 0.5 Pa and the plasma exposure time is 1 hour. The member for a semiconductor manufacturing apparatus is made of silicon adsorbed by an electrostatic chuck provided in the inductively coupled reactive ion etching apparatus so that the surface of the structure is exposed to the plasma atmosphere formed under these conditions. Place on wafer.

(2) Method for measuring the concentration of fluorine atoms in the depth direction on the surface of the structure. The atomic concentration (%) of fluorine (F) atoms with respect to the sputtering time was measured by longitudinal analysis. Subsequently, in order to convert the sputtering time to the depth, the step (s) between the portion sputtered by ion sputtering and the portion not sputtered was measured with a stylus surface profiler. From the step (s) and the total sputtering time (t) used in the XPS measurement, the depth (e) for the unit time of sputtering is calculated by e=s/t, and the depth (e) for the unit time of sputtering is used to determine the sputtering time. was converted to depth. Finally, the depth from the surface 20a and the fluorine (F) atomic concentration (%) at that depth position were calculated.

In this embodiment, the composite structure according to the invention, after quasi-plasma tests 1-3 above, satisfies the following fluorine atomic concentrations at depths from the surface, respectively:

After standard plasma test 1:
At least either the fluorine atom concentration F1 ₃₀ nm at a depth of 30 nm from the surface is less than 3% or the fluorine atom concentration F1 _{20 nm} at a depth of 20 nm from the surface is less than 4% is satisfied. More preferably, at least either F1 _{30 nm} or F1 _{20 nm} is 2% or less.

After standard plasma test 2:
At least either the fluorine atom concentration F2 ₃₀ nm at a depth of 30 nm from the surface is less than 2% or the fluorine atom concentration F2 _{15 nm} at a depth of 15 nm from the surface is less than 3% is satisfied. More preferably, at least either F2 _{30 nm} is 1% or less or F2 _{15 nm} is 2% or less.

After standard plasma test 3:
At least either the fluorine atom concentration F3 ₂₀ nm at a depth of 20 nm from the surface is less than 8% or the fluorine atom concentration F3 _{10 nm} at a depth of 10 nm from the surface is less than 9% is satisfied. More preferably, at least either F3 _{20 nm} is 7% or less or F3 _{10 nm} is 8% or less. More preferably, at least either F3 _{20 nm} is 1% or less or F3 _{10 nm} is 2% or less.

Manufacture of Composite Structure The composite structure according to the present invention can be formed, for example, by arranging fine particles such as a brittle material on the surface of a base material and applying a mechanical impact force to the fine particles. Here, the method of "applying a mechanical impact force" includes using a high-hardness brush or roller that rotates at high speed, a piston that moves up and down at high speed, or the like, using compressive force due to a shock wave generated at the time of explosion, or , applying ultrasonic waves, or a combination thereof.

Also, the composite structure according to the present invention can be preferably formed by an aerosol deposition method. In the "aerosol deposition method", an "aerosol" in which fine particles containing brittle materials are dispersed in gas is sprayed from a nozzle toward the base material, and the fine particles collide with the base material such as metal, glass, ceramics, and plastic. The impact of this collision deforms or crushes the brittle material particles, thereby bonding them together to form a structure containing the constituent material of the particles on the base material, for example, as a layered structure or a film-like structure. This is a method of direct formation. According to this method, a structure can be formed at room temperature without the need for a heating means or a cooling means, and a structure having a mechanical strength equal to or greater than that of a sintered body can be obtained. In addition, by controlling the particle collision conditions, particle shape, composition, etc., it is possible to vary the density, mechanical strength, electrical properties, etc. of the structure.

In the present specification, the term "fine particles" refers to particles having an average particle diameter of 5 micrometers (μm) or less as identified by particle size distribution measurement, scanning electron microscopy, etc., when the primary particles are dense particles. . When the primary particles are porous particles that are easily crushed by impact, they have an average particle size of 50 μm or less.

In the present specification, the term "aerosol" refers to a solid-gas mixed phase body in which the above fine particles are dispersed in a gas (carrier gas) such as helium, nitrogen, argon, oxygen, dry air, and a mixed gas containing these. It also includes the case of including "aggregate", but preferably refers to a state in which fine particles are substantially dispersed singly. The gas pressure and temperature of the aerosol may be arbitrarily set in consideration of the physical properties of the desired structure. , preferably within the range of 0.0003 mL/L to 5 mL/L at the time of ejection from the ejection port.

The process of aerosol deposition is usually carried out at ambient temperature and allows the formation of structures at temperatures well below the melting point of the particulate material, ie several hundred degrees Celsius or less. In the specification of the present application, "normal temperature" means a room temperature environment of substantially 0 to 100° C., which is significantly lower than the sintering temperature of ceramics. In the specification of the present application, "powder" refers to a state in which the fine particles described above are naturally agglomerated.

The invention is further illustrated by the following examples, but the invention is not limited to these examples.

Materials shown in the table below were prepared as raw materials for the structures used in the examples.

In the table, the median diameter (D50 (μm)) is the diameter of 50% in the cumulative distribution of particle diameters of each raw material. For the diameter of each particle, the diameter determined by circular approximation was used.

A plurality of samples having structures on substrates were produced by changing combinations of these raw materials and film forming conditions (type and flow rate of carrier gas, etc.). The obtained samples were evaluated for particle resistance after standard plasma tests 1 to 3. Note that, in this example, the aerosol deposition method is used to prepare the sample.

As shown in the table, the carrier gas is nitrogen ( _N2 ) or helium (He). Aerosol is obtained by mixing carrier gas and raw material powder (raw material fine particles) in an aerosol generator. The resulting aerosol is sprayed from a nozzle connected to an aerosol generator by a pressure difference toward a substrate placed inside the film-forming chamber. At this time, the air in the film-forming chamber is exhausted to the outside by a vacuum pump.

Samples Each of the structures of Samples 1 to 6 obtained as described above contained YAG polycrystals as a main component, and the average crystallite size of the polycrystals was all less than 30 nm.

XRD was used to measure the crystallite size. That is, "X'PertPRO/manufactured by Panalytical" was used as the XRD apparatus. The XRD measurement conditions were a characteristic X-ray of CuKα (λ=1.5418 Å), a tube voltage of 45 kV, a tube current of 40 mA, a Step Size of 0.0084°, and a Time per Step of 80 seconds or more. As the average crystallite size, the crystallite size was calculated according to the above Scherrer formula. A value of 0.94 was used as the value of K in the Scherrer formula.

XRD was used to measure the main component of the YAG crystal phase on the substrate. As the XRD device, "X'PertPRO/manufactured by Panalytical" was used. The XRD measurement conditions were a characteristic X-ray of CuKα (λ=1.5418 Å), a tube voltage of 45 kV, a tube current of 40 mA, a Step Size of 0.0084°, and a Time per Step of 80 seconds or more. XRD analysis software "High Score Plus/manufactured by Panalytical" was used to calculate the main components. Using the semi-quantitative value (RIR=Reference Intensity Ratio) described in the ICDD card, it was calculated from the relative intensity ratio obtained when performing a peak search for diffraction peaks. In the measurement of the polycrystalline main component of YAG in the case of a laminated structure, it is desirable to use the measurement result of a depth region of less than 1 μm from the outermost surface by thin film XRD.

Standard Plasma Test Further, these samples 1 to 6 were subjected to the standard plasma tests 1 to 3 under the conditions described above, and the particle resistance after the tests was evaluated by the following procedure. As the ICP-RIE apparatus, "Muc-21 Rv-Aps-Se/manufactured by Sumitomo Seimitsu Kogyo Co., Ltd." was used. Common to standard plasma tests 1 to 3, the chamber pressure was 0.5 Pa and the plasma exposure time was 1 hour. A sample was placed on a silicon wafer attracted by an electrostatic chuck provided in an inductively coupled reactive ion etching apparatus so that the sample surface was exposed to the plasma atmosphere formed under these conditions.

Measurement of Indentation Hardness The indentation hardness of the structure on the base material was evaluated by the following procedure by a micro-indentation hardness test (nanoindentation). "ENT-2100/manufactured by Elionix" was used as a micro-indentation hardness tester (nanoindenter). As the conditions for the ultra-micro indentation hardness test, a Berkovich indenter was used as the indenter, the test mode was an indentation depth setting test, and the indentation depth was 200 nm. The indentation hardness (indentation hardness) _HIT was measured. The _HIT measurement points were set randomly on the surface of the structure, and the number of measurement points was at least 25 points. The average value of _HIT at 25 or more measured points was defined as hardness. The results were as shown in Table 2.

Depth profiling analysis using X-ray photoelectron spectroscopy (XPS) using ion sputtering for the surfaces of samples 2, 4, 5, and 6 after standard plasma tests 1-3. , the atomic concentration (%) of fluorine (F) atoms with respect to the sputtering time was measured. Subsequently, in order to convert the sputtering time to the depth, the step (s) between the portion sputtered by ion sputtering and the portion not sputtered was measured with a stylus surface profiler. From the step (s) and the total sputtering time (t) used in the XPS measurement, the depth (e) for the unit time of sputtering is calculated by e=s/t, and the depth (e) for the unit time of sputtering is used to determine the sputtering time. was converted to depth. Finally, the depth from the sample surface and the fluorine (F) atomic concentration (%) at that depth position were calculated.

標準プラズマ試験２後：

標準プラズマ試験３後：

The depth from the structure surface and fluorine atomic concentration after standard plasma tests 1-3 were as shown in the table below.
After standard plasma test 1:

After standard plasma test 2:

After standard plasma test 3:

Graphs of the above data are shown in FIGS.

SEM Images SEM images of the surfaces of structures after standard plasma tests 1-3 were taken as follows. That is, using a scanning electron microscope (SEM), evaluation was made from the corroded state of the plasma-exposed surface. The SEM used was "SU-8220/manufactured by Hitachi Ltd.". The acceleration voltage was set to 3 kV. A photograph of the result was as shown in FIG.

As shown in the result evaluation table 2, the indentation hardness of the structure is 8.4 GPa, and the sample 6, which is smaller than 8.5 GPa, has a large effect of plasma corrosion under any condition of the standard plasma tests 1 to 3. , On the surface of the structure after the plasma test, large crater-like depressions and many fine irregularities superimposed on the depressions were confirmed, indicating that the particle resistance is low.

On the other hand, in Sample 5, whose indentation hardness of the structure is 10.6 GPa, which is greater than 10 GPa, multiple large crater-shaped depressions were formed after the standard plasma tests 1 and 2, but compared to Sample 6, the number of depressions increased. There are almost no superimposed fine irregularities, and the corrosion in the standard plasma test 3 is moderate, indicating that it has particle resistance.

In Samples 2 and 4, where the indentation hardness of the structures is 13.8 GPa and 13.1 GPa, respectively, and greater than 13 GPa, a few large crater-like depressions on plasma exposure were observed after standard plasma tests 1 and 2. was only In addition, almost no corrosion was observed after the standard plasma test 3, indicating extremely high particle resistance.

After standard plasma test 1 with CHF ₃ gas, the atomic fluorine concentration F1 _{30 nm} at a depth of 30 nm from the surface is 0%, 0.26%, and 1.33% for samples 2, 4, and 5, respectively. and all were less than 3%. Also, the fluorine atom concentrations F1 _{20 nm} at a depth of 20 nm from the surface were 0.35%, 0%, and 1.97%, respectively, all of which were less than 4%. Samples 2, 4, and 5 were found to be less affected by plasma corrosion inside the structure. Moreover, in Samples 2 and 4, both F1 _{30 nm} and F1 _{20 nm} are 1% or less, and it can be seen that the influence of plasma corrosion on the inside of the structure is particularly small.

On the other hand, in sample 6, the fluorine atom concentration F1 _{30 nm} was as high as 3.85% and the fluorine atom concentration F1 _{20 nm} was as high as 4.97%, and plasma corrosion was confirmed inside the structure.

After standard plasma test 2 with SF ₆ gas and bias applied, fluorine atomic concentrations F _{30 nm} at a depth of 30 nm from the surface are 0%, 0%, and 0.90 for samples 2, 4, and 5, respectively. %, all less than 2%. Also, the fluorine atom concentrations F2 _{15 nm} at a depth of 15 nm from the surface were 0%, 0.37% and 1.15%, respectively, all of which were less than 3%. Samples 2, 4, and 5 were found to be less affected by plasma corrosion inside the structure. Moreover, in samples 2 and 4, both F2 _{30 nm} and F2 _{15 nm} are 1% or less, and it can be seen that the effect of plasma corrosion on the inside of the structure is particularly small.

On the other hand, in sample 6, the fluorine atom concentration F2 _{30 nm} was as high as 2.58% and the fluorine atom concentration F2 _{15 nm} was as high as 3.11%, confirming plasma corrosion inside the structure.

After standard plasma test 3 with SF ₆ gas and no bias applied, the fluorine atomic concentration F _{20 nm} at a depth of 20 nm from the surface is 0.55% and 0.45% for samples 2 and 4, respectively. , all of which were 1% or less. Also, the fluorine atom concentrations F3 _{10 nm} at a depth of 10 nm from the surface were 0.83% and 1.32%, respectively, both of which were 2% or less. It was found that samples 2 and 4 were particularly less affected by plasma corrosion inside the structure.

Sample 5 had a fluorine atom concentration F3 _{20 nm} of 6.65%, which was less than 8%. Also, the fluorine atom concentration F3 _{10 nm} was 7.15%, which was less than 9%. In sample 5, compared with samples 2 and 4, plasma corrosion inside the structure was confirmed.

On the other hand, in sample 6, the fluorine atom concentration F3 _{20 nm} is 8.09% and the fluorine atom concentration F3 _{10 nm} is 9.03%, which is the highest, indicating that the plasma corrosion inside the structure is large.

Based on the above results, in Table 2 above, "◎" indicates that the effect of plasma corrosion was small in any of the standard plasma tests 1 to 3, and plasma corrosion was observed in any one of the standard plasma tests 1 to 3. A case where the influence was small was evaluated as "O", and a case where the plasma corrosion had an influence under any of the conditions of the standard plasma tests 1 to 3 was evaluated as "X".

The embodiments of the present invention have been described above. However, the invention is not limited to these descriptions. Appropriate design changes made by those skilled in the art with respect to the above-described embodiments are also included in the scope of the present invention as long as they have the features of the present invention. For example, the shape, size, material, arrangement, etc. of the structure, base material, etc. are not limited to those exemplified and can be changed as appropriate. Moreover, each element provided in each of the above-described embodiments can be combined as long as it is technically possible, and a combination of these is also included in the scope of the present invention as long as it includes the features of the present invention.

DESCRIPTION OF SYMBOLS 10... Composite structure, 15... Base material, 20... Structure, 20a... Surface of structure

Claims (13)

A composite structure comprising a substrate and a structure provided on the substrate and having a surface,
The structure contains Y ₃ Al ₅ O ₁₂ as a main component, the proportion of the main component in the structure is greater than 90% by weight, and the indentation hardness is greater than 13 GPa, the particle resistance Composite structures used in environments where 2. The composite structure according to claim 1, wherein the main component accounts for 100% by weight. 3. The composite structure according to claim 1 or 2 , wherein said indentation hardness is 20 GPa or less. A composite structure according to any one of claims 1 to 3, wherein said structure has an average crystallite size of less than 50 nm. After the standard plasma test 1, the fluorine atomic concentration F1 ₃₀ nm at a depth of 30 nm from the surface of the structure is less than 3%, or the fluorine atomic concentration F1 _{20 nm} at a depth of 20 nm from the surface is less than 4%, The composite structure according to any one of claims 1 to 4 , satisfying at least one of 6. The composite structure according to claim 5 , wherein at least one of said fluorine atom concentration F1 _{30 nm} and said fluorine atom concentration F1 _{20 nm} is 2% or less. After the standard plasma test 2, the fluorine atomic concentration F2 _30nm at a depth of 30nm from the surface of the structure is less than 2%, or the fluorine atomic concentration F2 _15nm at a depth of 15nm from the surface is less than 3%, The composite structure according to any one of claims 1 to 4 , satisfying at least one of 8. The composite structure according to claim 7 , wherein at least one of the fluorine atom concentration F2 _{30 nm} is 1% or less, or the fluorine atom concentration F2 _{15 nm} is 2% or less. After standard plasma test 3, the fluorine atomic concentration F3 _20nm at a depth of 20nm from the surface of the structure is less than 8%, or the fluorine atomic concentration F3 _10nm at a depth of 10nm from the surface is less than 9%, The composite structure according to any one of claims 1 to 4 , satisfying at least one of 10. The composite structure according to claim 9 , wherein at least one of the fluorine atom concentration F3 _{20 nm} is 7% or less, or the fluorine atom concentration F3 _{10 nm} is 8% or less. 10. The composite structure according to claim 9 , wherein at least one of the fluorine atom concentration F3 _{20 nm} is 1% or less, or the fluorine atom concentration F3 _{10 nm} is 2% or less. The composite structure according to any one of claims 1 to 11, which is a member for semiconductor manufacturing equipment. A semiconductor manufacturing apparatus comprising the composite structure according to any one of claims 1 to 12 .

Images