KR102542911B1 - Semiconductor manufacturing equipment including composite structures and composite structures - Google Patents

Abstract

It is an object of the present invention to provide a member for a semiconductor manufacturing apparatus and a semiconductor manufacturing apparatus capable of increasing low-particle generation.
A substrate;
a＝d·(h ² +k ² +l ² ) ^1/2 . (Equation 1)
(In Equation 1, d is the lattice spacing, (hkl) is the mirror index)
A composite structure having a lattice constant a greater than 12.080 Å calculated in has excellent particle resistance and is preferably used as a member for semiconductor manufacturing equipment.

Description

Semiconductor manufacturing apparatus having a composite structure and a composite structure

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

BACKGROUND OF THE INVENTION [0002] A technique for imparting a function to a substrate by coating the surface of the substrate with ceramics is known. For example, as a member for semiconductor manufacturing equipment used in a plasma irradiation environment, such as a semiconductor manufacturing equipment, what formed a film with high plasma resistance on the surface is used. For the film, 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) are used.

Examples of oxide-based ceramics include erbium oxide (Er ₂ O ₃ ) or Er ₃ Al ₅ O ₁₂ , gadolinium oxide (Gd ₂ O ₃ ) or Gd ₃ Al ₅ O ₁₂ , yttrium aluminum garnet (YAG: Y ₃ Al ₅ A proposal has been made to use a protective layer using O ₁₂ ) or Y ₄ Al ₂ O ₉ or the like (Patent Document 1). With miniaturization of semiconductors, particle resistance at a higher level is required for various members in semiconductor manufacturing equipment.

Japanese Patent Publication No. 2016-528380

The present inventors this time determined the lattice constant of a structure containing yttrium and aluminum oxide Y ₃ Al ₅ O ₁₂ (hereinafter abbreviated as “YAG”) as main components, and particle resistance, which is an index of particle contamination accompanying plasma corrosion. It was found that there is a correlation between the two, and a structure with excellent particle resistance was successfully fabricated.

Accordingly, an object of the present invention is to provide a composite structure excellent in particle resistance (low-particle generation). Moreover, it aims at the use of this composite structure as a member for semiconductor manufacturing equipment, and provision of the semiconductor manufacturing equipment using it.

And, the composite structure according to the present invention is a composite structure including a base material and a structure provided on the base material and having a surface, the structure containing Y ₃ Al ₅ O ₁₂ as a main component, and the following formula (1 ) is characterized in that the lattice constant a calculated from is greater than 12.080 Å.

a＝d·(h ² +k ² +l ² ) ^1/2 . (Equation 1)

In Equation 1, d is the lattice spacing and (hkl) is the mirror index.

In addition, the composite structure according to the present invention is used in an environment requiring particle resistance.

In addition, the semiconductor manufacturing apparatus according to the present invention is provided with the composite structure according to the present invention described above.

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

composite structure

The basic structure of the composite structure according to the present invention will be described using FIG. 1 . 1 is a schematic cross-sectional view of a composite structure 10 according to the present invention. The composite structure 10 consists of a structure 20 provided on a substrate 15, and the structure 20 has a surface 20a.

The structure 20 included in the composite structure according to the present invention is a so-called ceramic coating. By applying the ceramic coating, various physical properties and characteristics can be imparted to the base material 15 . In addition, in this specification, a structure (or ceramic structure) and a ceramic coating are used as the same meaning unless otherwise specified.

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

write

In the present invention, the substrate 15 is not particularly limited as long as it is used for that purpose, and is composed of alumina, quartz, alumite, metal or glass, and preferably includes alumina. According to a preferred embodiment of the present invention, the arithmetic average roughness Ra (JISB0601: 2001) of the surface of the substrate 15 on which the structure 20 is formed is, for example, less than 5 micrometers (μm), preferably less than 1 μm. , more preferably 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 present invention, YAG is a polycrystal.

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

In the present invention, as components that may be further included in the YAG structure, oxides such as yttrium oxide, scandium oxide, europium oxide, gadolinium oxide, erbium oxide, and ytterbium oxide, and fluorides such as yttrium fluoride and yttrium oxyfluoride 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 containing YAG as a main component with different compositions may be provided, and another layer, for example, a layer containing Y ₂ O ₃ may be provided between the substrate and the structure.

lattice constant

In the present invention, the structure containing YAG as a main component has a lattice constant a calculated from the above equation (1) greater than 12.080 Å. Thereby, particle resistance can be improved. According to a preferred aspect of the present invention, the lattice constant is preferably 12.100 Å or more, more preferably 12.120 Å or more. The upper limit of the lattice constant is not particularly limited and may be determined according to the required properties, but is, for example, 12.15 Å or less.

Although the lattice constant of the YAG sintered body depends on the production conditions, it is known that it is about 12.01 Å to 12.04 Å (Journal of Industrial Chemistry, Vol. 69, No. 6 (1966) P1112-1116, “Production and pressurization effect”). The present invention is a novel structure having a lattice constant greater than 12.080 Å, which has excellent particle resistance.

Here, the lattice constant is calculated by the following method. That is, X-ray diffraction (XRD) is performed on the structure 20 containing YAG as a main component on the substrate by θ-2θ scan by out-of-plane measurement. By XRD of the structure 20, in the cubic crystal of YAG, the peak at the diffraction angle 2θ = 18.1 ° attributed to the mirror index (hkl) = (211), the peak attributed to the mirror index (hkl) = (321) Peak at diffraction angle 2θ = 27.8°, peak at diffraction angle 2θ = 29.7° attributed to mirror index (hkl) = (400), peak at diffraction angle 2θ = 33.3° attributed to mirror index (hkl) = (420) For , the peak position (2θ) is measured. In addition, since the structure 20 in the present invention is a novel structure having a lattice constant greater than a = 12.080, the peak position 2θ attributed to each mirror index hlk actually measured by XRD is They are each shifted by 0.1 to 0.4 degrees to the lower angle side than the theoretical peak position (2θ) attributed to the exponent hkl. Subsequently, the lattice spacing d for each peak is calculated from Bragg's equation λ=2d·sinθ. Here, λ is the wavelength of the characteristic X-ray used in XRD. Finally, the lattice constant a in the cubic crystal for each peak is calculated from Formula 1, and the average value is taken as the lattice constant. In Formula 1, d is the lattice spacing, and (hkl) is the mirror index.

a＝d·(h ² +k ² +l ² ) ^1/2 . (Equation 1)

Procedures related to the measurement of other lattice constants are based on JISK0131.

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 shows little change in crystal structure even when it is fluorinated by exposure to such a fluorine-based plasma. Therefore, it is thought that it is possible to suppress the crystal structure change on the surface of the structure even during use exposed to corrosive plasma, and to realize a lower particle size.

According to one aspect of the present invention, when YAG included in the structure is a polycrystal, the average crystallite size is, for example, less than 100 nm, preferably less than 50 nm, more preferably less than 30 nm, most preferably is less than 20 nm. When the average crystallite size is small, particles generated by the plasma can be reduced.

In the present specification, "polycrystal" refers to a structure in which crystal grains are bonded and accumulated. It is preferable that substantially one crystal grain constitutes a crystal. The diameter of the crystal grains is, for example, 5 nanometers (nm) or more.

In the present invention, the crystallite size is measured by, for example, X-ray diffraction. As the average crystallite size, the crystallite size can be calculated by Scherrer's formula below.

D=Kλ/(βcosθ)

Here, D is the crystallite size, β is the peak half width (unit: radians (rad)), θ is the Bragg angle (unit: rad), and λ is the wavelength of the characteristic X-ray used for XRD.

In Scherrer's equation, 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 around the diffraction angle 2θ = 17.9 °, which is attributed to the mirror index (hkl) = (211) in the cubic crystal of YAG, and the mirror index (hkl) ) = (321), the peak around the diffraction angle 2θ = 27.6 °, the mirror index (hkl) = (400), the peak around the diffraction angle 2θ = 29.5 °, the mirror index (hkl) = (420) It is a peak around the diffraction angle 2θ = 33.1° to be attributed.

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

In the aspect in which YAG is a polycrystal, the distance between adjacent crystallites is preferably 0 nm or more and less than 10 nm. The interval between adjacent crystallites refers to the interval where crystallites are closest to each other, and does not include voids composed of a plurality of crystallites. The space|interval between crystallites can be calculated|required from the image obtained by observation using TEM.

penetration depth of fluorine

According to a preferred aspect of the present invention, when the structure provided in the composite structure according to the present invention is exposed to a specific fluorine-based plasma, the fluorine atom concentration at a predetermined depth from the surface is preferably smaller than a predetermined value. Particle resistance is exhibited. . The composite structure according to this aspect of the present invention, after being exposed to fluorine-based plasma under the following three conditions, satisfies the predetermined value of the fluorine atom concentration at depth from each surface shown below. In the present invention, tests exposed 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 it is assumed that the structure is used as a member such as a focus ring located around a silicon wafer in the chamber and exposed to a corrosive environment caused by radical and ion collisions. is a test condition. 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, and the structure is used as a side wall member located in a direction substantially perpendicular to the silicon wafer or a top plate member facing the silicon wafer in the chamber, with little ion collision, mainly These are test conditions that assume exposure to a corrosive environment caused by radicals. According to a preferred aspect of the present invention, the composite structure according to the present invention satisfies at least the predetermined value of the fluorine concentration in any one of these tests.

(1) Plasma exposure conditions

For a structure containing YAG as a main component on a substrate, the surface thereof is exposed to a plasma atmosphere using an inductively coupled reactive ion etching (ICP-RIE) apparatus. The conditions for forming the plasma atmosphere are the following three conditions.

Standard Plasma Test 1:

A mixed gas of 100 sccm of CHF ₃ and 10 sccm of O ₂ was used as a process gas, and the output power of the ICP coil was 1500 W and the bias output was 750 W.

Standard Plasma Test 2:

SF ₆ was 100 sccm as a process gas, and the power supply output was 1500 W for ICP coil output and 750 W for bias output.

Standard Plasma Test 3:

SF ₆ 100sccm as process gas, 1500W coil output for ICP as power output, and bias output OFF (0W). That is, high-frequency power for biasing the electrostatic chuck is not applied.

Common to standard plasma tests 1 to 3, the chamber pressure was 0.5 Pa and the plasma exposure time was 1 hour. The semiconductor manufacturing apparatus member is placed on a silicon wafer 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 by this condition.

(2) Method for measuring fluorine atom concentration in the depth direction on the surface of the structure

For the surfaces of the structures after standard plasma tests 1 to 3, atomic concentration (%) of fluorine (F) atoms versus sputtering time was determined by depth direction analysis using ion sputtering using X-ray photoelectron spectroscopy (XPS). measured. Subsequently, in order to convert the sputtering time into depth, the step difference (s) between the sputtered and non-sputtered areas was measured with a stylus-type surface profile measuring instrument. From the step (s) and the total sputter time (t) used for XPS measurement, the depth (e) for the sputter unit time is calculated by e=s/t, and the depth (e) for the sputter unit time is used to calculate the sputter time was converted to depth. Finally, the depth from the surface 20a and the fluorine (F) atom concentration (%) at the depth position were calculated.

In this aspect, after the standard plasma test 1 to 3, the composite structure according to the present invention satisfies the fluorine atom concentration at depth from each surface shown below.

After Standard Plasma Test 1:

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%. More preferably, at least either of F1 _30nm or F1 _20nm is 2% or less.

After Standard Plasma Test 2:

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 satisfies at least one of less than 3%. More preferably, F2 _30nm satisfies at least one of 1% or less and F2 _15nm 2% or less.

After Standard Plasma Test 3:

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 satisfies at least one of less than 9%. More preferably, F3 _20nm satisfies at least one of 7% or less and F3 _10nm 8% or less. More preferably, F3 _20nm satisfies at least one of 1% or less and F3 _10nm 2% or less.

Manufacture of composite structures

The composite structure according to the present invention can be formed, for example, by disposing fine particles such as a brittle material on the surface of a substrate and applying a mechanical impact force to the fine particles. Here, in the "applying mechanical impact force" method, a high-hardness brush or roller rotating at high speed, a piston moving up and down at high speed, or the like, using a compressive force by a shock wave generated during an explosion, or applying ultrasonic waves or a combination thereof.

In addition, 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 including brittle materials are dispersed in a gas is sprayed from a nozzle toward a substrate, and the fine particles collide with a substrate such as metal, glass, ceramics, or plastic, and the collision occurs. This is a method in which brittle material microparticles are deformed or crushed by an impact of the brittle material, and thereby bonded to form a structure containing the constituting material of the microparticles directly on a substrate, for example, as a layered structure or a film-like structure. According to this method, it is possible to form a structure at room temperature without particularly requiring a heating means or a cooling means, and it is possible to obtain a structure having a mechanical strength equal to or higher than that of a fired body. In addition, it is possible to variously change the density, mechanical strength, electrical characteristics, etc. of a structure by controlling the conditions for colliding the particles or the shape and composition of the particles.

In the present specification, "fine particles" refers to those having an average particle diameter of 5 micrometers (μm) or less as identified by particle size distribution measurement or a scanning electron microscope, when the primary particles are dense particles. When the primary particles are porous particles that are easily crushed by impact, it means that the average particle diameter is 50 μm or less.

In the present specification, "aerosol" refers to a meat mixture in which the above-mentioned fine particles are dispersed in a gas (carrier gas) such as helium, nitrogen, argon, oxygen, dry air, and a mixed gas containing these, , "aggregate" is included, but preferably refers to a state in which the fine particles are substantially independently dispersed. The gas pressure and temperature of the aerosol may be arbitrarily set in view of the physical properties of the structure to be obtained, but the concentration of particulates in the gas is at the time of ejection from the discharge port when the gas pressure is converted to 1 atm and the temperature is 20 degrees Celsius. It is preferably within the range of 0.0003 mL/L to 5 mL/L.

The process of aerosol deposition is usually carried out at room temperature, and it is possible to form a structure at a temperature sufficiently lower than the melting point of the particulate material, that is, several hundred degrees Celsius or less. In the present specification, “normal temperature” is a temperature significantly lower than the sintering temperature of ceramics, and substantially refers to a room temperature environment of 0 to 100°C. In the present specification, "powder" refers to a state in which the above-mentioned fine particles are naturally aggregated.

[Example]

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

As raw materials for the structures used in Examples, those shown in the table below were prepared.

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

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

As shown in the table, nitrogen (N ₂ ) or helium (He) is used for the carrier gas. An aerosol is obtained by mixing a carrier gas and raw material powder (raw material fine particles) in an aerosol generator. The resulting aerosol is sprayed from a nozzle connected to the aerosol generator toward a substrate disposed inside the film forming chamber by a pressure difference. At this time, the air in the film forming chamber is exhausted to the outside by a vacuum pump.

Sample

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

In addition, XRD was used for the measurement of the crystallite size. That is, "X'Pert PRO/manufactured by Panalytical" was used as the XRD device. As the XRD measurement conditions, the characteristic X-rays were CuKα (λ = 1.5418 Å), tube voltage 45 kV, tube current 40 mA, step size 0.0084 °, and time per step 80 seconds or more. As the average crystallite size, the crystallite size according to Scherrer's equation described above was calculated. 0.94 was used as the value of K in Scherer's equation.

The main component of the crystalline phase of YAG on the substrate was measured by XRD. As an XRD device, "X'Pert PRO/manufactured by Panalytical" was used. As the XRD measurement conditions, the characteristic X-rays were CuKα (λ = 1.5418 Å), tube voltage 45 kV, tube current 40 mA, step size 0.0084 °, and time per step 80 seconds or more. XRD analysis software "High Score Plus/Panalytical Manufacturing" was used for the calculation of the main component. It was calculated by the relative intensity ratio obtained when a peak search was performed for the diffraction peak using the quasi-quantitative value (RIR = Reference Intensity Ratio) described on the ICDD card. In addition, in the measurement of the main component of the YAG polycrystal in the case of a multilayer structure, it is preferable 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, for these samples 1 to 6, standard plasma tests 1 to 3 under the conditions described above were conducted, and particle resistance was evaluated after the tests in the following procedure. "Muc-21 Rv-Aps-Se/manufactured by Sumitomo Seimitsu Kogyo" was used for the ICP-RIE device. Common to standard plasma tests 1 to 3, the chamber pressure was 0.5 Pa and the plasma exposure time was 1 hour. The sample was placed on a silicon wafer adsorbed 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 by these conditions.

Measurement of lattice constant

Using X-ray diffraction, the lattice constant of YAG of the sample was evaluated in the following procedure. As an XRD device, "X'Pert PRO/manufactured by Panalytical" was used. As the XRD measurement conditions, the characteristic X-rays were CuKα (λ = 1.5418 Å), tube voltage 45 kV, tube current 40 mA, step size 0.0084 °, and time per step 80 seconds or more. In addition, in order to increase the measurement accuracy, it is more preferable to set the Time per Step to 240 seconds or more. In the cubic crystal of YAG, the peak at the diffraction angle 2θ = 18.1° attributed to the mirror index (hkl) = (211), the peak at the diffraction angle 2θ = 27.8° attributed to the mirror index (hkl) = (321), and the mirror For the peak at the diffraction angle 2θ = 29.7° attributed to the index (hkl) = (400) and the peak at the diffraction angle 2θ = 33.3° attributed to the mirror index (hkl) = (420), the peak position (2θ) is measured. do. In addition, since the structure 20 in the present invention is a novel structure having a lattice constant greater than 12.080, the peak position 2θ attributed to each mirror index hlk actually measured by XRD is hkl), respectively, shifted by 0.1 to 0.4° to the low angle side from the theoretical peak position (2θ). Subsequently, the lattice plane spacing (d) for each peak was calculated from Bragg's equation λ=2d·sinθ. Finally, the lattice constant a in the cubic crystal for each peak was calculated from (Equation 1), and the average value was used as the lattice constant.

a＝d·(h ² +k ² +l ² ) ^1/2 . (Equation 1)

The lattice constants of each sample were as shown in Table 2.

Measurement of penetration depth of fluorine

For the surfaces of samples 2, 4, 5, and 6 after standard plasma tests 1 to 3, X-ray photoelectron spectroscopy (XPS) was used to analyze the depth direction using ion sputter to determine the fluorine (F ) The atomic concentration (%) of atoms was measured. Subsequently, in order to convert the sputtering time into depth, the step difference (s) between the sputtered and non-sputtered areas was measured with a stylus-type surface profile measuring instrument. From the step (s) and the total sputter time (t) used for XPS measurement, the depth (e) for the sputter unit time is calculated by e=s/t, and the depth (e) for the sputter unit time is used to calculate the sputter time was converted to depth. Finally, the depth from the sample surface and the fluorine (F) atom concentration (%) at that depth were calculated.

The depth from the structure surface and the fluorine atom concentration after standard plasma tests 1 to 3 were as shown in the table below.

After Standard Plasma Test 1:

After Standard Plasma Test 2:

After Standard Plasma Test 3:

Further, when the above data is represented as a graph, it is as shown in FIGS. 2 to 4.

SEM phase

SEM images of the surface of the structure after standard plasma tests 1 to 3 were taken as follows. That is, the corrosion state of the plasma-exposed surface was evaluated using a scanning electron microscope (SEM). For SEM, "SU-8220/manufactured by Hitachi Seisakusho" was used. The accelerating voltage was 3 kV. The photograph of the result was as shown in FIG. 5 .

Evaluation of results

As shown in Table 2, in sample 6, where the lattice constant of the structure is 12.078 Å, which is smaller than 12.080 Å, the effect of plasma corrosion is large under any conditions of standard plasma tests 1 to 3, and the surface of the structure after the plasma test has a crater shape. Large recesses and a large number of fine irregularities superimposed on the recesses were confirmed, indicating low particle resistance.

On the other hand, in sample 5, where the lattice constant of the structure is 12.109 Å, which is greater than 12.100 Å, a plurality of large crater-shaped recesses were formed after standard plasma tests 1 and 2, but compared to sample 6, fine irregularities overlapped with the recesses. It can be seen that there is almost no silver, and corrosion in standard plasma test 3 is alleviated, and particle resistance is provided.

In Samples 2 and 4, where the lattice constants of the structures were 12.129 Å and 12.127 Å, respectively, and were larger than 12.120 Å, only a few large crater-shaped dents were confirmed in the plasma exposure after standard plasma tests 1 and 2. In addition, almost no corrosion was observed after the standard plasma test 3, indicating that it has very high particle resistance.

Claims (14)

A composite structure including 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% in terms of mass ratio, and the lattice constant a calculated from the following formula (1) is greater than 12.109 Å, Composite structures used in environments requiring particle resistance:
a＝d·(h ² +k ² +l ² ) ^1/2 . (Equation 1)
In Equation 1, d is the lattice spacing and (hkl) is the mirror index. According to claim 1,
A composite structure in which the ratio occupied by the main component is 100% in terms of mass ratio. According to claim 1,
The composite structure having the lattice constant of 12.120 Å or more. According to claim 1,
The composite structure having the lattice constant of 12.15 Å or more. According to any one of claims 1 to 4,
After the standard plasma test 1, the fluorine atom concentration F1 30 nm at a depth of 30 _nm from the surface of the structure 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% A composite structure, which satisfies at least one of According to claim 5,
A composite structure wherein at least either of the fluorine atom concentration F1 _{of 30 nm} or the fluorine atom concentration of _{20 nm} is 2% or less. According to any one of claims 1 to 4,
After the standard plasma test 2, the fluorine atom concentration F2 30 nm at a depth of 30 _nm from the surface of the structure 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%, either A composite structure that satisfies at least one of the following. According to claim 7,
The composite structure, wherein the fluorine atom concentration F2 _{of 30 nm} is 1% or less, or the fluorine atom concentration F2 _{of 15 nm} is 2% or less. According to any one of claims 1 to 4,
After the standard plasma test 3, the fluorine atom concentration F3 20 nm at a depth of 20 _nm from the surface of the structure 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% A composite structure, which satisfies at least one of According to claim 9,
The composite structure, wherein the fluorine atom concentration F3 _{of 20 nm} is 7% or less, or the fluorine atom concentration F3 _{of 10 nm} is 8% or less. According to claim 9,
The composite structure, wherein the fluorine atom concentration F3 _{of 20 nm} is 1% or less, or the fluorine atom concentration F3 _{of 10 nm} is 2% or less. According to any one of claims 1 to 4,
A composite structure that is a member for semiconductor manufacturing equipment. A semiconductor manufacturing apparatus provided with the composite structure according to any one of claims 1 to 4. delete

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