Composite structures and semiconductor manufacturing apparatus equipped with composite structures

Abstract

To provide semiconductor manufacturing equipment components and semiconductor manufacturing equipment capable of improving low-particle generation.SOLUTION: A composite structure 10 has a base material 15 and a structure 20 having a surface on the base material 15 that is exposed to a plasma atmosphere. The structure contains Y4Al2O9 as a major component and the lattice constant and / or the intensity ratio of certain peaks in the X-ray diffraction meet certain conditions.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a composite structure with excellent particle resistance (low-particle generation), which is preferably used as a component for semiconductor manufacturing equipment, and to a semiconductor manufacturing equipment equipped therewith. [Background technology]

[0002] A technique is known in which ceramics are coated onto the surface of a substrate to impart functionality to it. For example, components for semiconductor manufacturing equipment used in plasma irradiation environments, such as semiconductor manufacturing equipment, have a highly plasma-resistant coating formed on their surface. The coating can be made of oxide ceramics such as alumina (Al2O3) or yttria (Y2O3), or fluorides such as yttrium fluoride (YF3) or yttrium oxyfluoride (YOF).

[0003] Furthermore, oxide-based ceramics include erbium oxide (Er2O3) or Er3Al5O 12 , gadolinium oxide (Gd2O3) or Gd3Al5O 12 Yttrium aluminum garnet (YAG:Y3Al5O 12 Alternatively, proposals have been made to use a protective layer made of Y4Al2O9 or the like (Patent Documents 1 to 3). With the miniaturization of semiconductors, higher levels of particle resistance are required for various components in semiconductor manufacturing equipment. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Special Publication No. 2016-528380 [Patent Document 2] Special Publication No. 2020-172702 [Patent Document 3] Special Publication No. 2017-514991 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] The inventors have now discovered a correlation between the lattice constant of a structure containing yttrium and aluminum oxide Y4Al2O9 (hereinafter abbreviated as "YAM") as the main component and particle resistance, which is an indicator of particle contamination associated with plasma corrosion, and have succeeded in creating a structure with excellent particle resistance.

[0006] Furthermore, the inventors have found a correlation between the intensity ratio of X-ray diffraction peaks at diffraction angles attributed to two specific Miller indices in the YAM monoclinic crystal, and particle resistance, in structures containing YAM as the main component. The present invention is also based on these findings.

[0007] Therefore, the present invention aims to provide a composite structure with excellent particle resistance (low-particle generation). Furthermore, it aims to provide this composite structure as a component for semiconductor manufacturing equipment, and semiconductor manufacturing equipment using it. [Means for solving the problem]

[0008] Furthermore, the composite structure according to the present invention is a composite structure comprising a base material and a structure provided on the base material and having a surface, wherein the structure contains Y4Al2O9 as a main component, and the lattice constant calculated by the following formula (1) satisfies at least one of a>7.382, b>10.592, and c>11.160.

number

[0009] In addition, the composite structure according to the present invention is a composite structure including a substrate and a structure provided on the substrate and having a surface, wherein the structure contains Y4Al2O9 as a main component, and the peak intensity ratio γ calculated by the following formula (2) is 1.15 or more and 2.0 or less. γ = β / α ··· (2) (In formula (2), α is the intensity of the peak with a diffraction angle 2θ = 29.6° attributed to the Miller index (hkl) = (122) in monoclinic Y4Al2O9, and β is the intensity of the peak with a diffraction angle 2θ = 30.6° attributed to the Miller index (hkl) = (211).)

[0010] The composite structure according to the present invention is also used in an environment where particle resistance is required.

[0011] Furthermore, the semiconductor manufacturing apparatus according to the present invention includes the composite structure according to the above-mentioned present invention.

Brief Description of the Drawings

[0012] <000​​​​​​​​​​​​​​​​​​​​

[0014] The structure 20 included in the composite structure according to the present invention is a so-called ceramic coat. By applying the ceramic coat, various physical properties and characteristics can be imparted to the base material 15. In this specification, the structure (or ceramic structure) and the ceramic coat are used synonymously unless otherwise specified.

[0015] The composite structure 10 is provided, for example, inside a chamber of a semiconductor manufacturing apparatus having a chamber. The composite structure 10 may form the inner wall of the chamber. Inside the chamber, a fluorine-based gas such as an SF-based or CF-based gas is introduced 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. Further, 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 in the meaning of including any semiconductor manufacturing apparatus (semiconductor processing apparatus) that performs processes such as annealing, etching, sputtering, and CVD.

[0016] Base material In the present invention, the base material 15 is not particularly limited as long as it is used for its intended purpose, and is composed of, for example, alumina, quartz, anodized aluminum, metal, or glass, and is preferably composed of alumina. According to a preferred embodiment of the present invention, the arithmetic mean roughness Ra (JIS B0601: 2001) of the surface on which the structure 20 of the base material 15 is formed is, for example, less than 5 micrometers (μm), preferably less than 1 μm, and more preferably less than 0.5 μm.

[0017] structure In the present invention, the structure contains YAM as a main component. According to one embodiment of the present invention, YAM is a polycrystal.

[0018] In the present invention, the main component of a structure refers to a compound that is present in relatively greater amounts than other compounds in the structure 20, as determined by quantitative or semi-quantitative analysis of the structure by X-ray diffraction (XRD). For example, the main component is the compound present in the largest amount in the structure, and the proportion of the main component in the structure is greater than 50% by volume or mass. More preferably, the proportion of the main component is greater than 70%, and it is also preferable that it is greater than 90%. The proportion of the main component may be 100%.

[0019] In the present invention, components that the structure may contain in addition to YAM include oxides such as yttrium oxide, scandium oxide, eurobium oxide, gadolinium oxide, erbium oxide, and ytterbium oxide, and fluorides such as yttrium fluoride and yttrium oxyfluoride, and may contain two or more of these.

[0020] In the present invention, the structure is not limited to a single-layer structure, but may also be a multi-layer structure. It may have multiple layers mainly composed of YAM with different compositions, and another layer, such as a layer containing Y2O3, may be provided between the substrate and the structure.

[0021] Lattice constant In the present invention, a structure containing YAM as the main component is said to satisfy at least one of the following conditions for the lattice constant a calculated by formula (1) above: a>7.382, b>10.592, c>11.160. This makes it possible to improve particle resistance. According to a preferred embodiment of the present invention, the lattice constant is preferably a > 7.393, b > 10.608, c > Satisfying at least one of 11.179, more preferably a > 7.404, b > 10.627, c > Satisfying at least one of 11.192. More preferably, a is 7.430 or higher and / or c is 11.230 or higher.

[0022] According to the ICDD card (reference code: 01-083-0933), the lattice constants of YAM are a=7.3781(Å), b=10.4735(Å), and c=11.1253(Å). The present invention is a novel composite structure in which lattice constants a, b, and c satisfy at least one of a>7.382, b>10.592, and c>11.160, and which has excellent particle resistance.

[0023] Here, the lattice constant is calculated by the following method. Specifically, X-ray diffraction (XRD) is performed on a structure 20 containing YAM as the main component on the substrate using an out-of-plane θ-2θ scan. By XRD on the structure 20, the peak positions (2θ) are measured for the peak at a diffraction angle 2θ = 26.7° attributed to Miller index (hkl) = (013), the peak at a diffraction angle 2θ = 29.6° attributed to Miller index (hkl) = (122), and the peak at a diffraction angle 2θ = 30.6° attributed to Miller index (hkl) = (211) in the monoclinic form of YAM. Furthermore, since the structure 20 in this invention is a novel structure with lattice constants greater than a=7.3781, b=10.4735, and c=11.1253, the peak positions (2θ) assigned to each Miller index (hlk) actually measured by XRD are shifted by 0.1 to 0.4° to the lower angle side compared to the theoretical peak positions (2θ) assigned to each Miller index (hkl). Next, the lattice plane spacing (d) for each peak is calculated using Bragg's equation λ=2d·sinθ, where λ is the wavelength of the characteristic X-ray used in the XRD. Finally, the lattice constants a, b, and c are calculated using Equation 1, where d is the lattice plane spacing and (hkl) is the Miller index. Also, β=108.54° was used in the calculation of the lattice constants a, b, and c. Other than that, the measurement of the lattice constants conforms to JIS K0131.

number

[0024] Peak intensity ratio According to one aspect of the present invention, in the monoclinic form of YAM, when the intensity of the peak near the diffraction angle 2θ = 29.6°, which is attributed to Miller index (hkl) = (122), is α, and the intensity of the peak near the diffraction angle 2θ = 30.6°, which is attributed to Miller index (hkl) = (211), is β, the peak intensity ratio calculated as γ = β / α is greater than 1.1. This improves particle resistance. According to a preferred aspect of the present invention, the peak intensity ratio γ is 1.2 or greater, more preferably 1.3 or greater.

[0025] According to another aspect of the present invention, independently of or in addition to the conditions defined by formula (1) above, a structure containing YAM as a main component has excellent particle resistance if the peak intensity ratio γ calculated by the following formula (2) is 1.15 or more and 2.0 or less. That is, a composite structure comprising a base material and a structure provided on the base material and having a surface, wherein the structure contains YAM as a main component and the peak intensity ratio γ calculated by the following formula (2) is 1.15 or more and 2.0 or less. γ = β / α ···(2) In equation (2), α is the intensity of the peak at a diffraction angle of 2θ = 29.6° in the monoclinic Y4Al2O9 crystal, which is attributed to Miller index (hkl) = (122), and β is the intensity of the peak at a diffraction angle of 2θ = 30.6°, which is attributed to Miller index (hkl) = (211).

[0026] In this invention, the "diffraction angle 2θ = 29.6° peak" means that, taking into account the influence of residual stress in the film due to manufacturing, an angular range is permitted during measurement, for example, a peak in the range of 29.6 ± 0.4° (29.2° to 30.0°) is permitted, and similarly, the "diffraction angle 2θ = 30.6°" means that a peak in the range of 30.6° ± 0.4° (30.2° to 31.0°) is permitted.

[0027] In a preferred embodiment of the present invention, the peak intensity ratio γ satisfies 1.20 or more, or 1.22 or more. It is more preferable that the peak intensity ratio γ satisfies 1.24 or more, or 1.30 or more. The upper limit of the peak intensity ratio γ is 2.0 or less, more preferably 1.80 or less.

[0028] The method for measuring the peak intensity ratio γ is preferably as follows: An XRD instrument is used, and the characteristic X-ray is set to CuKα (λ=1.5418 Å). In the monoclinic YAM, the intensity of the peak near the diffraction angle 2θ = approximately 29.6 ± 0.4° (29.2° to 30.0°) attributed to Miller index (hkl) = (122) is taken as α, and the intensity of the peak at the diffraction angle 2θ = approximately 30.6° ± 0.4° (30.2° to 31.0°) attributed to Miller index (hkl) = (211) is taken as β. The peak intensity ratio is calculated as γ = β / α. The intensities α and β at this time were calculated by profile fitting to the measured spectrum using the second derivative method. Furthermore, since the structure 20 in this invention is a novel structure with lattice constants greater than a=7.3781, b=10.4735, and c=11.1253, the peak positions (2θ) assigned to each Miller index (hlk) actually measured by XRD are shifted by 0.1 to 0.4° towards the lower angle side compared to the theoretical peak positions (2θ) assigned to each Miller index (hkl).

[0029] Fluorine penetration depth According to a preferred embodiment of the present invention, a composite structure comprising the present invention exhibits preferable particle resistance if, when exposed to a specific fluorine-based plasma, the fluorine atom concentration at a predetermined depth from the surface is less than a predetermined value. The composite structure according to this embodiment of the present invention satisfies the fluorine atom concentration at each of the depths from the surface shown below after being exposed to a fluorine-based plasma under the following two conditions. In the present invention, the tests of exposure to a fluorine-based plasma under the two conditions will be referred to as standard plasma tests 1 and 2, respectively.

[0030] Standard plasma tests 1 and 2 simulate various conditions expected within semiconductor manufacturing equipment. Standard plasma test 1 is a test condition in which bias power is applied, and the structure is used as a component 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 collisions. Standard plasma test 1 evaluates performance against SF6 plasma. On the other hand, standard plasma test 2 is a test condition in which no bias is applied, and the structure is used as a side wall component located approximately perpendicular to the silicon wafer inside the chamber, or as a top plate component facing the silicon wafer, and is exposed to a corrosive environment with few ion collisions and mainly due to radicals. According to a preferred embodiment of the present invention, the composite structure according to the present invention satisfies a predetermined value for fluorine concentration in at least one of these tests.

[0031] (1) Plasma exposure conditions For structures containing YAM as the main component on a substrate, the surface is exposed to a plasma atmosphere using an inductively coupled reactive ion etching (ICP-RIE) apparatus. The plasma atmosphere formation conditions are as follows:

[0032] Standard plasma test 1: The process gas used is SF6100 sccm, and the power output consists of a 1500W coil output for the ICP and a 750W bias output.

[0033] Standard plasma test 2: The process gas is SF6100 sccm, the power output is 1500W for the ICP coil, and the bias output is OFF (0W). In other words, no high-frequency power is applied to the electrostatic chuck bias.

[0034] Common to Standard Plasma Tests 1 and 2, the chamber pressure is 0.5 Pa and the plasma exposure time is 1 hour. The member for the semiconductor manufacturing apparatus 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 under this condition.

[0035] (2) Method for measuring the fluorine atom concentration in the depth direction on the surface of a structure For the surface of the structure after Standard Plasma Tests 1 to 2, the atomic concentration (%) of fluorine (F) atoms with respect to the sputtering time was measured by depth-direction analysis using ion sputtering with X-ray photoelectron spectroscopy (XPS). Subsequently, in order to convert the sputtering time into depth, the step (s) between the sputtered portion and the non-sputtered portion by ion sputtering was measured with a stylus surface profiler. The depth (e) per sputtering unit time was calculated as e = s / t from the step (s) and the total sputtering time (t) used for the XPS measurement, and the sputtering time was converted into depth using the depth (e) per sputtering unit time. Finally, the depth from the surface 20a and the atomic concentration (%) of fluorine (F) atoms at that depth position were calculated.

[0036] In this aspect, the composite structure according to the present invention satisfies the fluorine atom concentration at the depth from each of the following surfaces after the above-mentioned Standard Plasma Tests 1 and 2.

[0037] After Standard Plasma Test 1: The fluorine atom concentration F1 at a depth of 10 nm from the surface 10nm is less than 3.0%, more preferably, F1 10nm is 1.5% or less, and even more preferably, F1 10nm is 1.0% or less.

[0038] After Standard Plasma Test 2: The fluorine atom concentration F3 at a depth of 10 nm from the surface 10nm is less than 3.0%, more preferably, F3 10nm is 1.0% or less, and even more preferably, F3 10nm is 0.5% or less.

[0039] Manufacturing of composite structures The composite structure according to the present invention may be manufactured by various purposeful manufacturing methods, as long as a structure having the above-described lattice constant can be realized on a substrate. That is, it may be manufactured by a method that can form a structure containing Y4Al2O9 as the main component and having the above-described lattice constant on a substrate, for example, the structure can be formed on the substrate by physical vapor deposition (PVD) or chemical vapor deposition (CVD). Examples of PVD methods include electron beam physical vapor deposition (EB-PVD), ion beam assisted deposition (IAD), electron beam ion assisted deposition (EB-IAD), ion plating, and sputtering. Examples of CVD methods include thermal CVD, plasma CVD (PECVD), organometallic CVD (MOCVD), mist CVD, laser CVD, and atomic layer deposition (ALD). Furthermore, according to another aspect of the present invention, it can be formed by arranging fine particles of a brittle material or the like on the surface of a substrate and applying a mechanical impact force to the fine particles. Methods for "applying mechanical impact force" include using high-speed rotating, high-hardness brushes or rollers, or pistons that move up and down at high speed, utilizing the compressive force produced by shock waves generated during an explosion, applying ultrasound, or a combination of these.

[0040] Furthermore, the composite structure according to the present invention can preferably be formed by the aerosol deposition method (AD method). The AD method involves injecting an aerosol, which is a mixture of fine particles containing brittle materials such as ceramics dispersed in a gas, from a nozzle toward a substrate. The fine particles collide with the substrate, such as metal, glass, ceramics, or plastic, at high speed. The impact of this collision causes deformation and fracture of the brittle material fine particles, thereby joining them together and directly forming a structure (ceramic coating) containing the constituent materials of the fine particles on the substrate, for example, as a layered or film-like structure. This method does not require heating or cooling means, and the structure can be formed at room temperature, and a structure with mechanical strength equal to or greater than that of a fired body can be obtained. In addition, by controlling the conditions for impacting the fine particles, as well as the shape and composition of the fine particles, it is possible to vary the density, mechanical strength, and electrical properties of the structure in various ways. Furthermore, by setting the conditions described below to realize the composite structure according to the present invention, that is, so that the lattice constants a, b, and c calculated by equation (1) are satisfied, or so that the peak intensity ratio γ calculated by equation (2) is satisfied, the composite structure according to the present invention can be manufactured.

[0041] In this specification, "fine particles" means particles with an average particle size of 5 micrometers (μm) or less, as identified by particle size distribution measurement or scanning electron microscopy, when the primary particles are dense particles. When the primary particles are porous particles that are easily broken by impact, it means particles with an average particle size of 50 μm or less.

[0042] Furthermore, in this specification, "aerosol" refers to a solid-gas mixed phase in which the aforementioned fine particles are dispersed in a gas (carrier gas) such as helium, nitrogen, argon, oxygen, dry air, or a mixture of these gases, and also includes cases where "aggregates" are present, but preferably refers to a state in which the fine particles are substantially dispersed individually. The gas pressure and temperature of the aerosol may be set arbitrarily considering the physical properties of the desired structure, but the concentration of fine particles in the gas is preferably in the range of 0.0003 mL / L to 5 mL / L at the time of injection from the discharge port, when the gas pressure is converted to 1 atmosphere and the temperature to 20 degrees Celsius.

[0043] The aerosol deposition process is typically carried out at room temperature, and structures can be formed at a temperature well below the melting point of the particulate material, i.e., below several hundred degrees Celsius. In this specification, "room temperature" means a temperature significantly lower than the sintering temperature of the ceramics, and substantially refers to a room temperature environment of 0 to 100°C. In this specification, "powder" refers to the state in which the aforementioned particulate matter has naturally aggregated. [Examples]

[0044] The present invention will be further described by the following examples, but the present invention is not limited to these examples.

[0045] The materials used for the structures in the examples are shown in the table below. [Table 1]

[0046] In the table, the median diameter (D50 (μm)) is the diameter representing 50% of the cumulative particle size distribution for each raw material. The diameter of each particle was determined using a circular approximation.

[0047] Multiple samples were prepared by varying the combination of these raw materials and film formation conditions (type and flow rate of carrier gas, etc.) to create structures on substrates. The particle resistance of the obtained samples was evaluated after standard plasma tests 1 and 2. In this example, the aerosol deposition method was used to prepare the samples.

[0048] [Table 2]

[0049] As shown in the table, nitrogen (N2) or helium (He) is used as the carrier gas. The aerosol is obtained by mixing the carrier gas with the raw material powder (raw material fine particles) in the aerosol generator. The resulting aerosol is then injected from a nozzle connected to the aerosol generator towards the substrate placed inside the film-forming chamber due to the pressure difference. At this time, the air inside the film-forming chamber is exhausted to the outside by a vacuum pump.

[0050] sample Each of the structures obtained as described above contained polycrystalline YAM as its main component, and the average crystallite size in all of these polycrystalline structures was less than 30 nm.

[0051] XRD was used to measure the crystallite size. Specifically, the "X'PertPRO / Panalytical" XRD instrument was used. The XRD measurement conditions were as follows: characteristic X-ray CuKα (λ=1.5418Å), tube voltage 45kV, tube current 40mA, step size 0.0084°, and time per step 80 seconds or more. The average crystallite size was calculated using Scherrer's formula. A value of 0.94 was used for K in Scherrer's formula.

[0052] The main components of the crystalline phase of YAM on the substrate were measured by XRD. The XRD instrument used was "X'PertPRO / Panalytical". The XRD measurement conditions were: characteristic X-ray CuKα (λ=1.5418Å), tube voltage 45kV, tube current 40mA, step size 0.0084°, and time per step 80 seconds or more. The XRD analysis software "High Score Plus / Panalytical" was used to calculate the main components. The relative intensity ratio obtained by performing a peak search on the diffraction peak using the quasi-quantitative value (RIR = Reference Intensity Ratio) listed on the ICDD card was used. For polycrystalline YAM in the case of multilayer structures, it is desirable to use measurement results from a depth region of less than 1 μm from the outermost surface using thin-film XRD.

[0053] Standard plasma testing Furthermore, standard plasma tests 1 and 2 were performed on samples 1 to 5 under the conditions described above, and the particle resistance after these tests was evaluated using the following procedure. A "Muc-21 Rv-Aps-Se / Sumitomo Precision Products" ICP-RIE apparatus was used. For both standard plasma tests 1 and 2, the chamber pressure was 0.5 Pa and the plasma exposure time was 1 hour. The samples were placed on silicon wafers adsorbed by an electrostatic chuck provided in an inductively coupled reactive ion etching apparatus so that their surface was exposed to the plasma atmosphere formed under these conditions.

[0054] Measurement of fluorine penetration depth For the surface of samples after standard plasma tests 1 and 2, the atomic concentration (%) of fluorine (F) atoms relative to sputtering time was measured using X-ray photoelectron spectroscopy (XPS) for depth profiling with ion sputtering. A K-Alpha / Thermo Fisher Scientific XPS instrument was used. Next, to convert sputtering time to depth, the step difference (s) between the sputtered and unsputtered areas was measured using a stylus-type surface profile analyzer. From the step difference (s) and the total sputtering time (t) used for XPS measurement, the depth per unit time (e) was calculated using the formula e = s / t, and the sputtering time was converted to depth using this depth per unit time (e). Finally, the depth from the sample surface and the fluorine (F) atomic concentration (%) at that depth were calculated.

[0055] The depth from the structural surface and the fluorine atom concentration after standard plasma tests 1 and 2 were as shown in the table below. After standard plasma test 1: [Table 3] After standard plasma test 2: [Table 4]

[0056] Furthermore, the above data can be shown as graphs in Figures 2 and 3.

[0057] SEM image SEM images of the structure surface after standard plasma tests 1 and 2 were taken as follows. Specifically, the corrosion state of the plasma-exposed surface was evaluated using a scanning electron microscope (SEM). The SEM used was a "SU-8220 / Hitachi, Ltd." The acceleration voltage was set to 3kV. The resulting images are shown in Figure 4.

[0058] Surface roughness (arithmetic mean height Sa) The surface roughness of the structure after standard plasma test 1 was evaluated using a laser microscope to determine the arithmetic mean height (Sa) as defined in ISO 25178. An Olympus OLS4500 laser microscope was used. An MPLAPON100XLEXT objective lens was used, with a cutoff value λc of 25 μm. The results are shown in the table below. [Table 5]

[0059] Measurement of lattice constants The lattice constant of the YAM sample was evaluated using X-ray diffraction according to the following procedure. An "Aeris / Panalytical" XRD instrument was used. The XRD measurement conditions were as follows: characteristic X-ray CuKα (λ=1.5418Å), tube voltage 40kV, tube current 15mA, step size 0.0054°, and time per step 300 seconds or more. The peak positions (2θ) were measured for the peak at diffraction angle 2θ=26.7° attributed to Miller index (hkl)=(013), the peak at diffraction angle 2θ=29.6° attributed to Miller index (hkl)=(122), and the peak at diffraction angle 2θ=30.6° attributed to Miller index (hkl)=(211) in the monoclinic YAM. Furthermore, since the structure 20 in this invention is a novel structure with lattice constants greater than a=7.3781, b=10.4735, and c=11.1253, the peak positions (2θ) assigned to each Miller index (hlk) actually measured by XRD are shifted by 0.1 to 0.4° to the lower angle side compared to the theoretical peak positions (2θ) assigned to each Miller index (hkl). Next, the lattice plane spacing (d) for each peak is calculated using Bragg's equation λ=2d·sinθ, where λ is the wavelength of the characteristic X-ray used in the XRD. Finally, the lattice constants a, b, and c are calculated using Equation 1, where d is the lattice plane spacing and (hkl) is the Miller index. In addition, β=108.54° was used in the calculation of lattice constants a, b, and c. Other than that, the measurement of lattice constants conforms to JIS K0131. The lattice constants for each sample are shown in Table 2.

[0060] Measurement of peak intensity ratio An Aeris / Panalytical XRD system was used. The XRD measurement conditions were as follows: characteristic X-ray: CuKα (λ=1.5418Å), tube voltage: 40kV, tube current: 15mA, step size: 0.0054°, time per step: 300 seconds or more. For monoclinic YAM, the peak intensity near diffraction angle 2θ=29.6°, attributed to Miller index (hkl)=(122), was defined as α, and the peak intensity near diffraction angle 2θ=30.6°, attributed to Miller index (hkl)=(211), was defined as β. The peak intensity ratio was calculated using γ=β / α. The intensities α and β were calculated by profile fitting to the measured spectrum using the second derivative method. Furthermore, since the structure 20 in this invention is a novel structure with lattice constants greater than a=7.3781, b=10.4735, and c=11.1253, the peak positions (2θ) assigned to each Miller index (hlk) actually measured by XRD are shifted by 0.1 to 0.4° towards the lower angle side compared to the theoretical peak positions (2θ) assigned to each Miller index (hkl).

[0061] [Table 6]

[0062] Measurement of peak intensity ratio A "Smart-Lab / Rigaku" XRD system was used. The XRD measurement conditions were as follows: characteristic X-ray was CuKα (λ=1.5418Å), tube voltage 45kV, tube current 200mA, step size 0.0054°, and speed / measurement time 2° / min or less. For monoclinic YAM, the peak intensity at diffraction angle 2θ=29.6°±0.4 (29.2°~30.0°) attributed to Miller index (hkl)=(122) was defined as α, and the peak intensity at diffraction angle 2θ=30.6°±0.4° (30.2°~31.0°) attributed to Miller index (hkl)=(211) was defined as β. The peak intensity ratio was calculated as γ=β / α. The intensities α and β were calculated by profile fitting using the second derivative method on the measured spectrum. Furthermore, since the structure 20 in this invention is a novel structure with lattice constants greater than a=7.3781, b=10.4735, and c=11.1253, the peak positions (2θ) assigned to each Miller index (hlk) actually measured by XRD are shifted by 0.1 to 0.4° towards the lower angle side compared to the theoretical peak positions (2θ) assigned to each Miller index (hkl).

[0063] [Table 7]

[0064] Evaluation of Results Based on the above results, in Table 2 above, the evaluation was as follows: "◎" if the effect of plasma corrosion was small in both Standard Plasma Test 1 and 2, "〇" if the effect of plasma corrosion was small in either Standard Plasma Test 1 or 2, and "×" if the effect of plasma corrosion was present in both conditions of Standard Plasma Test 1 and 2.

[0065] Embodiments of the present invention have been described above. However, the present invention is not limited to these descriptions. Modifications made by those skilled in the art to the above-described embodiments are also included within the scope of the present invention, as long as they retain the features of the present invention. For example, the shape, dimensions, material, and arrangement of structures, base materials, etc., are not limited to those exemplified and can be modified as appropriate. Furthermore, the elements of each of the above-described embodiments can be combined to the extent technically feasible, and combinations thereof are also included within the scope of the present invention, as long as they retain the features of the present invention. [Explanation of Symbols]

[0066] 10... Composite structures, 15... Base materials, 20... Structures, 20a... Surfaces of structures

Claims

1. A composite structure for use in an environment where particle resistance to fluorine-based plasma is required, comprising a base material and a structure provided on the base material and having a surface, The aforementioned structure is Y ４ Al ２ O ９ It contains as its main component, and the lattice constants a, b, and c calculated by the following formula (1) satisfy at least one of the following conditions: a > 7.382, b > 10.592, c > 11.

160. A composite structure is subjected to inductively coupled reactive ion etching (ICP-RIE) using an ICP-RIE apparatus, with SF6 100 sccm as the process gas, a power supply of 1500 W for the ICP coil, bias output OFF (0 W), and chamber pressure of 0.5 Pa. After exposure to the plasma atmosphere for 1 hour, the fluorine atom concentration F3 10 nm at a depth of 10 nm from the surface is less than 3.0%. [Math 1] (In Equation 1, d is the interplanar spacing, (hkl) is the Miller index, and β = 108.54° is assumed in the calculation of the lattice constants a, b, and c).

2. The composite structure according to claim 1, wherein the lattice constant satisfies at least one of a > 7.393, b > 10.608, and c > 11.

179.

3. The composite structure according to claim 1, wherein the lattice constant satisfies at least one of a > 7.404, b > 10.627, and c > 11.

192.

4. A composite structure for use in an environment where particle resistance to fluorine-based plasma is required, comprising a base material and a structure provided on the base material and having a surface, The aforementioned structure is Y ４ Al ２ O ９ It contains as its main component, and the peak intensity ratio γ calculated by the following formula (2) is 1.15 or more and 2.0 or less. A composite structure is subjected to inductively coupled reactive ion etching (ICP-RIE) using an ICP-RIE apparatus, with SF6 100 sccm as the process gas, a power supply of 1500 W for the ICP coil, bias output OFF (0 W), and chamber pressure of 0.5 Pa. After exposure to the plasma atmosphere for 1 hour, the fluorine atom concentration F3 10 nm at a depth of 10 nm from the surface is less than 3.0%. γ=β / α...(2) (In formula 2, α is Y ４ Al ２ O ９ It is the intensity of the peak with diffraction angle 2θ = 29.6° attributed to Miller index (hkl) = (122) in monoclinic crystal, and β is the intensity of the peak with diffraction angle 2θ = 30.6° attributed to Miller index (hkl) = (211)).

5. The composite structure according to claim 4, wherein the peak intensity ratio γ is 1.20 or more.

6. The composite structure according to claim 4, wherein the peak intensity ratio γ is 1.24 or more.

7. A composite structure for use in an environment where particle resistance to fluorine-based plasma is required, comprising a base material and a structure provided on the base material and having a surface, The aforementioned structure is Y ４ Al ２ O ９ It contains as its main component, Using an inductively coupled reactive ion etching (ICP-RIE) apparatus, after exposure for 1 hour in a plasma atmosphere under conditions of SF6 100 sccm as the process gas, ICP coil output of 1500 W, bias output OFF (0 W), and chamber pressure of 0.5 Pa, the fluorine atom concentration F3 10 nm at a depth of 10 nm from the surface is less than 3.0%. The lattice constants a, b, and c calculated by the following formula (1) as defined in claim 1 satisfy at least one of a > 7.382, b > 10.592, and c > 11.160, or A composite structure in which the peak intensity ratio γ calculated by the following formula (2) as defined in claim 4 is 1.15 or more and 2.0 or less.

8. A composite structure according to any one of claims 1 to 7, which is a component for semiconductor manufacturing equipment.

9. A semiconductor manufacturing apparatus comprising a composite structure according to any one of claims 1 to 7.

10. A method for operating a semiconductor manufacturing apparatus using a fluorine-based plasma, A method characterized by installing a composite structure according to any one of claims 1 to 7 at a location exposed to the fluorine-based plasma, thereby suppressing the generation of particles by suppressing the penetration of fluorine into the composite structure by the fluorine-based plasma.

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