KR20200021055A - Composite structure and display manufacturing apparatus and semiconductor manufacturing device having composite structure - Google Patents

Abstract

Provided are ceramic coating with excellent particle resistance and a method of evaluating particle resistance of ceramic coating. A composite structure includes: a base material; and a structure installed on the base material and having a surface, wherein the structure includes polycrystal ceramics. In the composite structure, brightness (Sa) calculated from TEM image analysis satisfies a predetermined value. Therefore, the composite structure can be properly used as an inner member of a semiconductor manufacturing device requiring the particle resistance.

Description

COMPOSITE STRUCTURE AND DISPLAY MANUFACTURING APPARATUS AND SEMICONDUCTOR MANUFACTURING DEVICE HAVING COMPOSITE STRUCTURE}

The present invention relates to a composite structure in which polycrystalline ceramics are coated on a surface of a substrate to impart a function to the substrate. Moreover, this invention relates to the semiconductor manufacturing apparatus provided with the said composite structure, and a display manufacturing apparatus. In particular, this invention relates to the composite structure excellent in particle resistance used in the environment exposed to corrosive plasma, such as a semiconductor manufacturing apparatus member, a semiconductor manufacturing apparatus provided with this composite structure, and a display manufacturing apparatus.

The technique which coats ceramics on the surface of a base material and gives a function to a base material is known. For example, as such a ceramic coating, the plasma-resistant coating of the chamber structural member in a semiconductor manufacturing apparatus etc., the insulating coating in a heat radiating base material, etc., the ultra smooth coating in an optical mirror, etc., the scratch resistance in a sliding member, etc. Wear resistant coating; Along with high functionalization of such a member, the required level is high, and in these ceramic coatings, not only the material composition but also its physical structure, in particular, a fine structure, may dominate the performance.

As a method for obtaining such a ceramic coating, the aerosol deposition method (AD method), the PVD (Physical Vapor Deposition) method (PEPVD (Plasma-Enhanced Physical Vapor Deposition) method, thickened by plasma or ion assist), Various ceramic coating technologies have been developed, such as the ion assisted deposition (IAD) method and the suspension spraying method using a suspension (suspension) of a fine raw material.

Carefully prepared ceramic coatings have some degree of microstructure control. In the report so far, the porosity confirmed by image analysis methods, such as SEM (Scanning Electron Microscope), is 0.01 to 0.1%.

For example, Japanese Patent Application Laid-Open No. 2005-217351 (Patent Document 1) discloses a layered structure composed of yttria polycrystals having a pore occupancy of 0.05 area% or less as a member for semiconductor manufacturing apparatus having plasma resistance. . This layered structure is said to have suitable plasma resistance.

In addition, Korean Patent 20170077830A (Patent Document 2) discloses a YF ₃ transparent fluorine-based thin film having high resistance to plasma and corrosive gas. This YF ₃ thin film has a high porosity of 0.01-0.1%, and is therefore highly resistant to plasma and the like. In addition, the breakdown voltage is 50-150 V / µm.

Japanese Patent Publication No. 2016-511796 (Patent Document 3) discloses a ceramic coating such as Y ₂ O ₃ , which comprises constituent particles in the range of particle size 200-900 nm and constituent particles in the range of particle size 900 nm-10 μm. Initiate. This coating has a high porosity of 0.01-0.1% and is said to have high resistance to plasma and the like. In addition, the breakdown voltage is 80-120 V / µm.

Japanese Chemical Society 1979, (8), p. 1106 to 1108 (Non-Patent Document 1) discloses refractive index and reflectance as optical properties of a yttrium sintered compact that is a transparent plate-like sample (see FIG. 10).

In the semiconductor manufacturing apparatus field, the miniaturization of semiconductor devices progresses year by year, and it is estimated that when extreme ultraviolet lithography (EUV) is put into practical use, it will reach several nm. According to the International Roadmap for Devices and Systems (IRDS), MORE MOORE WHITE PAPER 2016 EDITION by the Institute of Electrical and Electronics Engineers, Inc. It is predicted that 12.0nm will be smaller than 10.0nm after 2021.

For the purpose of high integration of such semiconductors, thinning of the circuit line width and miniaturization of the circuit pitch are further progressed. In addition, for example, a fluorine-containing plasma, or a plasma corrosion resistance, such as a chlorine-based plasma such as CF _4, NF ₃ is used in the etching process. And in the future, the process using the high density plasma of the above is performed, and the various members in a semiconductor manufacturing apparatus are required for low-particle generation at a higher level.

Conventionally, the plasma resistance of the ceramic coating correlates with the porosity, and by reducing the porosity of the structure to 0.01 to 0.1%, for example, under the idea that the generation of particles is suppressed when the consumption of the ceramic coating by plasma erosion is suppressed, We have solved the problem with particles. However, according to the findings obtained by the present inventors, even in a structure having a very small porosity during further miniaturization, the problem of suppressing particle generation could not be solved. That is to say, not only the consumption of ceramic coatings based on the porosity but also the understanding that the generation of particles at different time points must be controlled with higher precision.

That is, in recent years, in the miniaturization of devices and the high density of plasmas, even in a ceramic structure which is considered to contain almost no pores with a porosity of 0.01 to 0.1%, the particle problem still exists, and a structure having further particle resistance is required. have. In addition, there is a demand for a ceramic structure that can solve the particle problem even in a fine device having a line width of several nm level in a future semiconductor circuit.

Japanese Patent Laid-Open No. 2005-217351 Korean Patent 20170077830A publication Japanese Patent Publication No. 2016-511796

Japanese Chemical Society 1979, (8), p. 1106-1108 "Refractive Index and Reflectance of Yttria Sintered Body"

The present inventors succeeded in obtaining the composite structure which can make the influence of a particle very small in the ceramic coating used in the situation which is exposed to the corrosive plasma environment, such as a semiconductor manufacturing apparatus, for example. And after finding that some indicators have a high correlation with the particle resistance at a very high level, the particle resistance, which is defined by these indicators, specifically the indicators according to the first to fifth aspects described later. The fabrication of this excellent structure was successful.

Accordingly, the present invention provides a polycrystalline ceramic structure on a substrate which can solve the problem of providing a composite structure having a polycrystalline ceramic structure with a controlled microstructure, in particular, minimizing the generation of particles even in a highly refined and high-density plasma. The object of the present invention is to provide a composite structure.

Moreover, this invention aims at providing the semiconductor manufacturing apparatus provided with the said composite structure, and a display manufacturing apparatus.

1 is a schematic cross-sectional view of a composite structure 100 according to the present invention.
2 is a flowchart showing a method for evaluating luminance Sa according to the present invention.
3A to 3C are schematic views of the TEM observation sample 90.
4 is a schematic diagram illustrating a TEM image G of the structure 10.
Fig. 5 is a diagram showing luminance values for each TEM image G and one pixel.
6 is a diagram illustrating luminance correction of the TEM image G. FIG.
7A and 7B are diagrams showing luminance values in the luminance acquisition region R. FIG.
8 is a schematic diagram illustrating an example in which the composite structure 100 is used as the semiconductor manufacturing apparatus member 301.
9 is a schematic diagram illustrating an example in which the composite structure 100 is used as the semiconductor manufacturing apparatus member 302.
It is a schematic diagram which shows an example of the apparatus structure used for an aerosol deposition method.
11 is a TEM image of 400,000 times magnification of the structure 10.
12A-12D are scanning electron microscope (SEM) images of the structure 10.
13A-13J are transmission electron microscope (TEM) images G of structure 10.
14A-14H are scanning electron microscope (SEM) images of the surface of structure 10 after a reference plasma resistance test.
15 is a graph showing the area of corrosion traces on the surface of the structure 10 after the standard plasma resistance test.
FIG. 16 is a graph showing the relationship between the luminance Sa and the corrosion trace area on the surface 10a of the structure 10.
FIG. 17 is a graph showing the relationship between the amount of hydrogen and the corrosion trace area on the surface 10a of the structure 10.
It is typical sectional drawing for demonstrating the microstructure of a composite structure.
19 is a graph showing the relationship between the wavelength of the structure 10 and the refractive index.
It is a graph which shows the wavelength dispersion of the refractive index of the yttrium sintered compact which concerns on a prior art.

Composite structure

The basic structure of the composite structure by this invention is demonstrated using FIG. 1 is a schematic cross-sectional view of a composite structure 100 according to the present invention. The structure 10 is installed on the surface 70a of the substrate 70. This structure 10 has a surface 10a. The surface 10a is a surface exposed to the environment in an environment in which the physical properties and properties imparted by the structure 10 to the composite structure are required. Therefore, for example, in a composite structure in which the composite structure according to the present invention is provided with physical properties and characteristics such as particle resistance by the structure 10, the surface 10 of the composite structure is exposed to corrosive gas such as plasma. It is exposed side. In the present invention, the structure 10 includes polycrystalline ceramics. In addition, the structure 10 with which the composite structure by this invention is equipped shows a predetermined value in the index | index in the 1st-5th aspect mentioned later.

The structure 10 of 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 substrate 70. In addition, in this specification, a structure (ceramic structure) and a ceramic coating are used by the same meaning unless there is particular notice.

According to one aspect of the present invention, the structure 10 mainly includes polycrystalline ceramics. Content of polycrystal ceramics is 70% or more, Preferably it is 90% or more, More preferably, it is 95% or more. Most preferably, the structure 10 is made of 100% polycrystalline ceramics.

In addition, according to one aspect of the present invention, the structure 10 may include a polycrystalline region and an amorphous region, but it is more preferable that the structure 10 is composed of only polycrystals.

How to measure crystallite size

In this invention, the magnitude | size of the polycrystal ceramics which comprise the structure 10 is 3 nm or more and 50 nm or less as average crystallite size obtained by the following measurement conditions. More preferably, the upper limit is 30 nm, More preferably, it is 20 nm, More preferably, it is 15 nm. Moreover, the minimum with preferable is 5 nm. This "average crystallite size" in this invention image | photographed a transmission electron microscope (TEM: transmission electron microscope) image by 400,000 times or more magnification, and computed from the average value of the diameter by circular approximation of 15 crystallites in this image. Value. At this time, the sample thickness at the time of a converged ion beam (FIB) processing is made thin enough about 30 nm. Thereby, the determinant can be discriminated more clearly. A photographing magnification can be suitably selected in the range of 400,000 times or more. 11 is an example of a TEM image for crystallite size measurement. Specifically, FIG. 11 is a TEM image of the structure 10 at a magnification of 2 million times. In the figure, the region indicated by 10c is a determinant.

As described above, the ceramics constituting the structure 10 may be appropriately determined by the physical properties and characteristics desired to be imparted to the substrate 70, and may be a metal oxide, a metal fluoride, a metal nitride, a metal carbide, or a mixture thereof. It may be. According to one aspect of the present invention, examples of the compound having excellent particle resistance include oxides of rare earth elements, fluorides, acid fluorides (LnOF), and mixtures thereof as materials. More specifically, examples of the rare earth element (Ln) include Y, Sc, Yb, Ce, Pr, Eu, La, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, Lu.

In the case of the insulating structure 10, materials such as Al ₂ O ₃ , ZrO ₂ , AlN, SiC, Si ₃ N ₄ , cordierite, forsterite, mullite and silica may be used.

In the present invention, the film thickness of the structure 10 may be appropriately determined in consideration of the required use, characteristics, film strength, and the like. Generally, it is the range of 0.1-50 micrometers, and an upper limit may be 20 micrometers, 10 micrometers, or 5 micrometers, and 1 micrometer or less, for example. Here, the film thickness of the structure 10 can cut the structure 10, for example, and can confirm by SEM observation of the fracture surface.

In the present invention, the substrate 70 is an object to which a function is imparted by the structure 10 and may be appropriately determined. Examples of the material include ceramics, metals, resins, and the like, and composites thereof may be used. As an example of a composite material, the composite base material of resin and ceramics, the composite base material of fiber reinforced plastics and ceramics, etc. are mentioned. Moreover, the shape is not specifically limited, either, A flat plate, a recessed surface, a convex surface, etc. may be sufficient.

According to one aspect of the present invention, the surface 70a of the substrate 70 to be bonded to the structure 10 is smooth for the formation of the good structure 10. According to one aspect of the present invention, at least any one of blast, physical polishing, chemical mechanical polishing, lapping, and chemical polishing is applied to the surface 70a of the substrate 70 to remove the unevenness of the surface 70a. do. This unevenness | corrugation removes that the subsequent surface 70a has a 2-dimensional arithmetic mean roughness Ra of 0.2 micrometer or less, More preferably, 0.1 micrometer or less, or a two-dimensional arithmetic mean height Rz of 3 micrometers or less. It is preferable to do so.

The composite structure according to the present invention can be suitably used as a member used in various members in a semiconductor manufacturing apparatus, particularly in an environment exposed to a corrosive plasma atmosphere. As described above, the member inside the semiconductor manufacturing apparatus requires particle resistance. It is because the structure containing the polycrystal ceramics with which the composite structure by this invention is equipped has high particle resistance.

When the composite structure according to the present invention is used as a member used in an environment exposed to a corrosive plasma atmosphere, the composition of the ceramic constituting the structure 10 is Y ₂ O ₃ , yttrium oxyfluoride (YOF, Y _5). O ₄ F ₇ , Y ₆ O ₅ F ₈ , Y ₇ O ₆ F ₉ and Y ₁₇ O ₁₄ F ₂₃ ), (YO _0.826 F _0.17 ) F _1.174 , YF ₃ , Er ₂ O ₃ , Gd ₂ O ₃ , Nd ₂ O ₃ , Y ₃ Al ₅ O ₁₂ , Y ₄ Al ₂ O ₉ , Er ₃ Al ₅ O ₁₂ , Gd ₃ Al ₅ O ₁₂ , Er ₄ Al ₂ O ₉ , ErAlO ₃ , Gd ₄ Al ₂ O ₉ , GdAlO ₃ , Nd ₃ Al ₅ O ₁₂ , Nd ₄ Al ₂ O ₉ , NdAlO ₃ and the like.

Plasma resistance

The composite structure by this invention prescribed | regulated by the index | index by the 1st thru | or 5th aspect mentioned later is equipped with plasma resistance. The plasma resistance can evaluate the plasma resistance test demonstrated below as one reference method. Hereinafter, in this specification, this plasma resistance test is called "a reference plasma resistance test."

As one aspect of this invention, the composite structure whose arithmetic mean height Sa of the surface 10a of the structure 10 after the "reference plasma resistance test" is 0.060 or less is preferable, More preferably, it is 0.030 or less. Arithmetic mean height Sa is mentioned later.

As a plasma etching apparatus for the "standard plasma resistance test", an inductively coupled plasma reactive ion etching apparatus (manufactured by Muc-21 Rv-Aps-Se / Sumitomo Seimitsu Kogyo Co., Ltd.) is used. Plasma etching conditions include a mixed gas of 1500 W of inductively coupled plasma (ICP) as the power output, 750 W of bias output, and 100 ccm of CHF ₃ gas and 10 ccm of O ₂ gas as the process gas, and a pressure of 0.5 kPa, Plasma etching time is 1 hour.

The state of the surface 10a of the structure 10 after plasma irradiation is image | photographed with the laser microscope (for example, OLS4500 / Olympus make). Details, such as observation conditions, are mentioned later.

The arithmetic mean height Sa of the surface after plasma irradiation is computed from the obtained image. Here, the arithmetic mean height Sa is an extension of the two-dimensional arithmetic mean roughness Ra in three dimensions, and is a three-dimensional roughness parameter (three-dimensional height direction parameter). Specifically, the arithmetic mean height Sa is the volume of the part enclosed by the surface-shaped curved surface and the average surface divided by the measurement area. That is, if the average plane is the xy plane, the longitudinal direction is the z axis, and the measured surface shape curve is z (x, y), the arithmetic mean height Sa is defined by the following equation. Here, in formula (1), "A" is a measurement area.

Arithmetic mean height Sa is a value which does not depend on measurement method fundamentally, but is computed under the following conditions in the "reference plasma resistance test" in this specification. A laser microscope is used to calculate the arithmetic mean height Sa. Specifically, the laser microscope "OLS4500 / Olympus manufacture" is used. The objective lens uses MPLAPON100xLEXT (an aperture number of 0.95, an operating distance of 0.35 mm, a condensing spot diameter of 0.52 µm, and a measuring area of 128 x 128 µm), and the magnification is 100 times. The bend component removal lambda c filter is set to 25 mu m. The measurement is performed at three arbitrary places, and makes the average value the arithmetic mean height Sa. In addition, the international standard ISO25178 of the three-dimensional surface appearance is appropriately referred to.

First aspect of the invention

As a basis for the first aspect of the present invention, the present inventors, for example, in a composite structure having a structure comprising polycrystalline ceramics used in a situation exposed to a corrosive plasma environment such as a semiconductor manufacturing apparatus, particles It succeeded in making the effect of the car very small. And it was found out that the particle resistance performance can be evaluated at a very high level by using the amount of hydrogen contained in the structure as an index measured by a dynamic-secondary ion mass spectrometry_D-SIMS method.

The composite structure according to the first aspect of the present invention is a composite structure including a substrate and a structure provided on the substrate and having a surface, the structure comprising polycrystalline ceramics, and secondary ion mass spectrometry (Dynamic- The number of hydrogen atoms per unit volume in any of the measurement depth 500 nm or 2 micrometers measured by Secondary Ion Mass Spectrometry_D-SIMS method) is 7 * 10 <^21> atoms / cm <3> or less.

It is typical sectional drawing for demonstrating the microstructure of a composite structure. In Figure 18, (a) is a conventional composite structure 110, (b) is a composite structure 100 according to the present invention. In the figure, reference numeral 80 denotes a coarse structure at the nano level, and 90 denotes a water molecule (OH group). In FIG. 18, in order to facilitate understanding, the size of the nano-level bath structure 80 is increased, but in practice, the porosity in the conventional evaluation method by SEM or the like for both the composite structures 100 and 110 is 0.01 to 0.1. %to be.

The present inventors focused on the fact that even a structure having a low porosity of 0.01 to 0.1% still cannot solve the particle problem, and has succeeded in obtaining a new structure that can solve the particle problem at a higher level. As a cause which cannot solve a particle problem by the conventional structure, as a microstructure in a structure, there existed nano-level density fluctuations, and it was thought that plasma resistance in this structure 80 is low compared with a wheat structure. And it was thought that the water structure (OH group) contained in air | atmosphere exists, for example in the crude structure 80 which is narrow at the nano level, and it was thought that the correlation with particle resistance is obtained by performing this quantification. In other words, it was found that by quantifying the amount of hydrogen in the water molecule (OH group), it is possible to specify the configuration of a novel structure that can solve the particle problem at a higher level.

Specifically, in FIG. 18, in the composite structure 100 of the present invention, compared to the conventional composite structure 110, the water structure (OH) is less in the bath structure 80 and exists in the bath structure 80 (OH). It seems to be few. Particle resistance can be related by quantifying the amount of hydrogen (number of hydrogen atoms per unit volume) of the structure 10 by secondary ion mass spectrometry (D-SIMS method) described later.

Sample preparation for the amount of hydrogen measurement in 1st aspect of this invention

In the first aspect of the present invention, the sample for measuring the amount of hydrogen can be produced, for example, by the following method.

First, the composite structure provided with the structure 10 is cut out previously with a dicing machine or the like. At this time, the part corresponding to the sample acquisition location 40 of FIG. 8 and FIG. 9 is cut out. Although the size may be arbitrary, it is set as about 3 mm x 3 mm-7 mm x 7 mm, and thickness 3 mm, for example. In addition, the thickness of a sample may be suitably determined according to the measuring apparatus used, etc., and it adjusts by shaving the surface of the side in which the structure 10 is not formed in the base material 70, etc. The surface 10a of the structure 10 has arithmetic mean roughness Ra which is a parameter of the two-dimensional surface roughness by grinding | polishing etc. to 0.1 micrometer or less, More preferably, it is 0.01 micrometer. The thickness of the structure 10 is at least 500 nm, preferably at least 1 μm, more preferably at least 3 μm.

In the D-SIMS method, which is a method for measuring the amount of hydrogen in the present invention, the measurement is generally performed using a standard sample. As a standard sample, it is preferable to use the same composition and the same structure as the sample to be measured. For example, at least two samples may be produced and one of them may be a standard sample. The detail of a standard sample is mentioned later.

The state of the sample before hydrogen amount measurement is demonstrated.

As described above, in the present invention, the amount of hydrogen is used for the specific method of the nano-level bath structure of the structure 100. Therefore, management, such as leaving the sample before the amount of hydrogen measurement in a constant temperature and constant temperature bath, becomes important. Specifically, in the present invention, the amount of hydrogen is measured after leaving the sample at room temperature 20-25 ° C., humidity 60% ± 10%, and atmospheric pressure for 24 hours or longer.

Measurement of the amount of hydrogen in the first aspect of the present invention

Next, the measuring method of the amount of hydrogen in the 1st aspect of this invention is demonstrated.

In the present invention, the amount of hydrogen is measured by secondary ion mass spectrometry: Dynamic-Secondary Ion Mass Spectrometry (D-SIMS method). As the apparatus, for example, IMF-7f manufactured by CAMECA is used.

Next, it describes about measurement conditions.

First, conductive platinum (Pt) is deposited on the surface of the structure. As measurement conditions, cesium (Cs) ions are used for the primary ionic species. The primary acceleration voltage is 15.0 kV and the detection area is 8 μmφ. Measurement depths are 500 nm and 2 micrometers.

Particle resistance is highly dependent on the nature of the structure surface, which is directly exposed to the plasma atmosphere. Therefore, in the structure, the amount of hydrogen and the particle resistance can be effectively linked by quantifying the amount of hydrogen in the region at least about 500 nm from the surface. On the other hand, when the thickness of the structure is sufficiently large and the microstructure from the surface to the measurement target depth is substantially homogeneous, reliability of the quantitative result can be improved by making the measurement target up to an area of about 2 μm. In addition, the structure 10 has a lower region 10b on the substrate 70 side and an upper region 10u on the surface 10a side (see FIG. 1), and the particle resistance thereof, for example, the upper portion. In the case where the stack structure is higher than the lower region 10b in the region 10u, it is preferable to set the measurement depth so that the amount of hydrogen only in the region of the upper region 10u can be quantified. From this viewpoint, the amount of hydrogen prescribed | regulated in this invention should just be any of measurement depth 500 nm or 2 micrometers. Preferably, the hydrogen content of the present invention is also satisfied in any of the measurement depth of 500 nm and 2 µm.

For the measurement of the amount of hydrogen, a sample for measurement and a standard sample are prepared.

A standard sample is generally used in the SIMS method to standardize the signal intensity of the ionic species to be analyzed to the signal intensity of the ionic species containing the matrix element of the sample for the purpose of removing the factors related to the measurement conditions. More specifically, an evaluation sample, a standard sample for evaluation samples which is a sample having a matrix component equivalent to the evaluation sample, a Si single crystal, and a standard sample for Si single crystal are used. The standard sample for the evaluation sample is the injection of deuterium into a sample having a matrix component equivalent to that of the evaluation sample. At this time, deuterium is also injected into the Si single crystal, and it is assumed that deuterium equivalent to the standard sample for evaluation sample and the Si single crystal are injected. Thereafter, the amount of deuterium injected into the Si single crystal is identified using a standard sample for Si single crystal. About the standard sample for evaluation samples, the secondary ion intensity of deuterium and a structural element is computed using secondary ion mass spectrometry (D-SIMS method), and a sensitivity coefficient between phases is computed. The amount of hydrogen of an evaluation sample is computed using the phase sensitivity coefficient computed from the standard sample for evaluation samples. Otherwise, reference may be made to ISO 18114_ "Determining relative sensitivity factors from ion-implanted reference materials" (International Organization for Standardization, Geneva, 2003).

In the present invention, the unit in any of the measurement depth of 500 nm or 2 μm or less, which is measured by secondary ion mass spectrometry (Dynamic-Secondary Ion Mass Spectrometry_D-SIMS method) included in the structure constituting the composite structure. The number of hydrogen atoms per volume is 7 * 10 ²¹ atoms / cm 3 or less.

In the structure of this invention, the surface is exposed directly, for example in a plasma atmosphere. Therefore, the property of the surface of the structure is particularly important. The present inventors consider that even if the structure has a porosity of 0.01 to 0.1% and contains almost no pores, the particle problem is still not solved under the influence of the nano-level microstructure, and as a result, the nano-level microstructure is controlled. We succeeded in doing this and got a new structure to solve the particle challenge at a higher level. In addition, it was newly found that the structure of this new structure can be specified using the surface hydrogen amount (the number of hydrogen atoms per unit volume) as an index. And the correlation between the amount of hydrogen on the surface of the structure and the particle resistance is found in the present invention.

Specifically, for example, in the atmosphere, the hydrogen atom is considered to exist in a state such as hydroxyl group (-OH). The size of a molecule | numerator is about 3 kPa and a hydroxyl group is about 1 kPa as a water molecule, and it is thought that it exists slightly in the above-mentioned crude structure 80 of a structure. By using this amount of hydrogen as an index, a nanostructured microstructure can be exhibited.

In the present invention, as the amount of hydrogen in the structure, the number of hydrogen atoms per unit volume in any one of the measurement depth 500 nm or 2 μm measured by D-SIMS is 7 * 10 ²¹ atoms / cm 3 or less. The number of hydrogen atoms per unit volume is preferably 5 * 10 ²¹ atoms / cm 3 or less.

In addition, although the amount of hydrogen in the structure of the composite structure which concerns on this invention is so preferable that it is small, it is clear to those skilled in the art that there exist virtual measurement limits. Therefore, the lower limit of the amount of hydrogen in this aspect is a measurement limit. This point is the same also in the following 2nd aspect.

Second aspect of the present invention

In the second aspect of the present invention, similarly to the first aspect of the present invention, the hydrogen content is used as an index, but hydrogen forward scattering analysis (HFS) -Rutherford backscattering spectroscopy (RBS) (RBS-HFS method) and proton- The amount of hydrogen measured by the hydrogen forward scattering analysis method (p-RBS method) is taken as an index. That is, the present inventors, for example, in the composite structure having a structure containing Y (yttrium element) and O (oxygen element) used in a situation exposed to a corrosive plasma environment such as a semiconductor manufacturing apparatus, the effect of particles Succeeded in making it very small. And the amount of hydrogen contained in the structure, measured by hydrogen forward scattering analysis (HFS) -Rutherford backscattering spectroscopy (RBS) (RBS-HFS method) and proton-hydrogen forward scattering analysis (p-RBS method) as an index. By using it, we found that we can evaluate my particle performance at an extremely high level.

The composite structure according to the second aspect of the present invention is a composite structure comprising a substrate and a structure provided on the substrate and having a surface, the structure comprising polycrystalline ceramics, and hydrogen forward scattering analysis (HFS)- The hydrogen atom concentration measured by Rutherford backscattering spectroscopy (RBS) (RBS-HFS method) and proton-hydrogen forward scattering analysis method (p-RBS method) is 7 atomic% or less.

The second aspect of the present invention differs from the first aspect of the present invention in the method for measuring the amount of hydrogen, and the description of the first aspect in the present specification is second except for the case where a change due to it is made. The invention is explained.

Sample preparation for the amount of hydrogen measurement in 2nd aspect of this invention

In the second aspect of the present invention, the sample for measuring the amount of hydrogen can be produced, for example, by the following method.

First, the composite structure provided with the structure 10 is cut out previously with a dicing machine or the like. At this time, the part corresponding to the sample acquisition location 40 of FIG. 8 and FIG. 9 is cut out. Although the size may be arbitrary, it is set as about 20 mm x 20 mm and thickness 5 mm, for example. In addition, the thickness of a sample may be suitably determined according to the measuring apparatus used, etc., and it adjusts by shaving the surface of the side in which the structure 10 is not formed in the base material 70, etc. The surface 10a of the structure 10 has arithmetic mean roughness Ra which is a parameter of the two-dimensional surface roughness by grinding | polishing etc. to 0.1 micrometer or less, More preferably, it is 0.01 micrometer. The thickness of the structure 10 is at least 500 nm, preferably at least 1 μm, more preferably at least 3 μm.

The state of the sample before hydrogen amount measurement is demonstrated.

As described above, in the present invention, the amount of hydrogen is used for the specific method of the nano-level bath structure of the structure 100. Therefore, management, such as leaving the sample before the amount of hydrogen measurement in a constant temperature and constant temperature bath, becomes important. Specifically, in the present invention, the amount of hydrogen is measured after leaving the sample at room temperature 20-25 ° C., humidity 60% ± 10%, and atmospheric pressure for 24 hours or longer.

Measurement of the amount of hydrogen in the second aspect of the present invention

Next, the measuring method of hydrogen amount is demonstrated.

In the present invention, the hydrogen content is measured by Hydrogen Forward scattering Spectrometry (HFS) / Rutherford Backscattering Spectorometry (RBS) method (hereinafter referred to as RBS-HFS method) and RBS method using protons (hereinafter p) -Referred to as RBS). For example, Pelletron 3SDH manufactured by National Electrostatics Corporation can be used for the apparatus.

The method of quantifying the amount of hydrogen is further described.

RBS-HFS method using helium (He) element is performed. Helium (He atoms) is irradiated to the structure to detect back scattered He atoms and forward scattered H atoms. The energy spectrum of the back-scattered He atoms is fitted in order from the element having the largest energy spectrum, and the scattering intensity is calculated. The scattering intensity is also calculated by fitting the energy spectrum of the forward-scattered H atoms. Based on the calculated scattering intensities, the ratio of the average number of atoms of the elements in the structure can be calculated. For example, when the structure is yttrium oxide, the scattering intensity is calculated by fitting the element Y having the largest energy spectrum of the detected He atom to calculate the scattering intensity, and subsequently, the scattering intensity is calculated. In addition, it is preferable to combine other methods, such as an energy dispersive X-ray-analysis (EDX) method, for the specification of the element with the largest energy spectrum.

Although the ratio of the average number of atoms of the element in a structure is measured by the said RBS-HFS method, in order to improve the measurement precision, in this invention, also in the structure by the p-RBS method which used proton (H ⁺ ), The ratio of the average number of atoms other than hydrogen is measured again. At the time of calculation, fitting is performed in order from the element with the largest energy spectrum measured similarly to RBS-HFS method, and scattering intensity is computed. Based on the calculated scattering intensities, the ratio of the average number of atoms of the elements in the structure is calculated. And the element whose ratio of the average number of atoms measured by the p-RBS method and the energy spectrum of the detected He atom measured by the RBS-HFS method is the largest (for example, when the structure is yttrium oxide, the detected He atom The element having the largest energy spectrum of is combined with the ratio of Y) and the average number of atoms of hydrogen, and the amount of hydrogen is calculated as the hydrogen atom concentration (atomic%).

In the present invention, the order of performing the p-RBS method and the RBS-HFS method is not particularly limited.

Next, it describes about measurement conditions.

RBS-HFS method

4He ⁺ is used for incident ions. The incident energy is 2300 KeV, the incident angle is 75 degrees, the scattering angle is 160 degrees, and the reaction angle is 30 degrees. The sample current is 2 nA, the beam diameter is 1.5 mm phi, and the irradiation amount is 8 μC. There is no in-plane rotation.

p-RBS method

Hydrogen ions (H ⁺ ) are used as incident ions. Incident energy shall be 1740 KeV, incidence angle 0 degrees, scattering angle 160 degrees, and no recoil angle. The sample current is 1 nA, the beam diameter is 3 mm phi, and the irradiation amount is 19 μC. There is no in-plane rotation.

In addition to the RBS-HFS method, by combining the p-RBS method, the measurement accuracy of the hydrogen atom concentration can be further improved, and the amount of hydrogen (hydrogen atom concentration) can be quantified in association with the particles.

The hydrogen atom concentration contained in the structure which comprises the composite structure of this invention is 7 atomic% or less. In the structure of this invention, the surface is directly exposed, for example to a plasma atmosphere. Therefore, the property of the surface of the structure is particularly important. The present inventors consider that even if the structure has a porosity of 0.01 to 0.1% and contains almost no pores, the particle problem is still not solved under the influence of the nano-level microstructure, and as a result, the nano-level microstructure is controlled. We succeeded in doing this and got a new structure to solve the particle challenge at a higher level. In addition, the structure of this new structure was newly found to be able to be specified by using the surface hydrogen content (hydrogen atom concentration) as an index. And the correlation between the amount of hydrogen on the surface of the structure and the particle resistance is found in the present invention.

Specifically, for example, in the atmosphere, the hydrogen atom is considered to exist in a state such as hydroxyl group (-OH). The size of a molecule | numerator is about 3 kPa and a hydroxyl group is about 1 kPa as a water molecule, and it is thought that it exists slightly in the above-mentioned crude structure 80 of a structure. By using this amount of hydrogen (hydrogen atom concentration) as an index, a nano-level fine structure can be exhibited.

In this invention, the method which combined the p-RBS method and the RBS-HFS method is used as a specific method of hydrogen amount. In these methods, helium ions or hydrogen ions are incident on the surface of a sample, hydrogen is scattered forward and helium is scattered backward by elastic scattering, and the amount of hydrogen is quantified by detecting the hydrogen. At this time, the measurement depth of the amount of hydrogen becomes 400-500 nm from the surface 10a. Therefore, in the structure 10, it is possible to appropriately quantify the microstructure of the surface 10a that most affects the particles.

3rd aspect of this invention

As a basis for the third aspect of the present invention, it was found that a new index called luminance Sa had a high correlation with particle resistance at an extremely high level. Subsequently, the inventors succeeded in producing a structure having excellent particle resistance, in which the luminance Sa became a predetermined value or less. That is, it was found that a structure having a very high particle resistance can be obtained and that the particle resistance can be quantified by the luminance Sa. In addition, an evaluation method for obtaining luminance Sa was established.

Furthermore, the present inventors found out that the luminance Sa correlated with particle resistance is an index capable of evaluating further fine structure (fine structure) in the structure of ceramics, particularly the structure in which the porosity is evaluated to be 0.01 to 0.1%.

The composite structure according to the third aspect of the present invention,

A composite structure comprising a substrate and a structure installed on the substrate and having a surface,

The structure comprises polycrystalline ceramics,

A composite structure, characterized in that the luminance Sa value calculated by the following method is 19 or less:

The method of obtaining the luminance Sa,

(i) preparing a transmission electron microscope (TEM) observation sample of the structure;

(Ii) preparing a digital black and white image on the bright field of the TEM observation sample;

(Iii) acquiring a luminance value representing color data for each pixel in the digital monochrome image as a numerical value of gradation;

(Iii) correcting the luminance value;

(v) calculating a luminance Sa using the luminance value after the correction;

Made up,

In the step (i),

At least three said TEM observation samples are prepared from the said structure,

Each of the at least three TEM observation samples is produced by suppressing processing damage by using a focused ion beam method (FIB method: Focused Ion Beam method),

In the FIB processing, the surface of the structure is provided with a carbon layer and a tungsten layer for antistatic and sample protection,

When the FIB machining direction is in the longitudinal direction, the sample upper thickness, which is the length in the short axis direction of the structure surface, in a plane perpendicular to the longitudinal direction, is 100 ± 30 nm,

In the step (ii),

The digital black and white image is acquired for each of the at least three TEM observation samples,

Each of the digital black and white images includes the structure, the carbon layer, and the tungsten layer at a magnification of 100,000 times and an acceleration voltage of 200 kV using a transmission electron microscope (TEM).

In each of the digital black-and-white images, a luminance acquisition area having an area length of 0.5 μm in the longitudinal direction is set from the surface of the structure,

The plurality of digital black and white images are acquired from each of the at least three TEM observation samples so that the sum of the areas of the luminance acquisition area is 6.9 µm ² or more.

In the above step (iii),

The luminance value of the carbon layer is corrected relative to the luminance value of the carbon layer to 255 and the tungsten layer to zero, so that the corrected luminance value is obtained.

In the step (v),

For each of the luminance acquisition regions, an average of absolute values of the difference of the luminance values after the correction for each pixel is calculated using the least square method, and the average thereof is referred to as luminance Sa.

Moreover, the evaluation method by 3rd aspect of this invention,

It is a method for evaluating the microstructure of a structure including a polycrystalline ceramics and having a surface,

(i) preparing a transmission electron microscope (TEM) observation sample of the structure;

(Ii) preparing a digital black and white image on the bright field of the TEM observation sample;

(Iii) acquiring a luminance value representing color data for each pixel in the digital monochrome image as a numerical value of gradation;

(Iii) correcting the luminance value;

(v) calculating a luminance Sa using the luminance value after the correction;

Made up,

In the step (i),

At least three said TEM observation samples are prepared from the said structure,

Each of the at least three TEM observation samples is produced by suppressing processing damage using a focused ion beam method (FIB method),

In the FIB processing, the surface of the structure is provided with a carbon layer and a tungsten layer for antistatic and sample protection,

When the FIB machining direction is in the longitudinal direction, the sample upper thickness, which is the length in the short axis direction of the structure surface, in a plane perpendicular to the longitudinal direction, is 100 ± 30 nm,

In the step (ii),

The digital black and white image is acquired for each of the at least three TEM observation samples,

Each of the digital black and white images includes the structure, the carbon layer, and the tungsten layer at a magnification of 100,000 times and an acceleration voltage of 200 kV using a transmission electron microscope (TEM).

In each of the digital black and white images, a luminance acquisition area having an area length of 0.5 占 퐉 in the longitudinal direction is set from the surface of the structure,

The plurality of digital black and white images are acquired from each of the at least three TEM observation samples so that the sum of the areas of the luminance acquisition area is 6.9 µm ² or more.

In the above step (iii),

The luminance value of the carbon layer is corrected relative to the luminance value of the carbon layer to 255 and the tungsten layer to zero, so as to obtain the luminance value after correction.

In the step (v),

For each of the luminance acquisition regions, an average of absolute values of the difference of the luminance values after the correction for each pixel is calculated using the least square method, and the average thereof is referred to as luminance Sa.

Luminance Sa in the third aspect of the present invention

In the 3rd aspect of this invention, the microstructure of a structure is represented by the index called "luminance Sa". This "luminance Sa" is an index obtained by quantifying pixel information of a digital black and white image of the bright field image of the structure obtained by a transmission electron microscope (TEM) as described in detail below. The structure of the composite structure according to the present invention is characterized by having a luminance Sa of 19 or less, and preferably 13 or less.

The present inventors have found out that the luminance Sa correlated with the particle resistance is an index capable of evaluating further fine structures in the structure of the ceramics, especially the porosity of 0.01 to 0.1%. Therefore, in the present invention, the "fine structure" refers to a structure in which the porosity is evaluated to be 0.01 to 0.1%, having a particle resistance at a higher level, and having a difference in luminance Sa. Means a fine structure.

In the present specification, the term "luminance value" indicates color data for each pixel in a digital black and white image in numerical values of grayscales (0 to 255). Here, the "gradation" is a level of brightness. Specifically, what represents the color data for every pixel in a monochrome image by the numerical value according to 256 different brightness | luminance steps is called a luminance value ("Image processing apparatus and its use method" Nikkan Kogyo Shin-Bungsha, 1989, first edition, See page 227). Monochrome contrast in the TEM monochrome image is expressed as a luminance value.

In this specification, the term "luminance Sa" refers to the application of the concept of Sa (arithmetical mean height of the surface) defined in the international standard ISO25178 regarding three-dimensional surface constellation to image processing of a digital TEM image. will be. It demonstrates concretely using FIG. 5 which three-dimensionally displayed the luminance value of a digital TEM image. FIG. 5A is a digital black and white image of a structure that is a TEM bright field image. With respect to this digital monochrome image, the color data for each pixel is represented by numerical values of grayscales (0 to 255), and the numerical values are represented in the Z-axis direction in FIG. 5B. That is, in FIG. 5B, the Z axis represents the luminance value, and the luminance value of each pixel in the X-Y plane is shown in three dimensions. The three-dimensional image of this luminance value is converted into a three-dimensional image of the surface properties (for example, refer to the following URL: https://www.keyence.co.jp/ss/3dprofiler/arasa/surface/) specified in ISO25178. The average of the absolute value of the difference of the luminance value for every pixel is calculated using a least square method for a report and evaluation area, and it is set as "luminance Sa."

Next, "luminance Sa" in this specification is computed as outlined below.

-In the calculation of the luminance Sa in the present invention, the TEM observation sample for acquiring a digital black and white image is produced by suppressing processing damage using a focused ion beam method (FIB method). In FIB processing, the surface of the structure is provided with a carbon layer and a tungsten layer for antistatic and sample protection. When the FIB machining direction is in the longitudinal direction, the sample upper thickness, which is the length in the short axis direction of the structure surface in a plane perpendicular to the longitudinal direction, is 100 ± 30 nm. From one structure, at least three TEM observation samples are prepared.

-Digital monochrome image is acquired about each of at least 3 TEM observation samples. A digital black-and-white image is acquired by the transmission electron microscope (TEM) at 100,000 times magnification and 200 kV acceleration voltage. The digital black and white image includes a structure, a carbon layer, and a tungsten layer.

-In a digital black and white image, a luminance acquisition area of 0.5 m in the longitudinal direction is set from the surface of the structure. A plurality of said digital monochrome images are acquired from each of at least 3 TEM observation samples so that the sum total of the area of this brightness acquisition area may be 6.9 micrometer <^2> or more.

-The luminance value of the carbon layer is set to 255 and the tungsten layer is set to 0 with respect to the luminance value in which the color data for each pixel in the acquired digital monochrome image is represented by the numerical value of gradation.

Using the corrected luminance value, the luminance Sa is calculated as follows. That is, for each of the luminance acquisition regions, the average of the absolute values of the differences of the luminance values after the correction for each pixel is calculated using the least square method, and the average of these is the luminance Sa.

Hereinafter, the method of calculating the luminance Sa will be described in more detail with reference to FIGS. 2 to 9.

2 is a flowchart showing a method for calculating the luminance Sa. This flow chart is described below.

(i) TEM observation sample preparation

This step is a step of preparing a sample for TEM observation. This process is demonstrated with reference to FIG. The TEM observation sample is produced by a focused ion beam method (FIB method, Focused Ion Beam method). In the processing by the FIB method, the place for the purpose of observation can be determined and thinned ("Surface Analysis Technology Oath Transmission Electron Microscope", Japan Surface Chemical Society, Maruzen, Japan, issued March 30, 1999).

First, the structure 10 is cut out previously with a dicing machine or the like. At this time, the part corresponding to the sample acquisition location 40 of FIGS. 8 and 9 mentioned later is cut out first. And the FIB process is performed to the structure surface 10a, and it processes to the shape shown in FIG. At this time, arrow L in FIG. 3 is made into a longitudinal direction. The longitudinal direction L is substantially parallel to the thickness direction of the structure 10. In addition, the longitudinal direction L is a direction substantially the same as the longitudinal direction defined in the FIB processing direction mentioned above.

FIB processing is demonstrated in more detail. On the surface 10a of the structure 10 after dicing, a carbon layer 50 is deposited to suppress charge up and to protect the structure surface 10a. The deposition thickness of the carbon layer 50 is about 300 nm. Here, before the carbon layer 50 is formed, it is preferable to smooth the structure surface 10a by polishing or the like.

The structure 10 on which the carbon layer 50 is deposited is then sliced using a focused ion beam (FIB) device. Specifically, first, a portion of the structure 10 is cut out together with the carbon layer 50 by irradiating a Ga ion beam around the portion to be flaky with the carbon layer 50 upward. The cut out structure 10 is fixed to the TEM sample stage for FIB by using the tungsten deposition function by the FIB pick-up method. Subsequently, in order to obtain the TEM observation sample 90, the cut structure 10 is sliced. The order of this flaking is first formed on the carbon layer 50 of the structure 10, and the tungsten layer 60 is formed by the tungsten deposition process in the site | part which will be flaky for TEM observation. By providing the tungsten layer 60, breakage of the surface of the TEM observation sample by the Ga ion beam can be suppressed at the time of processing. The thickness of the tungsten layer 60 to be deposited is 500 to 600 nm. Then, the structure is cut from both sides at the flaking portion with Ga ions to prepare a TEM observation sample 90 having a predetermined thickness (length along the arrow T in the drawing).

In the present invention, the TEM observation sample 90 is produced so as to suppress processing damage such as uneven damage of the processing surface. Specifically, the acceleration voltage at the time of FIB processing starts from 40 kV which is the maximum voltage, and finally finishes at 5 kV which is the lowest voltage in order to avoid as much damage as possible on the surface of the structure and the formation of an amorphous layer. Alternatively, the damage layer is finally removed by Ar ions. You may observe after cleaning a surface by ion milling. About the details of these FIB processing, "fine processing using a FIB apparatus" (Muroy Matsuhiro, Tsukuba University technical report (24): 69-72, 2004), "FIB ion milling technique Q & A" (Masao Hirasaka, Genta Asakura) See Agne Shofusha.

(A) and (b) of FIG. 3A is a schematic diagram of the TEM observation sample 90 obtained as mentioned above. As shown to (a) and (b) of FIG. 3A, the TEM observation sample 90 has the shape of a thin rectangular parallelepiped. In FIG. 3A, the major axis direction is the horizontal direction W (arrow W in the figure) and the minor axis direction is the thickness direction T (arrow T in the drawing) with respect to two directions perpendicular to the longitudinal direction L. In FIG. do. As shown to (a) of FIG. 3A, in TEM observation, an electron beam permeate | transmits in the thickness direction T. As shown to FIG.

Because as shown in Fig. 3 (a), flaked by Ga ions, be done from the figures above, the sample 90 has a tendency to have a lower thickness 90 _b is larger than 90 _u thickness thereon. Here, the upper thickness of 90 _u is the length of the thickness direction T of the sample 90 on the surface 10a side. The thickness of the TEM observation sample 90 affects the transmission ability of the electron beam. Specifically, when the sample thickness is too large, the sensitivity of luminance Sa decreases, and there is a fear that correlation with particle resistance may not be obtained. When the sample thickness is too small, it is difficult to control the thickness at the time of processing, the thickness variation may occur in the TEM observation sample 90, and there is a fear that correlation with particle resistance may not be obtained. In the present invention, the upper thickness 90 _u is 100 nm ± 30 nm, more preferably 100 nm ± 20 nm.

Further, in order to calculate the luminance Sa from the image analysis using the TEM digital black-and-white image in the present invention, TEM observation sample (90) of the longitudinal difference of the thickness along the (L) (top thickness of 90 _u and a lower thickness 90 _b The processing is performed so that the difference is as small as possible. Usually, a sample becomes the form shown to Fig.3 (a), and the sample height 90h (length of the longitudinal direction L) is about 10 micrometers, and the sample width 90w (length of the horizontal direction W). ) Is about 10 µm to several tens of µm.

Check method of TEM observation sample 90, the upper thickness of 90 _u are as follows. About the TEM observation sample 90, a secondary electron image (refer FIG. 3B (c)) is acquired using a scanning electron microscope (SEM), and the upper thickness _90u is obtained from this secondary electron image. For example, Hitachi S-5500 manufactured by SEM is used. SEM observation conditions are set to 200,000 times magnification, acceleration voltage of 2 mA, scan time of 40 seconds, and number of images 2560 * 1920 pixels. At this time, the SEM image is a plane perpendicular to the longitudinal direction (L). Using the scale bar of this SEM image, upper thickness 90 _u is obtained. At this time, the upper thickness of 90 _u is taken as the average value of five times.

An alternative checking method of the upper thickness 90 _u is shown below. That is, for the digital image on the secondary electron, the luminance value is measured along the thickness direction T, and a luminance line profile is obtained. At this time, the line width is set to 11 pixels, and an average value of luminance values for 11 pixels in the line width direction is used. An example of the luminance line profile thus obtained is shown in Fig. 3C (d). Subsequently, the luminance line profile is firstly differentiated, and the maximum thickness and minimum value of the first derivative are used as the end portions of the structure 10 to obtain 90 _u of the upper thickness of the structure 10 (see (e) of FIG. 3C). At this time, upper thickness _90u is made into the average value of five luminance line profiles.

In calculating luminance Sa in the present invention, at least three TEM observation samples 90 described above are prepared from one composite structure. The preparation of at least three TEM observation samples is further described using FIGS. 8 and 9.

8 and 9 are schematic diagrams illustrating an example in which the composite structure 100 is used as the semiconductor manufacturing apparatus member 301. In FIG. 8, in the semiconductor manufacturing apparatus member 301, the structure 10 is provided on the surface 70a of the cylindrical base 70. In FIG. 9, in the semiconductor manufacturing apparatus member 302, the structure 10 is provided on the surface 70a of the columnar base material 70 in which the hole 31 is provided in the center.

In the semiconductor manufacturing apparatus members 301 and 302, the surface 10a of the structure 10 is exposed to corrosive plasma. The semiconductor manufacturing apparatus members 301 and 302 are members which comprise the inner wall of an etching chamber, such as a shower plate, a focus ring, a window, a sight glass, for example. When the structure 10 has the plasma irradiation area 30a and the plasma non-irradiation area 30b which is not exposed to plasma, the location where the sample acquisition point 40 for luminance Sa measurement corresponds to the plasma irradiation area 30a Set to. At this time, especially if there is an area irradiated with many plasmas, the correlation between particle resistance and luminance Sa can be improved by setting the structure surface 10a corresponding to the area to the sample acquisition point 40.

In the present invention, at least three sample acquisition points 40 for luminance Sa measurement for producing the TEM observation sample 90 are used. 8 and 9, the some sample acquisition location 40 is arrange | positioned evenly in the plasma irradiation area | region 30a, respectively. Thereby, high correlation between the brightness | luminance Sa and particle resistance of the composite structure 100 can be ensured.

(Ii): Acquisition of TEM image G (clear field view)

In this step, a cross section of each of the at least three TEM observation samples 90 obtained in (i) is observed at a magnification of 100,000 times and an acceleration voltage of 200 kV by TEM, and the structure 10 and the carbon layer ( TEM image G (refer FIG. 4) containing 50) and tungsten layer 60 is acquired. The cross section of the TEM observation sample 90 is a cross section of the composite structure 100 shown in FIG. 1, and more specifically, a cross section including the vicinity of the surface 10a of the structure 10. At this time, the bright field image is acquired. A bright field image is an image formed by passing only a transmitted wave through an object aperture ("Surface Analysis Technology Oath Transmittance Electron Microscope", Japan Surface Chemical Society, Maruzen, Japan, issued March 30, 11, 43-43). Page 44).

For the imaging of the TEM image G, for example, a transmission electron microscope (manufactured by H-9500 / Hitachi High Technologies) is used. The acceleration voltage is set at 200 Hz, and the digital camera (manufactured by OneView Camera Model 1095 / Gatan) sets the image capture mode at 4096 x 4096 pixels, capture speed 6 fps, and exposure time 2 sec at the exposure time and camera position bottom mount. It is performed on the conditions equivalent to the image | photographing conditions. As shown in FIG. 4, in the acquisition of this image G, the structure 10, the structure surface 10a, the carbon layer 50, and the tungsten layer 60 are set in the same field of view.

In the present invention, the luminance Sa is calculated by image analysis on the luminance information of the digital image. Therefore, the focus accuracy in photography is very important. Therefore, for example, when acquiring a 100,000-fold TEM image, 100,000-fold TEM images are acquired after focus adjustment is performed at a high magnification of 300,000 times or more.

The TEM image G which is a digital black and white image is demonstrated again using FIG. 4: is a schematic diagram of TEM image G (bright field image), and the square part of vertical length Gl and horizontal length Gw is TEM image G in a figure. In FIG. 4, on the surface 10a of the structure 10, there is an image corresponding to the carbon layer 50 deposited in the step (i) and the tungsten layer 60. The lower portion from the surface 10a corresponds to the structure 10. In the TEM image G, the carbon layer 50 becomes white to light gray, and the tungsten layer 60 becomes black.

In the present specification, in the TEM image G, the direction in which the structure 10, the carbon layer 50, and the tungsten layer 60 are arranged, that is, the direction indicated by the arrow L in FIG. ", The direction of the arrow W in the figure perpendicular | vertical with respect to a" vertical direction "is called" lateral direction. " This longitudinal direction L corresponds to the longitudinal direction L of FIG. 3A.

The physical properties and properties of the composite structure according to the present invention, for example, particle resistance, are governed by properties near the surface of the structure. The inventors found out that the luminance Sa in the region where the longitudinal length dL along the longitudinal direction L from the structure surface 10a is 0.5 µm correlates with the physical properties and characteristics such as particle resistance. The image longitudinal length Gl and the image lateral length Gw of the TEM image acquired at a magnification of 100,000 times vary depending on the camera, but are generally about 1.5 µm to 2.0 µm, respectively. Therefore, in the present invention, using a 100,000-fold TEM image, the luminance acquisition region R is set with an area vertical length dL of 0.5 µm, and the luminance Sa is determined from the luminance value in the luminance acquisition region R.

In the present invention, the luminance acquisition area R is set for each image G. Then, a plurality of digital black and white images are acquired from each of at least three TEM observation samples so that the sum of the areas of the luminance acquisition regions R is 6.9 µm ² or more. At this time, the number of images G obtained from each TEM observation sample is made equal. The detail of the sum total of the area of the luminance acquisition area | region R is mentioned later.

(Iii): Acquisition of luminance value

Next, in this step, the luminance value for each pixel corresponding to the &quot; longitudinal &quot; and &quot; lateral direction &quot; in the TEM image G which is the digital black and white image acquired in the step (ii) is obtained. This includes the luminance value of the tungsten layer in the image G and the luminance value of the carbon layer. FIG. 5A is a plan view illustrating an example of the acquired TEM image G. FIG. Arrow Y in FIG. 5A corresponds to the longitudinal direction L in FIGS. 3 and 4. An arrow X in FIG. 5A corresponds to the lateral direction W in FIGS. 3 and 4. FIG. 5B is a diagram showing three-dimensionally the luminance value of each pixel in the image G in the arrow Z direction.

(Iii): Process of correcting luminance value

Next, in this step, a correction operation of the luminance value of the TEM image G obtained in the step (iii) is performed. The specific content is demonstrated using FIG. FIG. 6A shows three-dimensionally the luminance value of the TEM image G obtained in the step (iii), and the luminance value of each pixel corresponding to the longitudinal and transverse coordinates of the structure 10 in three dimensions. Drawing. This includes the luminance value of the tungsten layer in the image G and the luminance value of the carbon layer in the same manner as in the step (i). In this step, the luminance value for each pixel is set as the luminance value of the tungsten layer 60 in the image G as 0 and the luminance value of the carbon layer 50 in the image G as 255, corresponding to the structure 10. Correct the value relative to each pixel. As described above, in the TEM image G, the tungsten layer 60 becomes black and the carbon layer 50 becomes white to pale gray. In this step, the luminance value for each pixel of the structure 10 is corrected as a relative value between the luminance value 0 of the tungsten layer and the luminance value 255 of the carbon layer, and is determined. FIG. 6B is a diagram showing three-dimensionally the luminance value of the corrected image G. FIG. In contrast to FIG. 5, it can be seen that the tungsten layer 60 is black and the carbon layer 50 is white to light gray, and the luminance value of the structure 10 is relatively corrected.

In the TEM image G, it is usual to see slight fluctuations in the luminance value for each pixel of the carbon layer 50 / tungsten layer 60. In order to eliminate the influence of this fluctuation, the luminance value 0 of the tungsten layer and the luminance value 255 of the carbon layer are determined as follows. As the luminance value of the tungsten layer 60, the average value of the luminance value for 10,000 pixels is used successively from the minimum value of the luminance value in the tungsten layer 60 in the image G in order. In addition, the average value of the luminance value for 100,000 pixels is used for the luminance value of the carbon layer 50 in order of succession from the maximum value of the luminance value in the carbon layer 50 continuously. Each average value obtained here is treated as a luminance value of the carbon layer 50 / tungsten layer 60 before correction. The luminance value is similarly corrected for the plurality of TEM images G.

(v): calculation of luminance Sa

In this step, the luminance Sa is calculated from the luminance value of the image G obtained in the step (iii). Specifically, for each of the above-described luminance acquisition regions R (hereinafter, each luminance acquisition region is represented by R _n ), the average of the absolute values of the differences in luminance values after correction for each pixel is calculated using the least square method. Let these averages be the luminance Sa _n of the region R _n . And the luminance acquisition region R _{1 + 2 +.} The average value of the luminance Sa _n computed about the some luminance acquisition area | region _Rn set so that the sum total of the area of _{+ n} may be set to 6.9 micrometer <^2> or more shall be the luminance Sa of the structure 10. As shown in FIG.

In the present invention, in order to increase the correlation between the properties Sa and the properties of the structure, for example, the particle resistance, the area of the brightness acquisition area R is set to 6.9 µm ² or more. . By determining the luminance Sa based on the area exceeding this area, even if there is a possibility that a change in the physical properties and characteristics may occur in the limited area in the structure 10, the correlation between the luminance Sa and the physical properties is accurately corrected. It can be represented properly.

The size of one TEM observation sample 90 is very small compared to the surface area of the structure 10, that is, the plasma irradiation area. On the other hand, physical properties and properties imparted to the structure, for example, particle resistance, are required in principle on the entire surface of the structure. In this regard, in the present invention, a total area of 6.9 µm ² or more of the luminance acquisition region R is required, and at least three TEM observation samples are produced from the structure 10. That is, in the present invention, a plurality of TEM observation samples are evenly obtained from the surface of the structure so that the information on the entire structure surface is covered as much as possible. In addition, when acquiring at least 3 or more TEM observation samples, consideration needs to be made so that the information on the entire structure surface is covered.

Luminance Sa correlates with physical properties and properties of the structure, for example, particle resistance. Therefore, according to the present invention, instead of evaluating the actual particle resistance of the structure, by calculating the luminance Sa of the structure, it is possible to grasp the performance such as the particle resistance of the structure before use thereof.

The process of calculating the luminance Sa will be described in more detail with reference to the description of the area of the luminance acquisition region R. FIG.

In order to improve the correlation between the luminance Sa and the particle resistance, in the present invention, the luminance acquisition region R in the image G is set so that the total area thereof is 6.9 µm ² or more. Specifically, a plurality (n) images G _n are obtained from at least three TEM observation samples, and an area R _n is set for each image. The average value of the luminance Sa _n of each image G _n is taken as the luminance Sa of the structure.

4, with reference to (a) ~ (b) (a) and Figure 7a of Figure 6, the description will be made as to how to calculate the intensity Sa ₁ from one of the image G _1.

As it is shown in (a) of Fig. 4 and 6, for a single image G _1, and sets the region R _1. In one region R ₁ , the region length dL is 0.5 μm. This is because, as described above, the properties near the surface of the structure are most correlated with the physical properties and properties of the structure, for example, particle resistance. Further, as the area of the transverse width of dW (W) in the region R _1, it is set to be the longest in the image G. As an example, at a magnification of 100,000 times, the area length dW is about 1.5 µm to 2.0 µm. That is, a single TEM image G configurable region R ₁ for the _first area up to 10 million times magnification is the 0.75~1.0㎛ ^2.

Therefore, in this example, the number of images G required to set the total area of the luminance acquisition region R _n to 6.9 µm ² is 7 to 9 sheets. As described above, in the present invention, at least three TEM observation samples 90 are prepared, and the same number of TEM images G are obtained from the respective TEM observation samples 90. Therefore, in this example, three images G are acquired for one TEM observation sample 90. When acquiring a plurality of TEM images G _n from a TEM observation sample (90), and acquires a plurality of images Ido G _n, as shown in 3b so that continuous in the lateral direction (W). In addition, the size of the image G _n of the plurality of (image longitudinal length Gl, image Gw lateral length), and are each substantially the same. Thereby, for example, the influence of the measurement variation between observers can be made small, and the correlation between luminance Sa and particle resistance can be improved further.

The inventors have found out that the luminance Sa in the region of 0.5 占 퐉 from the structure surface 10a correlates most with the physical properties and properties of the structure, for example, particle resistance. Therefore, in the region R at the time of calculating the luminance Sa, the region vertical length dL is 0.5 μm. In addition, in the step (i), as described with reference to FIG. 3, since the processing is performed from the surface 10a direction of the structure 10, even when the processing accuracy is increased, the sample upper thickness 90 of the TEM observation sample 90 is obtained. It is lower than the sample thickness 90 _{u b} is the larger tapered shape. Therefore, the greater the depth from the surface 10a of the structure 10, the more difficult the electron beam is to penetrate, and the less sensitive the luminance value is. That is, in the image G, as the depth is moved toward the depth than the surface 10a side, the image becomes an overall dark, ie darkish image. Therefore, in order to make the influence of a sample thickness small enough, it is necessary to make area length dL into 0.5 micrometer.

When setting the brightness | luminance acquisition area | region R, the area | region vertical length dL sets the vicinity of the surface 10a of the structure 10 as a starting point. In the TEM image G, when a gap is observed between the surface 10a and the carbon layer 50, it is necessary to avoid this and set the region R. The "near surface 10a" points out the range of about 5-50 nm from surface 10a. The detail of a specific setting can be made with reference to a later Example.

The processes in the above steps (i) to (v) can be performed continuously and collectively in the image analysis software. As such software, WinROOF2015 (available from Mitani Corporation) can be used.

The smaller the luminance Sa of the structure of the composite structure according to the present invention is, the smaller it is considered to be preferable. However, it is apparent to those skilled in the art that there is a limit in practical production. Since such a manufacturing limit becomes a lower limit of luminance Sa in this invention, it is not obscuring this invention by a 3rd aspect that a lower limit is not specifically specified. This point is the same also in the following 4th aspect.

Fourth aspect of the present invention

In the fourth aspect of the present invention, similarly to the third aspect of the present invention, the luminance Sa is used as an index, but the process (i) in the method of obtaining the luminance Sa in the first aspect, that is, the process of correcting the luminance value The method is characterized in that a step of removing a noise component is added. Therefore, description of the 3rd aspect in this specification other than the process of removing the noise component becomes a description of 4th invention.

And the composite structure according to the fourth aspect of the present invention,

A composite structure comprising a substrate and a structure installed on the substrate and having a surface,

The structure comprises polycrystalline ceramics,

A composite structure, characterized in that the luminance Sa value calculated from the following method is 10 or less:

The method of obtaining the luminance Sa,

(i) preparing a transmission electron microscope (TEM) observation sample of the structure;

(Ii) acquiring a digital black and white image of a bright field of the TEM observation sample;

(Iii) acquiring a luminance value representing color data for each pixel in the digital monochrome image as a numerical value of gradation;

(Iii) correcting the luminance value;

(v) calculating a luminance Sa using the luminance value after the correction;

Made up,

In the step (i),

At least three said TEM observation samples are prepared from the said structure,

Each of the at least three TEM observation samples is produced by suppressing processing damage using a focused ion beam method (FIB method),

In the FIB processing, the surface of the structure is provided with a carbon layer and a tungsten layer for antistatic and sample protection,

When the FIB machining direction is in the longitudinal direction, the sample upper thickness, which is the length in the short axis direction of the structure surface, in a plane perpendicular to the longitudinal direction, is 100 ± 30 nm,

In the step (ii),

The digital black and white image is acquired for each of the at least three TEM observation samples,

Each of the digital black and white images includes the structure, the carbon layer, and the tungsten layer at a magnification of 100,000 times and an acceleration voltage of 200 kV using a transmission electron microscope (TEM).

In each of the digital black-and-white images, a luminance acquisition area having an area length of 0.5 μm in the longitudinal direction is set from the surface of the structure,

The plurality of digital black and white images are acquired from each of the at least three TEM observation samples so that the sum of the areas of the luminance acquisition area is 6.9 µm ² or more.

In the above step (iii),

The luminance value of the carbon layer is corrected relative to the luminance value of the carbon layer to 255 and the tungsten layer to zero, so that the corrected luminance value is obtained.

Noise reduction using a low pass filter is performed on the digital black and white image in which the luminance value is corrected, and a cut-off frequency in noise removal using the low pass filter is 1 / (10 pixels). ego,

In the step (v),

For each of the luminance acquisition regions, an average of absolute values of the difference of the luminance values after the correction for each pixel is calculated using the least square method, and the average thereof is referred to as luminance Sa.

In addition, the evaluation method according to the present invention,

It is a method for evaluating the microstructure of a structure including a polycrystalline ceramics and having a surface,

(i) preparing a transmission electron microscope (TEM) observation sample of the structure;

(Ii) acquiring a digital black and white image of a bright field of the TEM observation sample;

(Iii) acquiring a luminance value representing color data for each pixel in the digital monochrome image as a numerical value of gradation;

(Iii) correcting the luminance value;

(v) calculating a luminance Sa using the luminance value after the correction;

Made up,

In the step (i),

At least three said TEM observation samples are prepared from the said structure,

Each of the at least three TEM observation samples is produced by suppressing processing damage using a focused ion beam method (FIB method),

In the FIB processing, the surface of the structure is provided with a carbon layer and a tungsten layer for antistatic and sample protection,

When the FIB machining direction is in the longitudinal direction, the sample upper thickness, which is the length in the short axis direction of the structure surface, in a plane perpendicular to the longitudinal direction, is 100 ± 30 nm,

In the step (ii),

The digital black and white image is acquired for each of the at least three TEM observation samples,

Each of the digital black and white images includes the structure, the carbon layer, and the tungsten layer at a magnification of 100,000 times and an acceleration voltage of 200 kV using a transmission electron microscope (TEM).

In each of the digital black-and-white images, a luminance acquisition area having an area length of 0.5 μm in the longitudinal direction is set from the surface of the structure,

The plurality of digital black and white images are acquired from each of the at least three TEM observation samples so that the sum of the areas of the luminance acquisition area is 6.9 µm ² or more.

In the above step (iii),

The luminance value of the carbon layer is corrected relative to the luminance value of the carbon layer to 255 and the tungsten layer to zero, so that the corrected luminance value is obtained.

Noise reduction using a low pass filter is performed on the digital black and white image in which the luminance value is corrected, and a cut-off frequency in noise removal using the low pass filter is 1 / (10 pixels). ego,

In the above step (v), for each of the luminance acquisition regions, an average of absolute values of the difference of the luminance values after the correction for each pixel is calculated using the least square method, and the average of them is the luminance Sa. It is characterized by.

Thus, the composite structure according to the fourth aspect is characterized in that the luminance Sa is 10 or less, preferably 5 or less.

In the fourth aspect of the present invention, the step (i), that is, the step of preparing a transmission electron microscope (TEM) observation sample of the structure, in order to determine the luminance Sa as in the third aspect of the present invention, and the step ( Ii), i.e., preparing a digital monochrome image on the bright field of the TEM observation sample; and (b) obtaining the luminance value representing the color data for each pixel of the digital monochrome image in grayscale values. Is done. In addition, in the step (iii), a step of removing the noise component in the image is performed as necessary so that the luminance Sa more accurately and appropriately represents the fine structure of the structure. The TEM image G contains noise having a high frequency component, which is removed by a filter in this addition step. In this embodiment, noise is removed from the image G using a low-pass filter (LPF). For details of the noise removal in image processing, refer to "Image processing-the 2nd edition from the foundation to application" (Ozaki Hiroshi-Taniguchi Gauge, Kyoritsu Shot Co., Ltd.).

In this aspect, the cut-off frequency in noise reduction using a low pass filter is set to 1 / (10 pixels). In other words, the cutoff period is 10 pixels. For example, when WinROOF2015 is used as the image processing software, the cutoff frequency is set using the noise cancel command.

7B and 7D show noise removal using a low pass filter as cutoff frequency 1 / (10 pixels) for FIGS. 7A and 7B which are images G after luminance value correction. It is an example of an image. By removing the noise, influences such as the focus accuracy of the TEM image G can be eliminated, and the correlation between the physical properties and properties of the structure, for example, particle resistance and luminance Sa, can be enhanced.

In the 4th aspect of this invention, the process (v) of calculating luminance Sa using the luminance value after correction obtained in this way is performed after that. This process (v) may also be the same as that of the 3rd aspect of this invention.

5th aspect of this invention

In the fifth aspect of the present invention, unlike the first to fourth aspects of the present invention, the object is limited to a structure containing Y (yttrium element) and O (oxygen element), and the microstructure of the structure is The refractive index is expressed as an index. That is, the present inventors, for example, in the composite structure having a structure containing Y (yttrium element) and O (oxygen element) used in a situation exposed to a corrosive plasma environment such as a semiconductor manufacturing apparatus, the effect of particles Succeeded in making it very small. And it was found that the particle resistance performance can be evaluated at an extremely high level by using the refractive index as an index.

The composite structure according to the fifth aspect of the present invention,

A composite structure comprising a substrate and a structure installed on the substrate and having a surface,

The structure comprises polycrystalline ceramics comprising Y (elemental yttrium) and O (elemental oxygen),

The refractive index in the wavelength 400nm-550nm is larger than 1.92,

The refractive index is calculated by reflection spectroscopy using a microscopic spectrophotometer,

As measurement conditions, measurement spot size is 10 micrometers, the average surface roughness Ra≤0.1micrometer of the said substrate surface and the said composite structure surface, the thickness of the said structure≤1micrometer, the measurement wavelength range 360-1100nm,

As analysis conditions, the analysis wavelength range 360-1100 nm, the optimization method, and the least square method are used.

Moreover, the composite structure by 5th another aspect of this invention is

A composite structure comprising a substrate and a structure installed on the substrate and having a surface,

The structure comprises polycrystalline ceramics comprising Y (elemental yttrium) and O (elemental oxygen),

The refractive index satisfies at least one of 1.99 or more at a wavelength of 400 nm, 1.96 or more at a wavelength of 500 nm, 1.94 or more at a wavelength of 600 nm, 1.93 or more at a wavelength of 700 nm, and 1.92 or more at a wavelength of 800 nm or more. ,

The refractive index is calculated by reflection spectroscopy using a microscopic spectrophotometer,

As measurement conditions, measurement spot size is 10 micrometers, the average surface roughness Ra≤0.1micrometer of the said substrate surface and the said composite structure surface, the thickness of the said structure≤1micrometer, the measurement wavelength range 360-1100nm,

As analysis conditions, the analysis wavelength range 360-1100 nm, the optimization method, and the least square method are used.

In general, the average refractive index of Y ₂ O ₃ is 1.92 (Japanese Chemical Society edition "Chemical Handbook", Maruzen (1962), p919, "Ceramic Chemistry" p220, Table 8-24, Japan Ceramics Association, 1994 9) 30/30 revision, etc.) In addition, Japanese Chemical Society 1979, (8), p. 1106 to 1108 (Non-Patent Document 1) discloses refractive index and reflectance as optical characteristics of a yttrium sintered compact that is a transparent plate-like sample (see FIG. 20). In contrast, in the composite structure according to the fifth aspect of the present invention, the refractive index at a wavelength of 400 to 550 nm is larger than 1.92, for example. Alternatively, at least one of 1.99 or more at a wavelength of 400 nm, 1.96 or more at a wavelength of 500 nm, 1.94 or more at a wavelength of 600 nm, 1.93 or more at a wavelength of 700 nm, and 1.92 or more at a wavelength of 800 nm or more are satisfied.

In the fifth aspect, the basic structure of the composite structure is the same as that of the composite structure according to the first to fourth aspects, except that in the basic structure in FIG. 1, the structure 10 is Y (yttrium element). And polycrystalline ceramics (hereinafter referred to as "YO compound" in some cases) containing O (oxygen element). The structure 10 included in the composite structure exhibits a predetermined refractive index.

Therefore, the structure 10 containing Y (yttrium element) and O (oxygen element) which the composite structure which concerns on 5th aspect is equipped is what is called Y-O compound coating. By coating the Y-O compound, various physical properties and characteristics can be imparted to the substrate 70. In addition, also in this aspect, a ceramic structure and a ceramic coating are used by the same meaning unless there is particular notice.

According to one preferred embodiment, the structure 10 is composed mainly of polycrystalline ceramics containing the YO compound, preferably greater than 50%, more preferably at least 70%, even more preferably at least 90%, of the YO compound, It contains 95% or more. Most preferably, structure 10 consists of a Y—O compound.

In this embodiment, a YO compound is an oxide of yttrium, for example. For example, Y ₂ O ₃ , Y _α O _β (non-stoichiometric composition) may be mentioned. In addition to the Y element and the O element, other elements may be included. For example, the YO compound containing at least any one of F element, Cl element, and Br element is mentioned. The structure 10 contains, for example, Y ₂ O ₃ as a main component. The content of Y ₂ O ₃ is, to more than 70%, preferably at least 90%, more preferably at least 95%. Most preferably, the structure 10 consists of 100% Y ₂ O ₃ .

Refractive Index in Fifth Aspect

The measurement of the refractive index may be performed by calculating by reflectance spectroscopy using a microscopic spectrophotometer (for example, Otsuka Denshi OPTM-F2, FE-37S). As measurement conditions, it is set as the measurement spot size of 10 micrometers, and the measurement wavelength range 360-1100 nm. In addition, as analysis conditions, it is set as the analysis wavelength range 360-1100 nm, and the optimization method and the least square method are used.

In the composite structure according to the fifth aspect of the present invention, the refractive index at wavelength 400nm to 550nm is larger than 1.92, preferably the refractive index at 400nm to 600nm is larger than 1.92, more preferably 400 The refractive index in nm-800 nm is larger than 1.92. In the composite structure according to the fifth aspect of the present invention, the refractive index is 1.99 or more at a wavelength of 400 nm, 1.96 or more at a wavelength of 500 nm, 1.94 or more at a wavelength of 600 nm, 1.93 or more at a wavelength of 700 nm, At least one of 1.92 or more is satisfied in wavelength 800nm or more. The present inventors newly found a novel structure in which the refractive index is increased as described above in the composite structure containing the Y-O compound. And surprisingly, in a composite structure containing a Y-O compound having a very high refractive index, it was found that the particle resistance was very excellent, and it was thus disclosed in the present invention. In one preferred embodiment of the present invention, the upper limit of the refractive index is 2.20.

Method of preparation of composite structure

The composite structure according to the present invention may be produced by various purposeful manufacturing methods as long as it can realize that the above-described indicators of the first to fifth aspects can be realized. According to one aspect of the present invention, the composite structure according to the present invention can be preferably produced by forming a structure on a substrate by the aerosol deposition method (AD method). According to one preferred aspect of the present invention, the structure of the composite structure according to the present invention can be realized by the AD method. In the AD method, an aerosol mixed with fine particles of a brittle material such as ceramics and a gas is sprayed onto the surface of a substrate to collide with the substrate at high speed, and the particles are pulverized or deformed by the collision to form a structure on the substrate ( Ceramic coating).

Device which enforces AD method

Although the apparatus used for the AD method of manufacturing the composite structure by the 1st-5th aspect of this invention is not specifically limited, It has the basic structure shown in FIG. That is, the apparatus 19 used for AD method is comprised by the chamber 14, the aerosol supply part 13, the gas supply part 11, the exhaust part 18, and the piping 12. As shown in FIG. In the chamber 14, the stage 16 on which the substrate 70 is disposed, the driving unit 17, and the nozzle 15 are disposed. The position of the base material 70 and the nozzle 15 arrange | positioned at the stage 16 by the drive part 17 can be changed relatively. At this time, the distance between the nozzle 15 and the base material 70 may be constant or may be variable. In this example, the drive unit 17 shows an aspect of driving the stage 16, but the drive unit 17 may drive the nozzle 15. The driving direction is, for example, the XYZθ direction.

In the apparatus of FIG. 10, the aerosol supply unit 13 is connected to the gas supply unit 11 by a pipe 12. In the aerosol supply unit 13, an aerosol in which raw material fine particles and a gas are mixed is supplied to the nozzle 15 through a pipe 12. The apparatus 19 is further provided with the powder supply part (not shown) which supplies a raw material fine particle. The powder supply unit may be disposed in the aerosol supply unit 13 or may be disposed separately from the aerosol supply unit 13. In addition to the aerosol supply unit 13, an aerosol forming unit for mixing the raw material fine particles and the gas may be provided. A homogeneous structure can be obtained by controlling the supply amount from the aerosol supply unit 13 so that the amount of the fine particles injected from the nozzle 15 is constant.

The gas supply part 11 supplies nitrogen gas, helium gas, argon gas, air, etc. When the gas supplied is air, it is preferable to use compressed air with few impurities, such as moisture and oil, or to provide the air processing part which removes impurities from air.

Next, operation | movement of the apparatus 19 used for AD method is demonstrated. In the state where the base material is arranged in the stage 16 in the chamber 14, the inside of the chamber 14 is reduced by atmospheric pressure, specifically several hundred kPa by the exhaust part 18, such as a vacuum pump. On the other hand, the internal pressure of the aerosol supply part 13 is set higher than the internal pressure of the chamber 14. The internal pressure of the aerosol supply part 13 is for example several hundreds to tens of thousands kPa. You may make a powder supply part atmospheric pressure. By the differential pressure between the chamber 14 and the aerosol supply unit 13, the fine particles in the aerosol are accelerated so that the injection speed of the raw material particles from the nozzle 15 is in the subsonic to supersonic speed (50 to 500 m / s) range. The injection speed is appropriately controlled by the flow rate of the gas supplied from the gas supply part 11, the gas type, the shape of the nozzle 15, the length and the inner diameter of the pipe 12, the displacement of the exhaust part 18, and the like. For example, as the nozzle 15, supersonic nozzles, such as a Laval nozzle, can also be used. Particulates in the aerosol ejected at high speed from the nozzle 15 impinge on the substrate, pulverize or deform, and are deposited as structures on the substrate. By changing the relative positions of the substrate and the nozzle 15, a composite structure having a structure having a predetermined area on the substrate is formed. Specific manufacturing conditions, such as a pressure in a chamber, gas flow volume, etc. change with combination of individual apparatus, These conditions can be adjusted suitably in the range which can form the structure of this invention.

In addition, before discharging from the nozzle 15, a disintegrating unit (not shown) for dissolving the fine particles may be provided. The disintegration method in a disintegration part can select arbitrary methods, as long as it satisfy | fills the form of collision to the base material of the microparticles mentioned later. For example, well-known methods, such as mechanical disintegration, such as a vibration and a collision, static electricity, plasma irradiation, classification, are mentioned.

In addition to the above, the composite structure according to the present invention is preferably used in the following uses. That is, aerospace coatings such as electric vehicles, touch panels, LEDs, solar cells, dental implants, satellite mirrors, sliding members, chemical plants, etc., corrosion-resistant coatings, all-solid-state batteries, thermal barrier coatings, high refractive index applications For example, it is used suitably in uses, such as an optical lens, an optical mirror, an optical element, a jewelry ornament.

EXAMPLE

Although this invention is further demonstrated by the following Example, this invention is not limited to these Examples.

1. Sample making

1-1 Raw Particles

As raw material particles, yttrium oxide, yttrium oxyfluoride, yttrium fluoride, aluminum oxide powder and zirconium oxide powder were prepared. Average particle diameters and particle states of various powders were as shown in Table 1.

Production of 1-2 samples

Using the said raw material particle and the base material shown in Table 1, the composite structure of the samples a-d and f-n was produced. As sample e, a commercially available sample produced by the ion plating method was used, and other samples were produced by the aerosol deposition method.

The basic structure of the apparatus used for AD method was the same as that of the apparatus shown in FIG. The raw material particles, the base material, the gas species, and the gas flow rate of each sample were as shown in Table 1, and the injection speed from the nozzle was 150 m / s or more. In addition, the formation thickness of the structure was all about 5 micrometers. Formation of the structure was performed at room temperature (around 20 ° C).

2. Characterization of the structure (1 of it)

2-1 Average Determinant Size

For sample e and sample c, the average crystallite size was calculated from a TEM image taken at a magnification of 400,000 times. Specifically, the average crystallite size was calculated from an average value obtained by circular approximation of 15 crystallites using an image acquired at a magnification of 400,000 times.

For sample c produced by the AD method, the average crystallite size calculated by the TEM image was 9 nm.

In sample e produced by ion plating, the average crystallite size calculated by the TEM image was 1 nm.

2-2 Porosity Measurement

The porosity was computed from image analysis using image analysis software WinRoof2015 using the image acquired with the scanning electron microscope (SEM) about the samples a-h. The magnification was 5000 to 20,000 times. The measurement of this porosity is conventionally used as a method of evaluating the density of a structure.

As a result, in all the samples a-h, the porosity was 0.01% or less. SEM images of samples a, c, e, f and g were as shown in Figs. 12A to 12D, respectively. As will be described later, the difference in the structure of the sample could not be specified by the measurement of the porosity conventionally performed for these samples having different particle resistance.

3. Characterization of the structure (2 of it)

3-1. Hydrogen content measurement by D-SIMS method

As a sample for hydrogen amount measurement, it produced using the following method. First, two samples a to c, f, i to k, m and n were prepared. The sample size was made into 3 mm x 3 mm and thickness 3 mm. For each sample, one was used as a standard sample and the other was used as a sample for measurement. For each sample, the surface 10a of the structure 10 was polished or the like to obtain a two-dimensional average surface roughness Ra of 0.01 µm. Next, about each sample, after leaving for 24 hours or more in the state of room temperature 20-25 degreeC, humidity 60% +/- 10%, and atmospheric pressure, the amount of hydrogen was measured by D-SIMS.

Secondary Ion Mass Spectrometry: The amount of hydrogen was measured by Dynamic-Secondary Ion Mass Spectrometry (D-SIMS method) as an apparatus using IMF-7f manufactured by CAMECA.

The preparation of the standard sample was as follows. The evaluation sample, the standard sample for evaluation samples which is a sample which has a matrix component equivalent to an evaluation sample, Si single crystal, and the standard sample for Si single crystal were prepared. About each sample prepared two, one was made into the evaluation sample and the other was made into the standard sample for evaluation samples. The standard sample for the evaluation sample is the injection of deuterium into a sample having a matrix component equivalent to that of the evaluation sample. At this time, deuterium was also injected into Si single crystal, and deuterium equivalent to the standard sample for evaluation sample and Si single crystal was injected. Then, the amount of deuterium injected into the said Si single crystal was identified using the standard sample for Si single crystal. About the standard sample for evaluation samples, secondary ion intensity of deuterium and a structural element was computed using the secondary ion mass spectrometry (D-SIMS method), and the sensitivity coefficient between phases was computed. The amount of hydrogen in the evaluation sample was calculated using the phase sensitivity coefficient calculated from the standard sample for evaluation sample. In other cases, ISO 18114_ "Determining relative sensitivity factors from ion-implanted reference materials" (International Organization for Standardization, Geneva, 2003) was appropriately referred to.

Conductive platinum (Pt) was deposited on the structure surface of each of the measurement sample and the standard sample. As measurement conditions of D-SIMS, cesium (Cs) ions were used for the primary ion species. The primary acceleration voltage was 15.0 kV, the detection area was 8 µm phi, and the measurement depth was set to three levels of 500 nm, 2 µm and 5 µm.

The number of hydrogen atoms (atoms / cm 3) per unit volume obtained was as shown in Table 2 described later.

3-2. Measurement of the amount of hydrogen by RBS-HFS method and p-RBS method

First, the surface 10a of the structure 10 was polished with respect to samples a, c, f, and j, and two-dimensional average surface roughness Ra was made into 0.01 micrometer. Next, the sample was allowed to stand at room temperature 20-25 ° C., humidity 60% ± 10%, and atmospheric pressure for 24 hours or longer, and then the amount of hydrogen (hydrogen atom concentration) was measured.

The amount of hydrogen was measured by combining RBS-HFS and p-RBS. As an apparatus, Pelletron 3SDH manufactured by National Electrostatics Corporation was used.

The measurement conditions of the RBS-HFS method were as follows.

Incident Ion: 4He ⁺

Incident energy: 2300KeV, Incidence angle: 75 °, Scattering angle: 160 °, Recoil angle: 30 °

Sample current: 2 nA, beam diameter: 1.5 mmφ, irradiation amount: 8 μC

In-plane rotation: none

The measurement conditions of the p-RBS method were as follows.

Incident ions: hydrogen ions (H ⁺ )

Incident energy: 1740KeV, Incident angle: 0 °, Scattering angle: 160 °, Recoil angle: None

Sample current: 1 nA, beam diameter: 3 mmφ, irradiation amount: 19 μC

In-plane rotation: none

The obtained hydrogen atom concentration was as showing in Table 2 mentioned later.

3-3-1. Preparation of TEM Observation Samples

For the samples a to n, TEM observation samples were prepared by a focused ion beam method (FIB method, Focused Ion Beam). First, each sample was cut. And the FIB process was performed about the structure surface of each sample. First, the carbon layer 50 was deposited on the structure surface of each sample. The target thickness of vapor deposition of a carbon layer was about 300 nm.

After carbon layer deposition, each sample was sliced using a FIB device. First, a Ga ion beam was irradiated to the periphery of the site | part to be flaky with the carbon layer up, and a part of the structure of each sample was cut out with the carbon layer. The cut out structure was fixed to the TEM sample stage for FIB by using the tungsten deposition function by the FIB pickup method. Next, a tungsten layer was formed on the carbon layer 50 by the tungsten deposition process on the portion to be flared for TEM observation. The target thickness of the tungsten layer was 500-600 nm. And the structure of each sample was carved from both surfaces in the flaky part with Ga ion, and the TEM observation sample was produced. The target thickness of the TEM observation sample at this time was 100 nm. Acceleration voltage at the time of FIB processing started from 40 kV which is the maximum voltage, and was finally finished to 5 kV which is the lowest voltage. In this way, each of three TEM observation samples was obtained.

Next, the upper thickness 90 _u of the TEM observation sample 90 was confirmed. The secondary electron image was acquired using the TEM observation sample and a scanning electron microscope (SEM), and the upper thickness _90u was obtained from the said secondary electron image. HITACHI S-5500 was used for SEM. SEM observation conditions were made into the magnification 200,000 times, the acceleration voltage 2 mA, the scan time 40 second, and the number of images 2560 * 1920 pixels. Using the scale bar of this SEM image, the upper thickness 90 _u of each TEM observation sample was obtained from the average of 5 times. The upper thickness 90 _u of each sample is shown in Table 1. When the sample upper thickness 90 _u is larger than 100 ± 30 nm, the luminance Sa is small, and when the sample upper thickness 90 _u is smaller than 100 ± 30 nm, the luminance Sa tends to be large. As for sample g, it is thought that the sample upper thickness is 138 nm, which is larger than the prescribed range, that is, the luminance Sa is smaller than the original, but it is confirmed that it is still outside the scope of the present invention.

3-3-2. TEM bright field shooting

The samples a-n obtained by FIB processing were photographed on the bright field by TEM. Using transmission electron microscope H-9500 (manufactured by Hitachi High-Technologies Corporation), acceleration voltage is 200 Hz, observation magnification is 100,000 times, and shooting pixel is 4096 * 4096 pixel by digital camera (manufactured by OneView Camera Model 1095 / Gatan) , Capture speed of 6fps, exposure time of 2sec, and setting of image capture mode were captured in exposure time, camera position bottom mount. TEM digital black-and-white image was acquired so that the carbon layer and tungsten layer which were deposited at the time of sample preparation may be included in the same visual field.

13A to 13J are respective TEM images of samples a to g, i, j and l photographed at a magnification of 100,000 times. Three TEM images were acquired so that each TEM observation sample may be continued in the horizontal direction, and a total of nine TEM images were obtained for one sample.

3-3-3. Calculation of luminance Sa by luminance value acquisition and image analysis

From the acquired TEM bright field image, the luminance value of the image was acquired using image analysis software WinROOF2015. Specifically, as shown in FIGS. 13A to 13J, for each image G, the region vertical length dL is 0.5 μm and the region horizontal length dw is the image lateral direction of the image G, starting from the vicinity of the structure surface 10a. The luminance acquisition area R was set to be approximately equal to the length Gw. For each luminance acquisition region R, a luminance value for each pixel was obtained, and the luminance value was relatively corrected with the luminance of the tungsten layer in the region R being 0 and the luminance of the carbon layer 255. Here, the average value of the luminance value for 10,000 pixels was used for the luminance value of the tungsten layer in the order which is small continuously from the minimum value of the luminance value in the tungsten layer in a TEM image. In addition, the average value of the luminance value for 100,000 pixels was used for the luminance value of a carbon layer continuously in order from a maximum value of the luminance value in a carbon layer. Each average value obtained here was treated as a luminance value of the carbon layer / tungsten layer before correction.

For each of the luminance acquisition regions R, the average of absolute values of differences in luminance values after correction for each pixel was calculated using the least square method. Thus, the value obtained from nine TEM images was averaged, and it was set as brightness Sa. The sum total of the area of the luminance acquisition area | region R at this time was 6.9 micrometer <^2> or more.

In addition, as shown to (e), (f), (g) of FIGS. 13E-13G, when the interface of the surface 10a of the structure 10 and tungsten layer 50 is not linear, the area | region is made into To avoid this, the luminance acquisition area R was set. In addition, when the unevenness | corrugation of the surface 10a of the structure 10 is observed like FIG.13E (e), the area | region vertical length dL was set starting from the point closest to the surface 10a.

The obtained luminance Sa value was as showing in Table 2 mentioned later.

3-4. Calculation of luminance Sa without noise component

3-3-3. In the process of obtaining the luminance value and calculating the luminance Sa by image analysis, the image analysis software WinROOF2015 was set as a mode for removing noise components, and the luminance value of the image was obtained.

The obtained luminance Sa value was as showing in Table 2 mentioned later.

3-5. Calculation of the refractive index

For samples a and c, the surface 10a of the structure 10 was polished, so that the two-dimensional average surface roughness Ra was 0.1 µm or less and the thickness of the structure 10 was 1 µm or less.

For the measurement of the refractive index, the refractive index was calculated by the reflection spectroscopy using a brown rice spectrometer (OPTM-F2 manufactured by Otsuka Denshi FE-37S manufactured by Otsuka Denshi). As measurement conditions, it was set as the measurement spot size of 10 micrometers, and the measurement wavelength range 360-1100 nm.

Analysis conditions were made into the analysis wavelength range 360-1100 nm, and the optimization method and the least square method were used. About each sample, the refractive index for each wavelength was as showing in Table 3 and FIG. 19 mentioned later.

Table 3 and as shown in Figure 19, the refractive index of the structure comprising the YO compound according to the present invention, was greater than the refractive index of Y ₂ O ₃ 1.92 conventionally known, having a high resistance to particle properties.

4. Structure Characterization

4-1. Plasma resistance evaluation

For the samples a to n, the "standard plasma resistance test" was performed.

Specifically, an inductively coupled plasma reactive ion etching apparatus (manufactured by Muc-21 Rv-Aps-Se / Sumitomo Seimitsu Kogyo Co., Ltd.) was used as the plasma etching apparatus. The conditions for plasma etching were 1500 W for the ICP output, 750 W for the bias output, and a mixed gas of CHF ₃ gas 100 ccm and O ₂ gas 10 ccm, the pressure was 0.5 Pa, and the plasma etching time was 1 hour as the power supply output.

The state of the surface 10a of the structure 10 after plasma irradiation was image | photographed by SEM. They were as shown to FIGS. 14A-14H. As SEM observation conditions, the magnification was 5000 times and the acceleration voltage was 3 kV.

Next, the area of the surface corrosion trace after plasma irradiation was computed from the obtained SEM image. The result was as showing in Table 2.

Moreover, the state of the surface 10a of the structure 10 after plasma irradiation was image | photographed with the laser microscope. Specifically, using a laser microscope "OLS4500 / Olympus", the objective lens is MPLAPON100xLEXT (opening number 0.95, operating distance 0.35mm, condensing spot diameter 0.52㎛, measuring area 128 × 128 ㎛), magnification 100 Doubled. The bend component removal lambda c filter was set to 25 µm. The measurement was performed at three arbitrary places, and the average value was made into the arithmetic mean height Sa. In addition, the international standard ISO 25178 of the three-dimensional surface appearance was appropriately referred to. The value of the arithmetic mean height Sa of the surface 10a after plasma irradiation was as showing in Table 4.

Fig. 15 is a graph of the corrosion trace area (µm ² ) for each sample. As shown in FIG. 15, the sample formed by the aerosol deposition method of the sample (e) formed by ion plating generally had a small area of corrosion traces, and was a favorable result.

In FIG. 16, the relationship between brightness | luminance Sa and corrosion trace area (micrometer <^2> ) is shown about each sample formed by the aerosol deposition method. As shown in FIG. 16, it turns out that corrosion area can be made remarkably small by setting luminance Sa to below a predetermined value.

Moreover, as shown in FIG. 17 and Table 2, it turns out that particle resistance can be improved by reducing the amount of hydrogen (the number of hydrogen atoms / hydrogen atom per unit volume) of the structure surface.

100: composite structure
10: Structure
10a: structure surface
10u: upper area
10b: lower region
11: gas supply unit
12: piping
13: aerosol supply unit
14 chamber
15: nozzle
16: stage
17 drive unit
18: exhaust
19: device
50: carbon layer
60: tungsten layer
70: description
70a: substrate surface
dL: Area height
dW: area width
R: luminance acquisition area
G: image area
Gl: Image longitudinal length
Gw: image lateral length
L: Longitudinal direction
W: transverse direction
90 TEM observation sample
90h: sample height
90 _u : sample top thickness
90 _b : Lower sample thickness
90w: sample width
301: semiconductor manufacturing device member
302: semiconductor manufacturing device member
30a: plasma irradiation area
30b: plasma non-irradiation area
40: Sample acquisition point for luminance Sa measurement
31: hole
81: primary particles
82: secondary particles
10c: determinant

Claims (28)

A composite structure comprising a substrate and a structure installed on the substrate and having a surface,
The structure comprises polycrystalline ceramics,
Compound having a hydrogen atom number per unit volume at a measurement depth of 500 nm or 2 μm measured by secondary ion mass spectrometry (Dynamic-Secondary Ion Mass Spectrometry_D-SIMS method) of 7 * 10 ²¹ atoms / cm 3 or less structure. The method of claim 1,
The composite structure of 5 * 10 <^21> atoms / cm <3> or less of hydrogen atoms per unit volume of the said structure. A composite structure comprising a substrate and a structure installed on the substrate and having a surface,
The structure comprises polycrystalline ceramics,
A composite structure having a hydrogen atom concentration of up to 7 atomic percent, as measured by hydrogen forward scattering assay (HFS) -Rutherford backscattering spectroscopy (RBS) and proton-hydrogen forward scattering assay (p-RBS). A composite structure comprising a substrate and a structure installed on the substrate and having a surface,
The structure comprises polycrystalline ceramics,
A composite structure, wherein the luminance Sa value calculated by the following method is 19 or less.
The method of obtaining the luminance Sa,
(i) preparing a transmission electron microscope (TEM) observation sample of the structure;
(Ii) preparing a digital black and white image on the bright field of the TEM observation sample;
(Iii) acquiring a luminance value representing color data for each pixel in the digital monochrome image as a numerical value of gradation;
(Iii) correcting the luminance value;
(v) calculating a luminance Sa using the luminance value after the correction;
Made up,
In the step (i),
At least three said TEM observation samples are prepared from the said structure,
Each of the at least three TEM observation samples is produced by suppressing processing damage using a focused ion beam method (FIB method),
In the FIB processing, the surface of the structure is provided with a carbon layer and a tungsten layer for antistatic and sample protection,
When the FIB machining direction is in the longitudinal direction, the sample upper thickness, which is the length in the short axis direction of the structure surface, in a plane perpendicular to the longitudinal direction, is 100 ± 30 nm,
In the step (ii),
The digital black and white image is acquired for each of the at least three TEM observation samples,
Each of the digital black and white images includes the structure, the carbon layer, and the tungsten layer at a magnification of 100,000 times and an acceleration voltage of 200 kV using a transmission electron microscope (TEM).
In each of the digital black-and-white images, a luminance acquisition area having an area length of 0.5 μm in the longitudinal direction is set from the surface of the structure,
The plurality of digital black and white images are acquired from each of the at least three TEM observation samples so that the sum of the areas of the luminance acquisition area is 6.9 µm ² or more.
In the above step (iii),
The luminance value of the carbon layer is corrected relative to the luminance value of the carbon layer to 255 and the tungsten layer to zero, so that the corrected luminance value is obtained.
In the step (v),
For each of the luminance acquisition areas, the average of absolute values of the difference of the luminance values after the correction for each pixel is calculated using the least square method, and the average of them is the luminance Sa. The method of claim 4, wherein
And the luminance Sa is 13 or less. A composite structure comprising a substrate and a structure installed on the substrate and having a surface,
The structure comprises polycrystalline ceramics,
A composite structure, wherein the luminance Sa value calculated from the following method is 10 or less.
The method of obtaining the luminance Sa,
(i) preparing a transmission electron microscope (TEM) observation sample of the structure;
(Ii) acquiring a digital black and white image of a bright field of the TEM observation sample;
(Iii) acquiring a luminance value representing color data for each pixel in the digital monochrome image as a numerical value of gradation;
(Iii) correcting the luminance value;
(v) calculating a luminance Sa using the luminance value after the correction;
In the step (i),
At least three said TEM observation samples are prepared from the said structure,
Each of the at least three TEM observation samples is produced by suppressing processing damage using a focused ion beam method (FIB method),
In the FIB processing, the surface of the structure is provided with a carbon layer and a tungsten layer for antistatic and sample protection,
When the FIB machining direction is in the longitudinal direction, the sample upper thickness, which is the length in the short axis direction of the structure surface, in a plane perpendicular to the longitudinal direction, is 100 ± 30 nm,
In the step (ii),
The digital black and white image is acquired for each of the at least three TEM observation samples,
Each of the digital black and white images includes the structure, the carbon layer, and the tungsten layer at a magnification of 100,000 times and an acceleration voltage of 200 kV using a transmission electron microscope (TEM).
In each of the digital black-and-white images, a luminance acquisition area having an area length of 0.5 μm in the longitudinal direction is set from the surface of the structure,
The plurality of digital black and white images are acquired from each of the at least three TEM observation samples so that the sum of the areas of the luminance acquisition area is 6.9 µm ² or more.
In the above step (iii),
The luminance value of the carbon layer is corrected relative to the luminance value of the carbon layer to 255 and the tungsten layer to zero, so that the corrected luminance value is obtained.
Noise reduction using a low pass filter is performed on the digital black and white image in which the luminance value is corrected, and a cut-off frequency in noise removal using the low pass filter is 1 / (10 pixels). ego,
In the step (v),
For each of the luminance acquisition areas, the average of absolute values of the difference of the luminance values after the correction for each pixel is calculated using the least square method, and the average of them is the luminance Sa. The method of claim 6,
And the luminance Sa is 5 or less. A composite structure comprising a substrate and a structure installed on the substrate and having a surface,
The structure comprises polycrystalline ceramics comprising Y (elemental yttrium) and O (elemental oxygen),
The refractive index in the wavelength 400nm-550nm is larger than 1.92,
The refractive index is calculated by reflection spectroscopy using a microscopic spectrophotometer,
As measurement conditions, measurement spot size is 10 micrometers, the average surface roughness Ra≤0.1micrometer of the said substrate surface and the said composite structure surface, the thickness of the said structure≤1micrometer, the measurement wavelength range 360-1100nm,
The composite structure which uses an analysis wavelength range 360-1100 nm, the optimization method, and the least square method as analysis conditions. A composite structure comprising a substrate and a structure installed on the substrate and having a surface,
The structure comprises polycrystalline ceramics comprising Y (elemental yttrium) and O (elemental oxygen),
The refractive index satisfies at least one of 1.99 or more at a wavelength of 400 nm, 1.96 or more at a wavelength of 500 nm, 1.94 or more at a wavelength of 600 nm, 1.93 or more at a wavelength of 700 nm, and 1.92 or more at a wavelength of 800 nm or more. ,
The refractive index is calculated by reflection spectroscopy using a microscopic spectrophotometer,
As measurement conditions, the measurement spot size is 10 micrometers, the average surface roughness Ra≤0.1micrometer of the said substrate surface and the said composite structure surface, the thickness of the said structure≤1micrometer, the measurement wavelength range 360-1100nm,
The composite structure which uses an analysis wavelength range 360-1100 nm, the optimization method, and the least square method as analysis conditions. It is a method for evaluating the microstructure of a structure including a polycrystalline ceramics and having a surface,
(i) preparing a transmission electron microscope (TEM) observation sample of the structure;
(Ii) preparing a digital black and white image on the bright field of the TEM observation sample;
(Iii) acquiring a luminance value representing color data for each pixel in the digital monochrome image as a numerical value of gradation;
(Iii) correcting the luminance value;
(v) calculating a luminance Sa using the luminance value after the correction;
Made up,
In the step (i),
At least three said TEM observation samples are prepared from the said structure,
Each of the at least three TEM observation samples is produced by suppressing processing damage using a focused ion beam method (FIB method),
In the FIB processing, the surface of the structure is provided with a carbon layer and a tungsten layer,
When the FIB machining direction is in the longitudinal direction, the sample upper thickness, which is the length in the short axis direction of the structure surface, in a plane perpendicular to the longitudinal direction, is 100 ± 30 nm,
In the step (ii),
The digital black and white image is acquired for each of the at least three TEM observation samples,
Each of the digital black and white images includes the structure, the carbon layer, and the tungsten layer at a magnification of 100,000 times and an acceleration voltage of 200 kV using a transmission electron microscope (TEM).
In each of the digital black-and-white images, a luminance acquisition area having an area length of 0.5 μm in the longitudinal direction is set from the surface of the structure,
The plurality of digital black and white images are acquired from each of the at least three TEM observation samples so that the sum of the areas of the luminance acquisition area is 6.9 µm ² or more.
In the above step (iii),
The luminance value of the carbon layer is corrected relative to the luminance value of the carbon layer to 255 and the tungsten layer to zero, so that the corrected luminance value is obtained.
In the step (v),
For each of the luminance acquisition areas, the average of absolute values of the difference of the luminance values after the correction for each pixel is calculated using the least square method, and the average of them is the luminance Sa,
Assessment Methods. The method of claim 10,
In the above step (iii),
And performing a step of removing noise using a low pass filter for the digital monochrome image correcting the luminance value, wherein a cut-off frequency in noise removal using the low pass filter is set. Evaluation method, which is 1 / (10 pixels). The method according to claim 10 or 11,
The method for suppressing the processing damage is at least one of performing a finishing work at a low voltage of 5 kV, removing the processing damage by Ar ions, and cleaning the surface by ion milling before the TEM observation. , Assessment Methods. The method according to claim 10 or 11,
The said sample upper thickness is obtained with the secondary electron image which used the scanning electron microscope (SEM) with respect to the said TEM observation sample,
Observation conditions of the SEM are 200,000 times magnification, acceleration voltage 2 kHz, scan time 40 seconds, number of images 2560 * 1920 pixels,
And the SEM image constitutes a plane perpendicular to the longitudinal direction. The method according to claim 10 or 11,
The at least three TEM observation samples are obtained evenly from the surface of the structure. The method according to claim 10 or 11,
In the acquisition of the digital black and white image, after the focus adjustment is performed at a magnification of 300,000 times or more, the digital monochrome image of 100,000 times is acquired. The method according to claim 10 or 11,
In the above step (iii),
As the luminance value of the tungsten layer before the correction, the average value of the luminance values for 10,000 pixels in the order of successively smallest from the minimum value in the luminance value of the tungsten layer in the digital monochrome image,
The evaluation method of the brightness value of the said carbon layer before correction | amendment uses the average value of the brightness value for 100,000 pixels sequentially from largest value to the brightness value of the said carbon layer in the said digital monochrome image. The method according to claim 10 or 11,
An evaluation method for setting the area horizontal length perpendicular to the area vertical length in the luminance acquisition area so as to be the longest among the digital monochrome images. The method according to claim 10 or 11,
When acquiring the plurality of digital black and white images from each of the at least three TEM observation samples, the plurality of digital black and white images are acquired so as to be continuous in the transverse direction perpendicular to the longitudinal direction of the digital black and white image. , Assessment Methods. The method according to claim 10 or 11,
The evaluation method which uses image analysis software for each process of the said process (i)-(iv). The method according to any one of claims 1 to 9,
The composite structure whose average crystallite size of the said polycrystal ceramics computed from the TEM image of 400,000 times-2 million times magnification is 3 nm or more and 50 nm or less. The method of claim 20,
And the crystallite size is 30 nm or less. The method of claim 21,
The composite structure of which the crystallite size is 5 nm or more. The method according to any one of claims 1 to 9,
Wherein said structure is selected from oxides, fluorides and acid fluorides of rare earth elements and mixtures thereof. The method of claim 23, wherein
Composite structure wherein the rare earth element is at least one selected from the group consisting of Y, Sc, Yb, Ce, Pr, Eu, La, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm and Lu . The method according to any one of claims 1 to 9,
And the structure exhibits an arithmetic mean height Sa of 0.060 or less after the reference plasma resistance test. The method according to any one of claims 1 to 9,
Composite structure for use in environments where particle resistance is required. The semiconductor manufacturing apparatus provided with the composite structure of any one of Claims 1-9. The display manufacturing apparatus provided with the composite structure of any one of Claims 1-9.

Images