WO2021002339A1

WO2021002339A1 - Composite film, component, and production method

Info

Publication number: WO2021002339A1
Application number: PCT/JP2020/025595
Authority: WO
Inventors: 時田　修二; 晋也市村
Original assignee: 時田シーブイディーシステムズ株式会社
Priority date: 2019-07-03
Filing date: 2020-06-29
Publication date: 2021-01-07
Also published as: JPWO2021002339A1; TW202116702A; JP7005082B2

Abstract

Provided are: a composite film that is not susceptible to corrosion, even when exposed to corrosive gas in a high-temperature environment; a component that includes the composite film; and a production method for the composite film. According to the present invention, a carrier gas is used to spray vaporized yttrium oxide and aluminum oxide onto a base material that has been heated to a prescribed temperature that is in the range of 250°C–600°C. The result is a composite film that includes amorphous Y_xAl_yO_z (0.24≤x/(x+y)≤0.82, z/(x+y)=1.5) and is not easily affected by corrosive gas, even when exposed thereto in a high-temperature environment.

Description

Composite membranes, parts and manufacturing methods

The present invention relates to a composite membrane having yttrium aluminate, a component having the composite membrane, and a method for manufacturing the composite membrane.

Processes such as a semiconductor manufacturing process and an FPD (Flat Panel Display) manufacturing process include a step of introducing a corrosive gas into a chamber in a high temperature environment. Therefore, in general, the inside of the chamber is coated with a corrosion-resistant and erosion-resistant coating by thermal spraying. At that time, yttrium oxide and zirconium oxide are used as the coating material. In addition, since some parts arranged in the chamber have complicated shapes such as nozzles and fastening parts, the base material for parts is coated with a coating material by the CVD (Chemical Vapor Deposition) method. There is.

In processes such as semiconductor manufacturing process and FPD manufacturing process, the cleaning process of F (fluorine) corrosive gas may be frequently performed in a high temperature environment of 300 ° C to 400 ° C or higher. When exposed to F-based corrosive gas, yttrium oxide is easily fluorinated to yttrium fluoride. At this time, the influence of the F-based corrosive gas extends not only to yttrium oxide but also to the underlying base material.

Amorphous aluminum oxide produced by the CVD method is fluorinated to aluminum fluoride when exposed to an F-based corrosive gas. In addition, aluminum oxide crystallizes at 400 ° C. or higher, crystal particles grow, and the denseness is impaired. The base material, sapphire glass, is represented by the chemical formula Al ₂ O ₃ , and when exposed to F-based corrosive gas, it is easily fluorinated to aluminum fluoride, and the surface of the sapphire glass is scraped. ..

In order to solve such a problem, the present invention provides a composite film that is not easily affected by corrosion even when exposed to a corrosive gas in a high temperature environment, a component having the same, and a method for manufacturing the composite film. The purpose.

One aspect of the present invention is a composite film having an amorphous Y _x Al _y _Oz (where 0.24 ≦ x / (x + y) ≦ 0.82, z / (x + y) = 1.5).

Another aspect of the present invention is a component having a base material and the composite film provided on the base material.

Another aspect of the present invention is to vaporize each of the yttrium oxide and aluminum oxide raw materials in a state where the base material is heated to a predetermined temperature in the range of 250 ° C. or higher and 600 ° C. or lower, and use a carrier gas to vaporize the raw materials. This is a method for producing a composite film, which is sprayed onto the substrate.

According to the present invention, there is provided a composite film that is not easily affected by corrosion even when exposed to a corrosive gas in a high temperature environment, a component having the composite film, and a method for manufacturing the composite film.

FIG. 1 is a block diagram of a manufacturing apparatus for manufacturing a composite film according to an embodiment of the present invention. FIG. 2A is a diagram showing a form of a crucible in the vaporizer of FIG. FIG. 2B is a diagram showing another form of the crucible in the vaporizer of FIG. FIG. 3 is a configuration diagram of a manufacturing apparatus different from that of FIG. FIG. 4 is a block diagram of the system used in the exposure test. FIG. 5A is a diagram showing XRD (X-ray Diffraction) measurement results of the sample prepared in Example 1 and the heat-treated sample. FIG. 5B is an XRD (X-ray Diffraction) measurement result of a sample in which an exposure test was performed on the composite membrane prepared in Example 1. FIG. 6A is a diagram showing the measurement results of XPS (X-ray Photoelectron Spectroscopy) when the sample was etched for 600 seconds with respect to the sample subjected to the exposure test on the composite film prepared in Example 1. FIG. 6B is a diagram showing the measurement results of XPS (X-ray Photoelectron Spectroscopy) when the sample was etched for 1200 seconds with respect to the sample subjected to the exposure test on the composite film prepared in Example 1. FIG. 7 is an XRD (X-ray Diffraction) measurement result of a sample subjected to an exposure test on the composite membrane prepared in Example 2. FIG. 8 summarizes the evaluation of the ClF ₃ exposure test. FIG. 9 is a microscopic image of a sample of x / (x + y) = 0.24 after heat treatment at 700 ° C. and an exposure test. FIG. 10 is a microscopic image of a sample of x / (x + y) = 0.43 after an exposure test. FIG. 11 is a microscopic image of a sample of x / (x + y) = 0.70 after an exposure test. FIG. 12 is a microscopic image of a sample of x / (x + y) = 0.76 after an exposure test. FIG. 13 is a microscopic image of a sample of x / (x + y) = 0.79 after an exposure test. FIG. 14 is a microscope image of a sample of x / (x + y) = 0.82 after heat treatment at 700 ° C. and an exposure test. FIG. 15 is a microscopic image of a sample of Al ₂ O ₃ after an exposure test. Figure 16 is a micrograph after exposure tests on samples of Y ₂ O _3.

Hereinafter, embodiments of the present invention will be described in detail.

1 composite film according to an embodiment of the composite film and the component present invention, amorphous _Y x _Al y _{O z} (however, 0.24 ≦ x / (x + y) ≦ 0.82, z / (x + y) = 1.5) Consists of. The composite membrane is a compound represented by the above chemical formula. Here, the composite film preferably has a thickness of 10 nm or more and 10 μm or less. More preferably, the composite film has a thickness of 100 nm or more and 1 μm or less. This is because when the composite film has a relatively flat shape, the composite film sufficiently functions as a corrosion-resistant coating film when the composite film has a thickness of at least 10 nm. This is because when the composite film has irregularities rather than a relatively flat shape, if it has an average thickness of at least 100 nm, the composite film sufficiently functions as a corrosion-resistant coating film even if an extremely thin portion is generated. This is because if the film is thick, it takes time to form a film, and if it exceeds 1 μm depending on the film forming conditions, cracks may occur in the composite film, resulting in poor productivity. The composite membrane may inevitably contain elements other than the above chemical formulas, for example, an element of a carrier gas during production, carbon, and the like.

The composite film has a property of being able to crystallize when heated to 900 ° C. or higher. Although it depends on the composition formula of the composite film, it has a crystallinity represented by any one of YAG (Y ₃ Al ₅ O ₁₂ ), YAP (YAlO ₃ ), and YAM (Y ₄ Al ₂ O ₉ ).

The composite film has corrosion resistance to corrosive gases containing halogen. Since the composite film has corrosion resistance, it has erosion resistance. The corrosive gas may contain halogen, and examples thereof include F ₂ , NF ₃ , and ClF ₃ . The corrosive gas may be turned into plasma.

Processed parts are provided by a base material, that is, a base material having various shapes such as a base material for fastening parts of bolts, nuts and washers, a nozzle, and a composite film having the above composition formula coated on the base material. .. Here, the base material may be formed by applying various surface treatments, or may be made of a plurality of materials different in the thickness direction.

2 Manufacturing method The manufacturing method of the composite film according to the embodiment of the present invention is as follows.

First, the base material is placed in the chamber. The base material is not limited to a flat plate shape, and may be a base material of parts having various shapes such as bolts, nuts, washer fastening parts, and nozzles. Further, the base material does not depend on the material as long as it can withstand the heating temperature during manufacturing.

Next, each raw material of yttrium oxide and aluminum oxide is placed in the vaporizer. The raw material is not particularly limited as long as it can vaporize yttrium and aluminum. Further, the number of raw materials does not have to be two, and may be three or more. As the raw material of yttrium oxide, for example, an acetylacetonate metal complex such as trisacetylacetonatoittrium, a metal complex of a di-piparoylmethane metal complex such as tris (di-piparoylmethanate) yttrium, and the like are preferably used. Examples of the raw material of aluminum oxide include an acetylacetonate metal complex such as trisacetylacetonate aluminum, a metal complex of a di-piparoylmethane metal complex such as tris (di-pipaloylmethanate) aluminum, and the like. The vaporization is selected from one or more of current heating, heater heating, electron beam, laser heating. Here, vaporization includes the meaning of sublimation.

Next, the substrate is heated to a predetermined temperature in the range of 250 ° C. or higher and 600 ° C. or lower. If it is heated to at least 250 ° C., a film can be formed on the substrate. Heating at a temperature lower than this temperature makes the deposition rate extremely slow, which is not preferable from the viewpoint of productivity. Further, in low temperature heating, elements other than oxygen, yttrium, and aluminum constituting the above-mentioned composition formula are unavoidably contained in the composite film, which impairs corrosion resistance, and therefore, from the viewpoint of functionality. Not preferable. On the other hand, if the temperature exceeds 600 ° C., the particles tend to grow in the gas phase and the density of the composite film deteriorates, which is not preferable. If the temperature exceeds 600 ° C., fine particles may be generated depending on the raw material. The method for heating the base material is selected from various methods such as heater heating, lamp heating, and laser heating.

Then, while introducing the carrier gas into the vaporizer, the raw material is heated, and the vapor of the raw material ejected from the vaporizer is introduced onto the base material along the flow of the carrier gas. Here, the heating temperature of the raw materials may be any temperature as long as each raw material vaporizes. The heating may be performed for each raw material, or a plurality of raw materials may be collectively performed. By performing this for each raw material, the amount of vapor of the raw material can be adjusted and a composite film having a predetermined composition can be obtained. When a plurality of raw materials are heated together, it is preferable to provide openings having different sizes for each raw material so that the amount of ejection for each raw material can be controlled.

According to the above procedure, the yttrium oxide and aluminum oxide raw materials are vaporized in a state where the base material is heated to a predetermined temperature in the range of 250 ° C. or higher and 600 ° C. or lower, and the vaporized raw materials are injected onto the base material by the carrier gas. I do. As a result, a composite film having a composition represented by the above-mentioned composition formula can be obtained.

The composite film thus obtained can be heated at a temperature higher than the temperature at the time of film formation to make the state of the film more appropriate. The treatment temperature at this time needs to be lower than the temperature at which the composite film crystallizes.

3 Manufacturing device The manufacturing device according to the embodiment of the present invention will be described. FIG. 1 is a block diagram of a manufacturing apparatus for manufacturing a composite film according to an embodiment of the present invention. In the manufacturing apparatus 10 according to the embodiment of the present invention, as shown in FIG. 1, a sample table 12 on which the base material 11 is placed is arranged in the chamber 13. For example, a heater is built in the sample base 12. The vaporizer 14 is arranged inside the chamber 13 and the carrier gas supply source 15 is arranged outside the chamber 13. The carrier gas may be a gas that does not react with the raw material, and is selected from a rare gas such as argon gas and a nitrogen gas. The carrier gas supply source 15 and the vaporizer 14 are connected to each other via a pipe 17a, a flow meter 16, and a pipe 17b, and the carrier gas is supplied to the vaporizer 14 at a predetermined flow rate.

The vaporizer 14 is configured so that a board or a crucible for accommodating the raw material is arranged so that the raw material can be heated and sublimated to generate steam. As a heating method, various methods such as resistance heating, heater heating, and laser heating are adopted. The pipe 18 from the vaporizer 14 is provided with its tip facing the sample base 12, and a nozzle 19 is attached to the outlet of the pipe 18. A slit 19a is provided in the nozzle 19, and a medium supplied by the pipe 18, a mixed medium of the carrier gas and the raw material vapor, is injected from the slit 19a into the base material 11.

A protective cover is used for the chamber 13 to distinguish the carrier gas and the raw material vapor from the installation area of the manufacturing apparatus 10. In the case of a protective cover, an opening 13a is provided. Such a device is called an atmospheric pressure CVD device.

FIG. 2A is a diagram showing a form of a crucible in the vaporizer 14 of FIG. A plate 22 having a plurality of

openings

21a and 21b is arranged above the crucible 21. The first raw material 1 is housed below the first opening 21a, the second raw material 2 is housed below the second opening 21b, and both the first raw material 1 and the second raw material 2 are substantially at the same time. It is heated to the same temperature. Since at least one or both of the shapes and sizes of the first opening 21a are different from either or both of the shapes and sizes of the second opening 21b, the supply amount of the first raw material is the supply of the second raw material. Different from the amount. When three or more kinds of raw materials are used, more slits such as a third opening may be provided.

FIG. 2B is a diagram showing another form of the crucible in the vaporizer 14 of FIG. A plurality of

crucibles

26 and 27 are provided, and the

respective crucibles

26 and 27 are provided with

plates

26b and 27b that shield a part of the

openings

26a and 27a as needed. The first crucible 26 accommodates the first raw material 1. The second crucible 27 accommodates the second raw material 2. It is easy to control the heating temperature of the first raw material 1 to be different from the heating temperature of the second raw material 2, and the supply amount of the first raw material 1 is different from the supply amount of the second raw material 2. When three or more kinds of raw materials are used, a third crucible or the like may be provided.

FIG. 3 is a configuration diagram of a manufacturing apparatus different from that of FIG. In the manufacturing apparatus 30 according to the embodiment of the present invention, as shown in FIG. 3, a sample table 32 on which the base material 31 is placed is arranged in the chamber 33. For example, a heater is built in the sample base 32. The manufacturing apparatus 30 shown in FIG. 3 is provided with a plurality of vaporizers, unlike the form shown in FIG. The first vaporizer 34a and the second vaporizer 34b are arranged inside the chamber 33, and the carrier gas supply source 35 is arranged outside the chamber 33. The carrier gas may be a gas that does not react with the raw material, and is selected from a rare gas such as argon gas and a nitrogen gas. The carrier gas supply source 35 and the first vaporizer 34a are connected via a pipe 37, a flow rate controller 36a (may include a flow meter), and a pipe 37a, and the carrier gas is predetermined. It is supplied to the first vaporizer 34a at a flow rate. The carrier gas supply source 35 and the second vaporizer 34b are connected via a pipe 37, a flow rate controller 36b (which may include a flow meter) and a pipe 37b, and the carrier gas is the first. Is supplied to the second vaporizer 34b at a predetermined flow rate that is the same as or different from the amount supplied to the vaporizer 34a.

The first vaporizer 34a and the second vaporizer 34b are respectively configured so that a board or a crucible for accommodating the raw materials is arranged so that each raw material can be heated and sublimated to generate steam. ing. As a heating method, various methods such as resistance heating, heater heating, and laser heating are adopted. Unlike the manufacturing apparatus 10 shown in FIG. 1, in the manufacturing apparatus 30 shown in FIG. 3, the first vaporizer 34a is easily controlled so that the heating temperature is the same as or different from that of the second vaporizer 34b.

The pipe 38a from the first vaporizer 34a and the pipe 38b from the second vaporizer 34b are connected to the mixer 40. Since the gas path inside the mixer 40 is configured to be zigzag, the medium from the first vaporizer 34a and the medium from the second vaporizer 34b can be sufficiently mixed. it can. The tip of the pipe 41 from the mixer 40 is provided toward the sample base 32, and the nozzle 39 is attached to the outlet of the pipe 41. The nozzle 39 is provided with a slit 39a, and a medium supplied to the nozzle 39 by a pipe 41, in which a mixed medium of a carrier gas and a raw material vapor, is injected from the slit 39a onto the base material 31.

A protective cover is used for the chamber 33 to distinguish the carrier gas and the raw material vapor from the installation area of the manufacturing apparatus 30. In the case of a protective cover, an opening 33a is provided.

Here, the first crucible is arranged in the first vaporizer 34a, and the second crucible is housed in the second vaporizer 34b. A plate for controlling the size of the opening may be provided in each of the first crucible and the second crucible. In the manufacturing apparatus 30 shown in FIG. 3, the supply amounts of the first raw material steam and the second raw material steam can be precisely adjusted. The heating temperature of the first 坩堝, the second 坩堝, the opening in the first 坩堝, the shape and size of the opening in the second 坩, the flow rate and gas of the carrier gas supplied to the first vaporizer 34a. The supply amounts of the first raw material steam and the second raw material steam are adjusted by either the pressure, the flow rate of the carrier gas supplied to the second vaporizer 34b, the gas pressure, or a combination thereof.

Hereinafter, examples will be described in detail. The examples do not limit the scope of the present invention.

To confirm the corrosion resistance of the films in Examples and Comparative Examples were subjected to exposure test by ClF ₃ gas. FIG. 4 is a schematic configuration diagram of the system 50 used in the exposure test. ClF ₃ gas is supplied into the quartz reaction tube 53 via the flow meter 52 from ClF ₃ gas supply source 51. The sample table 54 is arranged in the quartz reaction tube 53. The sample 55 is placed on the sample table 54. A temperature sensor 56 is attached to the sample table 54, and the temperature of the sample 55 can be monitored. The lamp heater 57 is installed outside the quartz reaction tube 53, and indirectly heats the sample base 54 and the sample 55. An exhaust device 59 is attached to the quartz reaction tube 53 via an exclusion device 58. ClF ₃ gas is removed by the exclusion device 58 and exhausted to the outside.

Example 1
Each raw material of aluminum oxide and yttrium oxide was put into a crucible in a predetermined amount, heated and vaporized, and supplied to a sapphire substrate together with carrier gas N ₂ . The sapphire substrate was heated to 500 ° C. to form a composite film on the sapphire substrate. Here, each raw material to be put into the crucible was adjusted so that the amount of aluminum (Al) in the composite film was larger than that of yttrium (Y).

The samples were subjected to energy dispersive X-ray analysis (Energy Dispersive X-ray Spectrometery, EDX, EDS). As a result, the composition formula of the produced composite film was Y _0.43 Al _0.57 O _1.5 .

The produced composite membrane was heated to 700 ° C., 800 ° C., and 900 ° C. in an air atmosphere for heat treatment. FIG. 5A is a diagram showing XRD (X-ray Diffraction) measurement results of the sample prepared in Example 1 and the heat-treated sample. Each of the uppermost to fourth stages of FIG. 5A shows a sample heat-treated at 900 ° C., a sample heat-treated at 800 ° C., a sample heat-treated at 700 ° C., and a sample not heat-treated, and the lowermost stage. Shows the spectrum of crystal YAG (Y ₃ Al ₅ O ₁₂ ). The horizontal axis is the diffraction angle 2θ (deg.), And the vertical axis is the diffraction intensity (cps). Note that θ is the angle of incidence of X-rays on the atomic plane. From FIG. 5A, the sample not heat-treated, the sample heat-treated at 700 ° C, and the sample heat-treated at 800 ° C are all in an amorphous state, but when heated to 900 ° C and fired, YAG (Y ₃ Al ₅ O ₁₂₎ ).

An exposure test for ClF ₃ was performed for 10 minutes using the system 50 shown in FIG. The temperature measured by the temperature sensor 56 was 600 ° C. The composite membrane did not change in appearance before and after the exposure test. There was also no change in the sapphire substrate after the exposure test.

FIG. 5B is a diagram showing XRD (X-ray Diffraction) measurement results of a sample subjected to an exposure test on the composite membrane prepared in Example 1. Each of the top to third stages of FIG. 5B shows the measurement results of the exposure test on the sample heat-treated at 900 ° C., the sample heat-treated at 700 ° C., and the sample not heat-treated. The lower part shows the spectrum of crystal AlF ₃ . The horizontal axis is the diffraction angle 2θ (deg.), And the vertical axis is the diffraction intensity (cps). Note that θ is the angle of incidence of X-rays on the atomic plane. From Figure 5B, the post-exposure test was also detected strong crystal peak of AlF ₃ in any of the samples.

6A and 6B are the measurement results of XPS (X-ray Photoelectron Spectroscopy) of the sample subjected to the exposure test on the composite film prepared in Example 1, and FIG. 6A shows the results of etching the sample for 600 seconds. FIG. 6B is a diagram showing each spectrum when etching for 1200 seconds. The etching depth of Ar ions for 1200 seconds corresponds to about 160 nm. The horizontal axis is the binding energy (eV), and the vertical axis is the intensity (cps). Comparing FIG. 6A and FIG. 6B with respect to the ratio of the spectral intensity of F1s and the spectral intensity of O1s minus the background, the spectral intensity of F1s / the spectral intensity of O1s is lower in the depth direction of the sample, and the depth of the composite film is high. It was found that it was difficult for fluorine to enter in the vertical direction. Furthermore, from the spectrum of Y3d, it is inferred that it is an oxide of yttrium.

From the measurement results of XRD of FIGS. 5A and 5B and XPS of FIGS. 6A and 6B, aluminum (Al) is easily fluorinated in the composite film produced in Example 1, but yttrium (Y) is corroded. It was found that the yttrium oxide was hard to be formed and the oxide of yttrium remained, and the composite film produced in Example 1 had corrosion resistance to ClF ₃ gas regardless of the presence or absence of heat treatment.

Example 2
Each raw material of aluminum oxide and yttrium oxide was put into a crucible in a predetermined amount, heated and vaporized, and supplied to a sapphire substrate together with carrier gas N ₂ . The sapphire substrate was heated to 500 ° C. to form a composite film on the sapphire substrate. Here, each raw material to be put into the crucible was adjusted so that the amount of yttrium (Y) in the composite film was larger than that in aluminum (Al).

The samples were subjected to energy dispersive X-ray analysis (Energy Dispersive X-ray Spectrometery, EDX, EDS). As a result, the composition formula of the produced composite film was Y _0.7 Al _0.3 O _1.5 .

The produced composite film was amorphous in both the sample without heat treatment and the sample heated to 700 ° C and 800 ° C, respectively, but when heated to 900 ° C and fired, it became crystalline YAM (Y ₄ Al ₂ O ₉ ). It was confirmed by the measurement of XRD.

An exposure test for ClF ₃ was performed for 10 minutes using the system 50 shown in FIG. The temperature measured by the temperature sensor 56 was 600 ° C. The composite membrane did not change in appearance before and after the exposure test. In addition, the exposure test did not change the sapphire substrate.

FIG. 7 is an XRD (X-ray Diffraction) measurement result of a sample subjected to an exposure test on the composite membrane prepared in Example 2. The horizontal axis is the diffraction angle 2θ (deg.), And the vertical axis is the diffraction intensity (cps). Note that θ is the angle of incidence of X-rays on the atomic plane. Each of the uppermost to third stages of FIG. 7 shows the measurement results of the exposure test on the sample heat-treated at 900 ° C., the sample heat-treated at 700 ° C., and the sample not heat-treated. The lower part shows the spectrum of crystal YF ₃ . From FIG. 7, after the exposure test, the crystal peak of YF ₃ was strongly detected in all the samples.

An exposure test was performed on both the sample prepared in Example 2 and the sample heat-treated at 700 ° C. and 900 ° C. As a result of FE-SEM and EDS analysis after the exposure test on the sample heat-treated at 700 ° C., it was confirmed that oxide remained.

Comparative Example 1
The raw material of yttrium oxide was put into a crucible, heated and vaporized, and supplied to the sapphire substrate together with the carrier gas N ₂ . The substrate was heated to 500 ° C. to form an yttrium oxide film on a sapphire substrate.

Produced yttrium oxide film, was the XRD measurement, it was found to consist of crystals of Y ₂ O _3. The membrane, 700 ℃, 800 ℃, even if a heat treatment by heating 60 min each at 900 ° _C., it was confirmed that the crystals of Y 2 _{O 3.}

It was exposed test ClF ₃ 10 minutes by the system 50 shown in FIG. 4 for manufacturing the yttrium oxide film. The temperature measured by the temperature sensor 56 was 600 ° C.

Before and after the exposure test, the area around the outer circumference of the base material was cloudy by visual confirmation.

In the sample subjected to the exposure test, it was confirmed that the oxygen of yttrium oxide was replaced by fluorine and changed to yttrium fluoride (YF ₃ ) by the measurement by XRD. Since the sapphire substrate was damaged from the optical microscope image, it was confirmed that the fluorine passed through the yttrium oxide film and reached the sapphire substrate. From the above, it was found that the yttrium oxide film does not have corrosion resistance.

Comparative Example 2
The raw material of aluminum oxide was put into a crucible, heated and vaporized, and supplied to the sapphire substrate together with the carrier gas N ₂ . The substrate was heated to 500 ° C. to form an aluminum oxide film on the sapphire substrate.

When the produced aluminum oxide film was subjected to XRD measurement, it was found to be made of Al ₂ O ₃ amorphous. It was confirmed that this film was amorphous of Al ₂ O ₃ even when it was heated at 700 ° C. and 800 ° C. for 60 minutes and heat-treated. When heated to 900 ° C. for 60 minutes, it was not possible to conclude that it was a crystal of Al ₂ O ₃ .

The amorphous aluminum oxide film was exposed to ClF ₃ for 10 minutes using the system 50 shown in FIG. The temperature measured by the temperature sensor 56 was 600 ° C.

After the exposure test, it was confirmed that the film had peeled off from the sapphire substrate. In addition, there were many corroded parts.

In the sample subjected to the exposure test, it was confirmed that the oxygen of the amorphous aluminum oxide was replaced by fluorine and changed to aluminum fluoride (AlF ₃ ) by the measurement by XRD. In addition, it was confirmed by a microscope image that the sapphire substrate was damaged. From these facts, it was found that amorphous aluminum oxide does not have corrosion resistance.

Examples 1 and 2, by comparison with Comparative Example 1 and 2, the amorphous _Y x _Al y _O z composite membrane (0 <x, y, z <1) is, even under a high temperature environment of 600 ° C., fluorine It was found that it is not easily affected by corrosive gas containing, and protects the underlying substrate.

Furthermore, we investigated in detail as follows.

Example 3
Each raw material of aluminum oxide and yttrium oxide was put into a crucible in a predetermined amount, heated and vaporized, and supplied to a sapphire substrate together with carrier gas N ₂ . The sapphire substrate was heated to 500 ° C. to form a composite film on the sapphire substrate. Here, each raw material to be put into the crucible was adjusted so that the amount of aluminum (Al) in the composite film was larger than that of yttrium (Y).

The samples were subjected to energy dispersive X-ray analysis (Energy Dispersive X-ray Spectrometery, EDX, EDS). As a result, the composition formula of the produced composite film was Y _0.24 Al _0.76 O _1.5 .

The produced composite film was amorphous, and maintained an amorphous state even when heated to 700 ° C.

A weak peak of YF ₃ was detected from the XRD (X-ray Diffraction) measurement results of the sample subjected to the exposure test to the composite membrane prepared in Example 3. From the results of the optical microscope image, no damage to the sapphire substrate was confirmed in either the sample not heat-treated or the sample heat-treated at 700 ° C.

Example 4
Each raw material of aluminum oxide and yttrium oxide was put into a crucible in a predetermined amount, heated and vaporized, and supplied to a sapphire substrate together with carrier gas N ₂ . The sapphire substrate was heated to 500 ° C. to form a composite film on the sapphire substrate. Here, each raw material to be put into the crucible was adjusted so that the amount of aluminum (Al) in the composite film was larger than that of yttrium (Y).

The samples were subjected to energy dispersive X-ray analysis (Energy Dispersive X-ray Spectrometery, EDX, EDS). As a result, the composition formula of the produced composite film was Y _0.47 Al _0.53 O _1.5 .

The produced composite film was found to be amorphous by XRD analysis. Even when the produced composite film was heated to 700 ° C., it maintained an amorphous state.

From the XRD (X-ray Diffraction) measurement results of the sample in which the exposure test was performed on the composite film prepared in Example 4, a strong peak of the AlF ₃ crystal and a relatively weak peak of the YF ₃ crystal were detected. From the results of the optical microscope image, no damage to the sapphire substrate was confirmed in either the sample not heat-treated or the sample heat-treated at 700 ° C.

Example 5
Each raw material of aluminum oxide and yttrium oxide was put into a crucible in a predetermined amount, heated and vaporized, and supplied to a quartz substrate together with a carrier gas N ₂ . The quartz substrate was heated to 500 ° C. to form a composite film on the quartz substrate. Here, each raw material to be put into the crucible was adjusted so that the amount of yttrium (Y) in the composite film was larger than that in aluminum (Al).

The samples were subjected to energy dispersive X-ray analysis (Energy Dispersive X-ray Spectrometery, EDX, EDS). As a result, the composition formula of the produced composite film was Y _0.82 Al _0.18 O _1.5 .

An exposure test for ClF ₃ was performed for 10 minutes using the system 50 shown in FIG. The temperature measured by the temperature sensor 56 was 600 ° C. After the exposure test, the composite membrane was confirmed to be partially corroded. In addition, in the composite membrane heated to 700 ° C., many corroded parts were confirmed after the exposure test.

The crystal peak of YF ₃ was detected from the XRD (X-ray Diffraction) measurement results of the sample in which the exposure test was performed on the composite film prepared in Example 5.

Example 6
Each raw material of aluminum oxide and yttrium oxide was put into a crucible in a predetermined amount, heated and vaporized, and supplied to a sapphire substrate together with carrier gas N ₂ . The sapphire substrate was heated to 500 ° C. to form a composite film on the sapphire substrate. Here, each raw material to be put into the crucible was adjusted so that the amount of yttrium (Y) in the composite film was larger than that in aluminum (Al).

The samples were subjected to energy dispersive X-ray analysis (Energy Dispersive X-ray Spectrometery, EDX, EDS). As a result, the composition formula of the produced composite film was Y _0.76 Al _0.24 O _1.5 .

The produced composite film was amorphous.

As a result of XRD (X-ray Diffraction) measurement of the sample subjected to the exposure test to the composite film prepared in Example 6, the crystal peak of YF _{3 and} the crystal peak of AlF ₃ were weakly detected.

Example 7
Each raw material of aluminum oxide and yttrium oxide was put into a crucible in a predetermined amount, heated and vaporized, and supplied to a sapphire substrate together with carrier gas N ₂ . The sapphire substrate was heated to 500 ° C. to form a composite film on the sapphire substrate. Here, each raw material to be put into the crucible was adjusted so that the amount of yttrium (Y) in the composite film was larger than that in aluminum (Al).

The samples were subjected to energy dispersive X-ray analysis (Energy Dispersive X-ray Spectrometery, EDX, EDS). As a result, the composition formula of the produced composite film was Y _0.79 Al _0.21 O _1.5 .

The produced composite film was amorphous.

As a result of XRD (X-ray Diffraction) measurement of the sample subjected to the exposure test to the composite film prepared in Example 7, the crystal peak of YF ₃ was weakly detected.

Table 1 summarizes Examples 1 to 7 and Comparative Examples 1 and 2. In addition, FIG. 8 summarizes the evaluation of the ClF ₃ exposure test. The horizontal axis of FIG. 8 is x / (x + y), and the vertical axis is the film formation temperature or the heat treatment temperature. The double circle plot (◎) indicates good and there is no significant change in the membrane surface, the circle plot (○) indicates good and there is a slight change in the membrane surface, and the triangular plot (△). Is generally good, but the substrate is damaged, and the cross plot (x) indicates that the substrate is damaged and most of the film is peeled off.

When showing the chemical formula of the composite film of amorphous and _{_{_{Y x Al y O z, 0.24}}} ≦ x / (x + y) <0.82, if z / (x + y) = 1.5, the amorphous composite film is corrosion It turned out to have sex. Corrosion resistance can be maintained even when a composite film is formed on the base material and then heat-treated at 700 ° C. and 800 ° C. The amorphous composite film represented by such a chemical formula is crystallized by heat treatment at 900 ° C. or higher for 1 hour or longer.

FIG. 9 is a microscope image of a sample of x / (x + y) = 0.24 after heat treatment at 700 ° C. and an exposure test. This image shows that there is no effect from the exposure test.

FIG. 10 is a microscopic image after an exposure test on a sample of x / (x + y) = 0.43. This image shows that there is no effect from the exposure test.

FIG. 11 is a microscopic image after an exposure test on a sample of x / (x + y) = 0.70. This image shows that there is no effect from the exposure test.

FIG. 12 is a microscopic image after an exposure test on a sample of x / (x + y) = 0.76. This image shows that there is no effect from the exposure test.

FIG. 13 is a microscopic image after an exposure test on a sample of x / (x + y) = 0.79. This image shows that there is no effect from the exposure test.

FIG. 14 is a microscope image of a sample of x / (x + y) = 0.82 after heat treatment at 700 ° C. and an exposure test. From this image, it can be seen that there is no corrosion resistance.

FIG. 15 is a microscopic image of a sample of Al ₂ O ₃ after an exposure test. From this image, it can be seen that there is no corrosion resistance.

Figure 16 is a micrograph after exposure tests on samples of Y ₂ O _3. From this image, it can be seen that there is no corrosion resistance.

The element ratios used in Examples and Comparative Examples are the ZAF correction method using an energy dispersive X-ray spectrometer (EDS) attached to a scanning electron microscope (SEM) (model number: JSM-IT500) manufactured by JEOL Ltd. Obtained by. The ZAF correction method is a ZAF effect (Z (atomic number effect), A (absorption effect), F (fluorescence), in addition to the relative intensity K of the characteristic X-rays emitted from the sample and the characteristic X-rays measured from the standard sample. This is a method of obtaining the concentration by theoretically correcting it in consideration of the excitation effect)).

1: First raw material 2: Second raw material 10, 30: Manufacturing equipment 11, 31: Base material 12, 32: Sample stand 13, 33:

Chamber

14, 34a, 34b: Vaporizer 15, 35: Carrier gas supply Sources 19, 39: Nozzle 50: System for exposure testing

Claims

A composite film having an amorphous Y x Al y Oz (where 0.24 ≦ x / (x + y) ≦ 0.82, z / (x + y) = 1.5).
The composite film according to claim 1, which has crystallinity when heated to 900 ° C. or higher and fired.
The composite film according to claim 1, which has corrosion resistance to a gas containing halogen.
With the base material
The composite film according to any one of claims 1 to 3 provided on the base material and
Parts with.
A composite membrane in which the yttrium oxide and aluminum oxide raw materials are vaporized and the vaporized raw materials are sprayed onto the base material by a carrier gas while the base material is heated to a predetermined temperature in the range of 250 ° C. or higher and 600 ° C. or lower. Production method.
The method for producing a composite film according to claim 5, wherein the heat treatment is performed by raising the temperature of the vaporization raw material to a temperature higher than the heating temperature of the base material when the vaporization raw material is sprayed onto the base material.