KR20210082085A - Corrosion resistant material for semiconductor manufacturing apparatus - Google Patents

Abstract

The objective of the present invention is to provide a material suitable for detecting a damaged spot on a surface of a semiconductor-fabricating apparatus or a component member thereof, the damaged spot being caused by dry etching, a method for producing the material, and a method for detecting the damaged spot. A corrosion-resistant material for a semiconductor-fabricating apparatus comprises: a base material having dry-etching resistance; and an element imparting a luminous ability of visible light by ultraviolet-light radiation to the base material. The base material is preferably an oxide containing a rare-earth element, a halide and an oxyhalogenated material, and the element imparting the luminous ability thereof to the base material is preferably europium and terbium. The corrosion-resistant material can be provided on a surface of a semiconductor-fabricating apparatus or a component member thereof by being formed into a molded body or a sintered body or by being formed into a film, thereby detecting a damaged spot caused by dry etching.

Description

Corrosion-resistant material for semiconductor manufacturing equipment {CORROSION RESISTANT MATERIAL FOR SEMICONDUCTOR MANUFACTURING APPARATUS}

The present invention relates to a corrosion-resistant material for a semiconductor manufacturing apparatus.

In the dry etching process of a semiconductor element, normally, a circuit is formed on a semiconductor wafer by plasma discharge while flowing in corrosive gas, such as a halogen-containing gas. At that time, the corrosive gas is not only applied to the wafer, but also to the container (chamber) of the semiconductor manufacturing apparatus, the wafer holding material (ring plate), the discharge substrate (etching plate), etc. (hereinafter referred to as "container etc."), and the member that does not require etching. Inflicts damage and deteriorates the surface of their members to generate suspended particles called particles. Particles are finally deposited on the wafer, causing short circuits in circuits or poor etching, thereby lowering productivity of semiconductor devices.

Since rare earth elements have high resistance to halogen-containing gases, it is known that high corrosion resistance can be expressed by coating them on the surface of a semiconductor etching apparatus or using a molded or sintered body containing rare earth elements in a semiconductor etching apparatus ( Patent Documents 1 and 2).

Apart from the above-mentioned techniques, fluorescent substances made of oxides containing europium and yttrium are conventionally known (Patent Documents 3 and 4).

Japanese Patent Laid-Open No. 2002-332559 Japanese Patent Laid-Open No. 2003-063883 Japanese Patent Laid-Open No. 2002-38150 Japanese Patent Laid-Open No. 2008-174690

When the conventional corrosion-resistant member described in Patent Documents 1 and 2 is used, even if particles are generated on the surface of a container or the like of a semiconductor manufacturing apparatus, it is difficult to specify the location of the occurrence or the degree of deterioration, All had to be exchanged. Since the degree of damage varies depending on the member, even in a container of a semiconductor manufacturing apparatus, etc., if it is possible to ascertain the location where particles are generated and the degree of deterioration, only the deteriorated member can be replaced without replacing all of the member, thereby prolonging the life of the member. or to reduce the replacement cost of the member.

In addition, Patent Documents 3 and 4 only describe a light emitting element, and a phosphor composed of an oxide containing europium and yttrium, and using it as a corrosion resistant material in a container for a semiconductor manufacturing apparatus, etc. is studied at all. there is not

When this inventor earnestly studied in order to solve the said subject, when a specific corrosion-resistant material corroded by a halogen-type component, it discovered that luminescence intensity became high. Based on this knowledge, by using this corrosion-resistant material for the container of a semiconductor manufacturing apparatus, etc., the method by which the deterioration state of a member and the location of deterioration can be determined easily was discovered.

Specifically, the present invention relates to a corrosion-resistant material for a semiconductor manufacturing apparatus comprising a base material having dry etching resistance and an element that imparts to the base material the ability to emit visible light by ultraviolet irradiation.

Moreover, this invention is a manufacturing method of a semiconductor manufacturing apparatus or its structural member,

By molding or sintering a base material having dry etching resistance and a corrosion-resistant material containing an element that imparts visible light emitting ability to the base material by ultraviolet irradiation, a semiconductor manufacturing apparatus or a component thereof is manufactured, or a semiconductor manufacturing apparatus or It is related with the manufacturing method of forming the said corrosion-resistant material into a film on the base material surface of the structural member.

Moreover, this invention is a detection method of the part deteriorated by the etching gas in a semiconductor manufacturing apparatus,

By molding or sintering a base material having dry etching resistance and a corrosion-resistant material containing an element that imparts visible light emitting ability to the base material by ultraviolet irradiation, a semiconductor manufacturing apparatus or a component thereof is manufactured, or a semiconductor manufacturing apparatus or Forming the corrosion-resistant material into a film on the surface of the base material of the constituent member,

It relates to a detection method for determining a location where visible light is emitted by irradiating an ultraviolet ray to the semiconductor manufacturing apparatus or its constituent member after dry etching of a semiconductor using the semiconductor manufacturing apparatus or its constituent member.

When the corrosion-resistant material according to the present invention is in contact with an etching gas in a dry etching process, a container made of the corrosion-resistant material or a structural member of a semiconductor manufacturing apparatus formed into a film is etched to increase the surface roughness, thereby increasing the surface roughness according to the present invention By increasing the light emission intensity from the corrosion-resistant material, it is possible to easily specify the particle generation location. Since the corrosion-resistant material according to the present invention is a material that emits light in a wavelength region of visible light by irradiation with ultraviolet rays, at least the location where the particle exists can be easily detected.

EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of this invention is described in detail.

The corrosion-resistant material according to the present invention is a corrosion-resistant material for a semiconductor manufacturing apparatus containing a base material having dry etching resistance and an element that imparts to the base material the luminous ability of visible light by ultraviolet irradiation.

Here, the base material is a material used as a main or base material such as a composite material. It is preferable that the base material which concerns on this specification means the compound which comprises the main phase of a corrosion-resistant material.

In this specification, the base material which has dry etching resistance refers to the material which can withstand corrosion by the etching gas containing a halogen element etc. used in the dry etching process in manufacture of a semiconductor element. Examples of the base material having dry etching resistance include rare-earth element-containing compounds and aluminum or silicon compounds, and rare-earth element-containing compounds are preferable. Among them, rare-earth element-containing oxides, halides, or oxyhalides are preferable. .

As the rare earth element, yttrium or gadolinium is particularly preferable from the viewpoint of improving resistance to dry etching. Here, dry etching resistance can be evaluated using the acid exposure method with a halogen acid etc. which are described in the Example mentioned later.

Examples of the oxide containing the rare earth element described above include oxides of rare earth elements and complex oxides of rare earth elements and other metal elements. The oxide containing the rare earth element is preferably a compound containing aluminum (Al) and/or silicon (Si) in addition to the rare earth element (Ln) and oxygen (O) from the viewpoint of corrosion resistance. From this point of view, the oxide containing a rare earth element _{is particularly preferably at least one selected from yttria (Y 2} O ₃ ), yttrium aluminate, gadolinium aluminate, yttrium silicate, and gadolinium silicate. Examples of the yttrium aluminate include Y ₃ Al ₅ O ₁₂ , Y ₄ Al ₂ O _{9 , YAlO 3} , and the like. Examples of gadolinium aluminate include Gd ₃ Al ₅ O ₁₂ , Gd ₄ Al ₂ O ₉ , and GdAlO ₃ . Examples of the yttrium silicate include Y ₂ Si ₂ O ₇ and Y ₂ SiO ₅ . Examples of the gadolinium silicate include Gd ₂ Si ₂ O ₇ and Gd ₂ SiO ₅ .

Examples of the halide containing a rare-earth element include a compound composed of a rare-earth element (Ln) and a halogen, and specific examples of the rare-earth element fluoride (fluoride) and chloride (chloride) are preferable. In view of corrosion resistance, the halide containing a rare earth element is particularly at least one selected from _{yttrium fluoride (YF 3} ), gadolinium fluoride (GdF ₃ ), yttrium chloride (YCl ₃ ) and gadolinium chloride (GdCl _{3 ).} desirable.

An oxyhalide containing a rare earth element (hereinafter also referred to as “Ln-OX”) is a compound composed of a rare earth element (Ln), oxygen (O), and halogen (X). _{Ln-OX is preferably represented by LnO a} X _b (0.3≤a≤1.7, 0.1≤b≤1.9) from the viewpoint of corrosion resistance and availability. In particular, from the above viewpoint, in the above formula, it is more preferable that 0.35 ? a ? 1.65, and even more preferably 0.4 ? a ? 1.6. Further, 0.2≤b≤1.8 is more preferred, and 0.5≤b≤1.5 is still more preferred. Moreover, from the viewpoint of availability, etc., in the above formula, it is preferable to satisfy 2.3≤2a+b≤5.3, particularly 2.35≤2a+b≤5.1, and particularly preferably satisfy 2a+b=3.

Moreover, as an oxyhalide containing a rare earth element, from the point of corrosion resistance, yttrium oxyfluoride (hereinafter also referred to as "YOF"), gadolinium oxyfluoride (hereinafter also referred to as "Gd-OF"), and yttrium oxyfluoride It is especially preferable that it is at least 1 sort(s) chosen from a chloride (it is also described hereafter as "YO-Cl") and a gadolinium oxychloride (it is also denoted as "Gd-O-Cl" hereafter). Examples of the yttrium oxyfluoride (YOF) include YOF, Y ₅ O ₄ F ₇ , Y ₇ O ₆ F ₉ , Y ₄ O ₃ F ₆ , and the like. Examples of the oxyfluoride of gadolinium include GdOF and Gd ₄ O ₃ F ₆ . As an oxychloride of yttrium, YOCl is mentioned. As an oxychloride of gadolinium, GdOCl is mentioned.

In addition, as the base material having dry etching resistance, a compound containing yttrium, fluorine and/or oxygen is preferable from the viewpoint of corrosion resistance, and in particular, in yttria, yttrium aluminate, yttrium silicate, yttrium fluoride and yttrium oxyfluoride. It is still more preferably at least one selected from Y ₂ O ₃ , Y ₃ Al ₅ O ₁₂ , Y ₂ Si ₂ O ₇ , YF ₃ , YOF and Y ₅ O ₄ F ₇ is preferably at least one selected from the group consisting of Y 2 O 3 , Y 3 Al 5 O 12 , Y 2 Si 2 O 7 , YF 3 , YOF and Y 5 O 4 F 7 . Do.

If the base material having dry etching resistance is contained in the corrosion-resistant material, for example, when the base material is made of a rare-earth element-containing compound, it is determined that the corrosion-resistant material contains a rare earth element in a predetermined amount in a wavelength dispersive fluorescence X-ray analyzer. It can be specified by measuring by the method and confirming that the corrosion-resistant material contains a rare-earth element-containing compound by X-ray diffraction measurement. For example, in the corrosion resistant material, the content of the rare earth element, preferably yttrium or gadolinium, is preferably 35 mass% or more, and accounts for 60 mass% or more as the amount of the rare earth element from the viewpoint of corrosion resistance stability. It is more preferable that it occupies 65 mass % or more, and it is especially preferable that it occupies 70 mass % or more. In the corrosion resistant material, the content of the rare earth element, preferably yttrium or gadolinium, is preferably 70 mass% or more, and 80 mass% or more as the amount of the rare earth element-containing compound from the viewpoint of corrosion resistance stability. It is particularly preferred. The upper limit of the content of yttrium or gadolinium in the corrosion-resistant material may be an amount that ensures the amount of the luminescent ability-imparting element described later. From the viewpoint of improving corrosion resistance, the corrosion-resistant material of the present invention has a peak of maximum intensity observed at 2θ = 10 degrees to 90 degrees in X-ray diffraction measurement using _{Cu-Kα ray or Cu-Kα 1 ray is that of yttrium or gadolinium.} It is preferably an oxide, halide or oxyhalide.

Next, a base material having dry etching resistance of the corrosion resistant material according to the present invention, and an element that imparts to the base material the luminous ability of visible light by ultraviolet irradiation contained therein (hereinafter referred to as "luminous ability imparting element") will be described. do.

Examples of the above-described luminescent ability imparting element include elements that are different from the rare-earth elements constituting the base material and which belong to lanthanoids in the rare-earth elements. Specifically, selected from europium (Eu), terbium (Tb), neodymium (Nd), erbium (Er), dysprosium (Dy), samarium (Sm), thulium (Tm), praseodymium (Pr), and ytterbium (Yb) At least one type used is preferably mentioned because it is difficult to reduce the corrosion resistance performance of the base material. Among them, europium (Eu) or terbium (Tb) having a high luminescence intensity is particularly preferable from the viewpoint of high luminescence imparting ability to the base material.

It is preferable that 0.05 mass % or more and 10 mass % or less of said luminescent ability imparting element are contained in the corrosion-resistant material which concerns on this invention. By setting it as 0.05 mass % or more, luminescent intensity becomes large, and deterioration of the container etc. of the semiconductor manufacturing apparatus mentioned later can be detected efficiently. From this point of view, more preferably, the amount of the above-described luminescent ability imparting element in the corrosion-resistant material is 0.1 mass% or more, and particularly preferably 0.5 mass% or more. In addition, since the luminescent ability imparting element has inferior dry etching resistance compared to the base material having dry etching resistance, adding the luminescent ability imparting element causes impurity contamination. It is preferable because the fall of impurity contamination, such as a container of a semiconductor manufacturing apparatus, can be effectively prevented by being set as 10 mass % or less. From this viewpoint, More preferably, it is 8 mass % or less, Especially preferably, it is 5 mass % or less. The amount of the luminescent ability imparting element in the corrosion-resistant material can be measured with a wavelength-dispersive fluorescence X-ray analyzer.

The amount of the above-mentioned luminescent ability imparting element in the corrosion-resistant material can also be measured by an inductively coupled plasma emission spectroscopy apparatus. A measurement sample can be prepared by dissolving a corrosion-resistant material with nitric acid, hydrochloric acid, or perchloric acid.

In the corrosion-resistant material according to the present invention, it is preferable that the above-described base material and the above-described luminescent ability imparting element are in a solid solution state. For example, when the base material is an oxide, halide or oxyhalide containing yttrium or gadolinium, it is in the form of a solid solution in which a part of yttrium or gadolinium in the base material is substituted with europium. When the luminescent ability imparting element itself or in the form of its sole oxide does not sufficiently emit visible light even when irradiated with ultraviolet rays, it is added to the base material, and ions of the luminescent ability imparting element are dispersed in an appropriate concentration in the base material. will glow strongly. For example, in the said base material, such as yttrium oxide to which light-emitting ability was provided by addition of europium, the Eu ³⁺ ion emits red light. This is because, when a europium element is added to the base material containing yttrium, such as yttrium oxide, the europium element is substituted with a part of the yttrium element and ^{becomes Eu 3+} ions and is activated. When ultraviolet rays are irradiated thereto, visible light is emitted from ^{Eu 3+ ions.} In the base material to which luminescence ability was imparted by addition of terbium, Tb ³⁺ ions emit green light. When the corrosion-resistant material of the present invention contains europium, the wavelength of light emitted by irradiating ultraviolet light is, for example, preferably 600 nm or more and 620 nm or less, and more preferably 605 nm or more and 615 nm or less. Further, when the corrosion resistant material of the present invention contains terbium, the wavelength of light emitted by irradiating ultraviolet light is preferably, for example, 530 nm or more and 550 nm or less, and more preferably 535 nm or more and 545 nm or less.

In addition, the corrosion-resistant material according to the present invention may contain unavoidable impurities in addition to the base material and the luminescent ability imparting element. Examples of unavoidable impurities include impurities contained in oxides, halides or oxyhalides containing rare earth elements as raw materials, compounds containing luminescent ability-imparting elements, etc., impurities mixed in during the production of the corrosion-resistant material, and the like. can

Next, the form of the corrosion-resistant material which concerns on this invention is demonstrated.

A powder is mentioned as a form of the corrosion-resistant material which concerns on this invention. Moreover, the film formed into a film by the molded object or sintered compact of the said powder, or this powder is also mentioned.

It is preferable that the specific surface area of the corrosion-resistant material which is powder is 0.1 m<2>/g or more and 30 m<2>/g or less. When the specific surface area of the corrosion-resistant material is 0.1 m 2 /g or more, there is an advantage that film formation or sintering becomes easy. In addition, when the specific surface area of the corrosion-resistant material is 30 m 2 /g or less, the luminous intensity of the corrosion-resistant material tends to increase, and the degree of improvement of the luminous intensity of the corrosion-resistant material at the time of generation of particles is increased, and the deterioration location is further efficiently removed. It has the advantage of being able to detect From these viewpoints, the specific surface area of the corrosion-resistant material is more preferably 0.3 m 2 /g or more and 20 m 2 /g or less, particularly preferably 0.5 m 2 /g or more and 18 m 2 /g or less, and most preferably 0.5 m 2 /g or more and 15 m 2 /g or less. The specific surface area can be measured by the BET one-point method, and specifically, it can be measured by the method described in Examples to be described later. The powder having the above specific surface area may be in the form of granules.

The powder corrosion-resistant material preferably has an average particle diameter of 10 µm or more and 100 µm or less, more preferably 15 µm or more and 80 µm or less, and more preferably 20 µm or more from the viewpoints of ease of manufacture, fluidity, and uniformity during filling of the material. It is especially preferable that it is 60 micrometers or less. An average particle diameter is an integrated volume particle diameter (D50) in 50 volume % of integration volumes by the laser diffraction/scattering type particle size distribution measuring method. In the present specification, D50 is a particle size measured without ultrasonic treatment, and can be measured by the method described in Examples. In particular, when the powdery corrosion-resistant material is granules, it is preferable that the average particle diameter is within the above range from the viewpoint of obtaining effects such as ease of manufacture, fluidity, and uniformity at the time of filling.

Then, the suitable manufacturing method of the corrosion-resistant material which concerns on this invention is demonstrated.

First, when the base material is a rare earth element-containing oxide, it is preferable to do as follows.

(Method A)

A method for manufacturing a corrosion-resistant material for a semiconductor manufacturing apparatus, comprising a base material having dry etching resistance and an element that imparts visible light emitting ability to the base material by ultraviolet irradiation, wherein the base material is an oxide containing rare earth elements,

1A step of mixing an aqueous solution containing a weak acid, an oxide of a rare earth element, and an oxide of the luminescent ability-imparting element to obtain a solution;

Step 2A of concentrating the solution obtained in Step 1A;

Step 3A of cooling the concentrated solution obtained in Step 2A to precipitate a mixed weak acid salt of a rare earth element and the element imparting luminescence ability;

A manufacturing method comprising a fourth A step of calcining the precipitate obtained in the third A step to obtain the corrosion resistant material as a rare earth element-containing oxide containing a luminescent ability imparting element.

It is preferable that this production method further has a step 5A of pulverizing the oxide obtained in step 4A, and further

Step 6A of granulating and drying the powder obtained in Step 5A to obtain a granulated product;

It is more preferable to have a 7th step of firing the granulated product obtained in the 6th step.

A suitable example of the said manufacturing method A is demonstrated.

In the step 1A, the weak acid in the aqueous solution containing the weak acid refers to an acid having a small acid dissociation constant, and preferably an acid having a pKa of 1.0 or more at 25°C. Here, pKa refers to _{pKa 1 .} It is preferable that pKa is 3.0 or more. Examples of the acid having a pKa of 1.0 or more include organic acids having a carboxylic acid group such as acetic acid, phosphoric acid, formic acid, butyric acid, lauric acid, lactic acid, malic acid, citric acid, oleic acid, linoleic acid, benzoic acid, oxalic acid, succinic acid, malonic acid, maleic acid, and tartaric acid. In addition, inorganic acids, such as boric acid, hypochlorous acid, hydrogen fluoride, and hydrosulfuric acid, are mentioned. Among them, an organic acid having a carboxylic acid group is preferable, and particularly, acetic acid is preferable from both viewpoints of suppression of manufacturing cost and ease of obtaining a corrosion-resistant material having desired physical properties. These can be used 1 type or in combination of 2 or more types.

The concentration of the weak acid in the mixture obtained by mixing the weak acid, the oxide of the rare earth element, and the oxide of the luminescent ability imparting element in the aqueous solution containing the weak acid obtained in step 1A is 10% by mass or more and 30% by mass or less, the rare earth element oxide And it is preferable from the point of being easy to melt|dissolve the oxide of the said luminescent ability imparting element, easy to obtain a corrosion-resistant material of desired physical property, and the point of improving the solubility of a raw material, and it is more preferable that it is 10 mass % or more and 25 mass % or less.

The amount of the oxide of the rare earth element and the weak acid used for dissolving the oxide of the luminescent ability-imparting element is 60 moles or more of the rare earth element oxide and the rare earth element oxide in the weak acid aqueous solution with respect to 100 moles of the total oxide of the rare earth element oxide and the luminescent ability-imparting element. , It is preferable from the viewpoint of sufficiently dissolving the oxide of the luminescent ability imparting element to easily obtain a corrosion-resistant material having desired physical properties, and preferably 70 mol or more. In addition, the amount of the weak acid is preferably 200 mol or less with respect to 100 mol of the total of the rare earth element oxide and the luminescent ability-imparting element oxide, since it can be produced at low cost.

At the time of dissolving the oxide of the rare earth element and the oxide of the element for imparting luminescence in the aqueous weak acid solution, the weak acid aqueous solution may be heated to room temperature or higher. This is because the oxide of the rare earth element and the oxide of the above-mentioned luminescent ability imparting element are sufficiently dissolved in an aqueous solution containing a weak acid, and this is preferable in terms of making it easy to obtain a corrosion-resistant material having desired properties. The heating temperature at this time is preferably 70°C or more and 95°C or less, and more preferably 80°C or more and 90°C or less from the viewpoint of suppressing the dissolution efficiency and the dissolution residue.

As the oxide of the rare earth element, yttrium oxide (Y ₂ O ₃ ), gadolinium oxide (Gd ₂ O ₃ ), or the like is preferable. Examples of the oxide of the luminescent ability imparting element include europium oxide (Eu ₂ O ₃ , EuO), terbium oxide (Tb ₂ O ₃ , Tb ₄ O ₇ ), neodymium oxide (Nd ₂ O ₃ ), and erbium oxide (Er ₂ O _{3 ).} ), dysprosium oxide (Dy ₂ O ₃ ), samarium oxide (Sm ₂ O ₃ , SmO), thulium oxide (Tm ₂ O ₃ ), praseodymium oxide (Pr ₆ O ₁₁ ) and ytterbium oxide (Yb ₂ O ₃ ) At least one kind of oxide is preferred. Among them, europium oxide or terbium oxide is more preferable.

Next, in the step 2A, the solution obtained in the step 1A is concentrated. As a concentration method, it can carry out by heating and/or reduced pressure. As for the degree of concentration, it is preferable from the viewpoint of obtaining uniform crystal nuclei to carry out so that the liquid amount is 60 to 80 vol% with respect to the original solution, and 65 to 75 vol% is preferable to carry out the crystal nuclei. It is more preferable at the point of making it more uniform.

Subsequently, in the step 3A, the concentrated solution obtained in the step 2A is cooled. The cooling method may be a general air cooling method or a water cooling method, and cooling to room temperature is preferable from the viewpoint of reducing unprecipitated content. Here, when the concentrated solution is cooled, a mixed weak acid salt comprising a weak acid salt of a rare earth element and a weak acid salt of an element imparting luminescence is precipitated.

Then, in the step 4A, when the precipitate obtained in the step 3A is fired, a target corrosion-resistant material powder is obtained. The firing atmosphere may be an oxygen-containing atmosphere such as an atmospheric atmosphere, or an inert atmosphere such as nitrogen or argon, and is preferably an oxygen-containing atmosphere from the viewpoint of reducing the amount of residual organic matter derived from the weak acid.

When the firing temperature is 1800°C or less, it is easy to obtain a suitable corrosion-resistant material from the viewpoint of production cost, and it is more preferably 1700°C or less, and even more preferably 1600°C or less. Moreover, it is easy to obtain the powder of a corrosion-resistant material preferable from the point of luminous efficiency that a firing temperature is 500 degreeC or more, and it is still more preferable that it is 550 degreeC or more. 10 hours or more and 50 hours or less are preferable from a viewpoint of reducing baking nonuniformity, and, as for the baking time in the said temperature range, 20 hours or more and 40 hours or less are more preferable.

The mixed weak acid salt of the precipitated rare earth element weak acid salt and the luminescent property imparting element weak acid acid salt is preferably dehydrated prior to calcination from the viewpoint of reducing the calcination unevenness in the calcination step. Dehydration can be performed by a conventional method using a centrifugal separator or the like. In addition, about the above-mentioned mixed weak acid salt, you may perform washing|cleaning, drying, etc. before baking.

Next, when setting it as the shape of granules, in the 5A process which is a suitable manufacturing process, it is preferable to grind|pulverize the oxide powder obtained in the said 4th process, and to set it as a desired particle size. You may perform grinding|pulverization by either dry grinding and wet grinding. In the case of dry grinding, a dry ball mill, a dry bead mill, a high-speed rotary impact mill, a jet mill, a millstone grinder, a roll mill, and the like can be used. In the case of wet grinding, it is preferable to carry out with a wet grinding apparatus using a grinding medium such as a spherical shape or a cylindrical shape. Examples of such a grinding device include a ball mill of a medium stirring mill, a vibrating mill, a bead mill, and the like. Examples of the material of the grinding medium include zirconia, alumina, silicon nitride, silicon carbide, tungsten carbide, abrasion-resistant steel and stainless steel. Zirconia may be stabilized by adding a metal oxide. In addition, as a dispersion medium for wet grinding, the same thing as given below can be used as an example of the dispersion medium of the slurry used at the time of granulation by the spray-drying method mentioned later. In the case of wet grinding, a slurry is obtained by adding a liquid medium to the object to be pulverized before pulverization. As said liquid medium, water and various organic solvents can be used 1 type or in combination of 2 or more types, The thing similar to the dispersion medium of the 6th A process mentioned later can be used. Especially, water is preferable at the point of production cost. It is preferable from the point of film-formability and moldability to perform grinding|pulverization until D50 becomes 0.01 micrometer or more and 2 micrometers or less, and it is more preferable to carry out until it becomes 0.02 micrometer or more and 1.5 micrometers or less.

In the case of granulation, step 6A, which is a granulation step, is performed. As the granulation method, a spray drying method, an extrusion granulation method, a rolling granulation method, etc. can be used, but the spray drying method is preferable because the resulting granulated powder has good fluidity and also has high film-forming properties when pressed against the substrate at high pressure. In the spray drying method, a slurry obtained by dispersing the rare earth element oxide powder obtained above in a dispersion medium is supplied to a spray dryer. As a dispersion medium, water and various organic solvents can be used 1 type or in combination of 2 or more types. Especially, it is preferable to use water, the organic solvent with respect to water solubility 5 mass % or more, or the mixture of this organic solvent and water, since it is easy to obtain a denser and uniform film|membrane. Here, the organic solvent having a solubility in water of 5% by mass or more includes free mixing with water. Examples of the organic solvent having a solubility in water of 5% by mass or more (including those freely mixed with water) include alcohols, ketones, cyclic ethers, formamides, and sulfoxides. Moreover, it is preferable that the mixing ratio of the said organic solvent and water in the mixture of the organic solvent and water whose solubility with respect to water is 5 mass % or more exists in the range of the solubility with respect to the water of this organic solvent. As conditions for spray drying, from the viewpoint of obtaining spherical granules and obtaining a uniform granule diameter, the operating conditions of the spray dryer are preferably slurry supply rate: 200 mL/min or more and 400 mL/min or less, and 250 mL/min. It is more preferable to set it as more than 350 mL/min or less. For a rotary atomizer method, the number of revolutions obtained from the atomiser the uniform granulate diameter point and not more than 7500min ^-1 at least 25000min ^-1 preferably, it is more preferable that at least a 22000min 10000min ^{-1 -1} or less. The inlet temperature is preferably 150°C or more and 300°C or less, more preferably 180°C or more and 270°C or less, from the viewpoint of obtaining a uniform granule diameter and bulk density.

Preferably, in the step 7A, the granulated product obtained in the step 6A is fired. The firing atmosphere may be an oxygen-containing atmosphere such as an atmospheric atmosphere, or an inert atmosphere such as nitrogen or argon.

When the firing temperature is 1800°C or less, a desired corrosion-resistant material powder is obtained from the viewpoint of suppressing impurity contamination derived from the furnace material, and it is more preferably 1700°C or less, and even more preferably 1650°C or less. In addition, if it is 800 degreeC or more, it is easy to obtain a desired corrosion-resistant material powder from the point of maintaining granular strength, It is more preferable that it is 900 degreeC or more, and it is still more preferable that it is 950 degreeC or more. The firing time in the above temperature range is preferably 5 hours or more and 20 hours or less, and more preferably 8 hours or more and 15 hours or less, from the viewpoint of reducing firing non-uniformity.

Next, when the base material is a halide containing a rare earth element, it is preferable to do as follows.

(Method B)

A method for manufacturing a corrosion-resistant material for a semiconductor manufacturing device, comprising a base material having dry etching resistance and an element that imparts to the base material the ability to emit visible light by ultraviolet irradiation, wherein the base material is a halide containing a rare earth element,

1B step of mixing an aqueous solution containing an acid, an oxide of a rare earth element, and an oxide of the element for imparting luminescence to obtain a solution;

A second B step of adding hydrohalic acid to the solution obtained in the first B step and precipitating;

A 3B step of dehydrating and drying the precipitate obtained in the 2B step;

A manufacturing method comprising a fourth B step of calcining the dried product obtained in the third B step to obtain the corrosion resistant material as a rare earth element halide containing a luminescent ability imparting element.

It is preferable that this manufacturing method further has a 5th step of pulverizing the halide obtained in the 4th step,

Step 6B of granulating and drying the powder obtained in Step 5B to obtain a granulated product;

It is more preferable to have a 7th process of baking the granulated material obtained in the said 6th process.

A suitable example of the said manufacturing method B is demonstrated.

In the step 1B, examples of the acid of the acid-containing aqueous solution include nitric acid, oxalic acid, acetic acid, amine complex, hydrochloric acid, and the like. Especially, nitric acid is preferable at the point which can be manufactured at availability and low cost. In addition, the concentration of the acid in the solution in which the aqueous solution containing the acid, the oxide of the rare earth element, and the oxide of the above-mentioned luminescent ability imparting element is mixed is 30% by mass or more and 80% by mass or less from the viewpoint of solubility and handling safety. It is preferable, and it is more preferable that they are 40 mass % or more and 60 mass % or less. The amount of the aqueous solution containing the oxide of the rare earth element and the acid used for dissolving the oxide of the luminescent element is 500 mol or more of the acid with respect to 100 mol of the total of the oxide of the rare earth element and the luminescent element. It is preferable from the viewpoint of sufficiently dissolving the oxide of the rare earth element and the oxide of the element for imparting luminescence in the aqueous solution containing it, thereby making it easy to obtain a corrosion-resistant material having desired physical properties, and preferably 700 mol or more. In addition, the amount of the acid is preferably 1000 mol or less with respect to 100 mol of the total of the rare earth element oxide and the luminescent ability-imparting element oxide, since it can be produced at low cost.

The oxide of the rare earth element and the oxide of the luminescent ability imparting element are the same as the oxides described in the above-mentioned production method A.

Next, in the step 2B, the aqueous solution of hydrohalic acid added to the solution obtained in the step 1B is used as an aqueous solution having a concentration of 40% by mass or more and 60% by mass or less. It is preferable from the point of ensuring the safety|security at the time of the point of reactivity and handling, and it is preferable to use it as an aqueous solution with a density|concentration of 45 mass % or more and 55 mass % or less.

The amount of hydrohalic acid used is 2.4 mol or more with respect to a total of 1 mol of the rare earth element and the luminescent ability-imparting element in the solution, which sufficiently reacts with the rare earth element and the oxide of the luminescent ability-imparting element, resulting in a uniform precipitate. The obtained point is preferable from the point of easy obtaining a favorable corrosion-resistant material, and it is more preferable that it is 2.7 mol or more. In addition, the amount of hydrohalic acid to be used is preferably 3.6 moles or less with respect to a total of 1 mole of the rare earth element and the luminescent ability imparting element in the solution from the viewpoint of reducing the manufacturing cost, and more preferably 3.3 moles or less.

The reaction between the solution and the hydrohalic acid is preferably carried out at 30°C or higher and 60°C or lower, from the viewpoint of easy to obtain a preferable corrosion-resistant material from the viewpoint of sufficiently reacting the rare earth element and obtaining precipitation in a high yield, and 35°C or more and 55°C or more It is more preferable to carry out at or below °C.

The deposit obtained in the said 2nd B process is dried in the said 3rd B process. It is preferable to dry this deposit after washing|cleaning with liquid media, such as water. An inert atmosphere, such as nitrogen or argon, may be sufficient as drying, and it is preferable at the point which dries the precipitate after washing|cleaning that it is an oxygen containing atmosphere efficiently. When the drying temperature is 200° C. or less, it is easy to obtain a preferable corrosion-resistant material from the viewpoint that uniform firing is possible in the subsequent firing step, and it is more preferably 180° C. or less, and even more preferably 160° C. or less. The drying temperature is preferably 100°C or higher, and more preferably 120°C or higher, in terms of drying efficiency and moisture retention can be suppressed. 10 hours or more and 30 hours or less are preferable, and, as for the drying time in the said temperature range, 15 hours or more and 25 hours or less are more preferable.

Subsequently, in the step 4B, by firing the dried product obtained in the step 3B, a powder of a corrosion-resistant material as a halide of a rare earth element containing a luminescent ability imparting element is obtained. The firing atmosphere may be an oxygen-containing atmosphere such as an atmospheric atmosphere, or an inert atmosphere such as nitrogen or argon, and is preferably an oxygen-containing atmosphere from the viewpoint of reducing the amount of residual organic matter derived from the weak acid.

When the firing temperature is 1000°C or less, a corrosion-resistant material suitable for suppressing excessive oxidation can be obtained, and it is more preferably 980°C or less, and even more preferably 950°C or less. Moreover, it is easy to obtain a preferable corrosion-resistant material at the point which makes crystallinity high that a firing temperature is 600 degreeC or more, and it is more preferable that it is 700 degreeC or more. 10 hours or more and 50 hours or less are preferable, and, as for the baking time in the said temperature range, 20 hours or more and 40 hours or less are more preferable.

Next, in the 5B process which is a suitable manufacturing process, it is preferable to grind|pulverize the corrosion-resistant material powder obtained in the said 4th process, and to manufacture granules by the 6th B process and the 7th process if necessary.

The contents of the operations in the steps 5B to 7B are the same as those in the steps 5A to 7A of the manufacturing method A. However, the firing temperature in step 7A is preferably 400°C or more and 800°C or less from the viewpoint of smoothly obtaining a rare-earth element halide containing a luminescent ability imparting element, and more preferably 500°C or more and 700°C or less.

In addition, when the said base material is an oxyhalide containing a rare earth element, it is preferable to carry out as follows.

(Method C)

A method for manufacturing a corrosion-resistant material for a semiconductor manufacturing device, comprising a base material having dry etching resistance and an element that imparts visible light emitting ability to the base material by ultraviolet irradiation, wherein the base material is an oxyhalide containing a rare earth element,

1C step of mixing an aqueous solution containing a weak acid, an oxide of a rare earth element, and an oxide of the luminescent ability-imparting element to obtain a solution;

a 2C step of concentrating the solution obtained in the 1C step;

a 3C step of cooling the concentrated solution obtained in the 2nd C step to precipitate a mixed weak acid salt of the rare earth element and the luminescent ability imparting element;

a fourth C step of calcining the precipitate obtained in the third C step to obtain a rare earth element oxide containing a luminescent ability imparting element;

a 5C step of dehydration after adding hydrohalic acid to a suspension obtained by adding a liquid medium to the oxide obtained in the 4th step;

A manufacturing method comprising a step 6C of calcining the dehydrated product obtained in step 5C to obtain the corrosion-resistant material as a rare earth element oxyhalide containing a luminescent ability imparting element.

This production method further comprises a 7C step of pulverizing the oxyhalide obtained in the 6C step;

an 8C step of granulating and drying the powder obtained in the 7C step to obtain a granulated product;

It is preferable to have a 9th C process of baking the granulated material obtained in the said 8th C process.

A suitable example of the said manufacturing method C is demonstrated.

The operation contents in the steps 1C to 4C described above are the same as the operation contents in the steps 1A to 4A of the manufacturing method A. In addition, the operation contents in the steps 7C to 9C, which are suitable manufacturing steps, are the same as those in the steps 5A to 7A of the manufacturing method A.

The steps specific to the present manufacturing method C are the 5th C step and the 6th C step, and the contents of the operation will be described below.

The step 5C is a step in which hydrohalic acid is added to a suspension obtained by adding a liquid medium to the oxide of a rare earth element containing the luminescent ability-imparting element obtained in the step 4C, and dehydration is performed.

In this production method C, it is preferable to use the oxide of a rare earth element containing the luminescent ability imparting element obtained in the production method A from the viewpoint that the composition of the oxyhalide can be strictly controlled. That is, the oxide powder of the rare earth element and the oxide powder of the luminescent ability-imparting element are dissolved in a heated aqueous weak acid solution and then cooled to precipitate a mixture of the rare earth element weak acid salt and the luminescent activity imparting element weak acid salt. It is preferable to use the luminescent ability-imparting element rare-earth element oxide obtained by calcining the mixture (that is, by the steps 1A to 4A above).

In step 5C, an oxide of a rare earth element containing a luminescent ability imparting element and hydrohalic acid are mixed to obtain a precursor of a rare earth element oxyhalide containing a luminescent ability imparting element. Examples of the hydrohalic acid include hydrofluoric acid (HF) and hydrochloric acid (HCl). It is preferable to perform mixing in water from a viewpoint of being easy to obtain a corrosion-resistant material with desirable physical properties efficiently, and a viewpoint of being able to perform reaction uniformly. From the same viewpoint, the temperature of the mixture of the rare earth element oxide powder containing the luminescent ability imparting element and the hydrohalic acid is preferably 20°C or more and 50°C or less, and 30°C or more and 40°C from the viewpoint of efficiently promoting the reaction. It is more preferable that it is below °C. When mixed with hydrohalic acid, the powder of the rare earth element oxide containing the luminescent ability imparting element is dispersed in water at a concentration of 50 g/L or more and 90 g/L or less, in terms of oxide of the rare earth element containing the luminescent ability imparting element, It is preferable at the point which an oxyhalogenation reaction advances efficiently, and it is more preferable to disperse|distribute at a density|concentration of 60 g/L or more and 80 g/L or less.

The amount of hydrohalic acid to be used is preferably 10 parts by mass or more and 50 parts by mass or less, and 15 parts by mass or more of hydrohalic acid with respect to 100 parts by mass of the oxide of a rare earth element containing a luminescent ability imparting element from the viewpoint of obtaining a composition exhibiting excellent corrosion resistance. It is more preferable that it is 40 mass parts or less. Mixing of the rare earth element oxide powder containing the luminescent ability-imparting element and the hydrohalic acid is preferably performed while stirring, and from the viewpoint of smoothly obtaining the target product and shortening the production time, the stirring time is, for example, 10 hours or more and 50 It is preferable that it is time or less, and it is more preferable that it is 15 hours or more and 40 hours or less.

Next, in the step 6C, the precursor of the rare earth element oxyhalide containing the element imparting luminescence obtained in the step 5C is fired, thereby containing a luminescence ability imparting element suitable for the corrosion resistant material according to the present invention. An oxyhalide powder of a rare earth element is obtained. Firing is preferably carried out in an oxygen-containing atmosphere such as an air atmosphere, because an oxyhalide containing a rare earth element containing a luminescent ability imparting element can be easily obtained.

Moreover, since it is easy to obtain a preferable corrosion-resistant material from having said high crystallinity, it is preferable that it is 500 degreeC or more, and, as for a calcination temperature, it is more preferable that it is 550 degreeC or more. Moreover, it is preferable that it is 800 degrees C or less, and, as for the calcination temperature, it is more preferable that it is 700 degrees C or less from the point of suppressing excessive oxidation. 10 hours or more and 50 hours or less are preferable, and, as for the baking time in the said temperature range, 20 hours or more and 40 hours or less are more preferable.

From the viewpoint of efficiently obtaining the rare earth element oxyhalide powder containing the luminescent ability imparting element, it is preferable to dry the rare earth element oxyhalide precursor before firing, for example, the drying temperature is 100° C. or more and 200° C. or less. is preferable, and 120°C or more and 180°C or less are more preferable.

By the above firing, a corrosion-resistant material containing an oxyhalide of a rare earth element containing a luminescent ability imparting element is obtained. In addition, it is preferable to perform the 9th step from the 7th C step. The calcination temperature in the 9th step is preferably 500°C or more and 900°C or less from the viewpoint of smoothly obtaining the rare earth element oxyhalide containing the luminescent ability imparting element, and more preferably 600°C or more and 800°C or less.

Next, when the base material is aluminum oxide containing a rare earth element, it is preferable to carry out the following.

(Method D)

A method for producing a corrosion-resistant material for a semiconductor manufacturing device, comprising a base material having dry etching resistance and an element that imparts visible light emitting ability to the base material by ultraviolet irradiation, wherein the base material is aluminum oxide containing rare earth elements,

1D step of mixing an oxide of a rare earth element, an oxide of the luminescent ability imparting element, and aluminum oxide;

a 2D step of pulverizing the mixture obtained in the 1D step;

a 3D process of granulating and drying the powder obtained in the 2D process;

a 4D step of firing the granulated product obtained in the 3D step to obtain a fired body of aluminum oxide containing a rare earth element containing a luminescent ability imparting element;

A method for manufacturing a corrosion-resistant material having

A suitable example of the said manufacturing method D is demonstrated.

In the 1D step, an extremely general aluminum oxide (alumina) powder or the like can be used as the aluminum oxide. In aluminum oxide, in addition to aluminum (III) oxide represented by the formula of _{Al 2} O ₃ , aluminum (II) oxide represented by the formula of AlO and aluminum (I) oxide represented by the formula of _{Al 2 O exist.} As the oxide of the rare earth element and the oxide of the element for imparting luminescence, the oxides exemplified in the production method A can be used.

In the first step and the second step, the aluminum oxide, the oxide of the rare earth element, and the oxide of the element imparting luminescence are mixed and pulverized in a desired ratio. The 1D process and the 2D process may be performed simultaneously. The pulverization of the 2nd step may be dry pulverization or wet pulverization. In the case of wet grinding, a dispersion medium is added to the aluminum oxide, the oxide of the rare earth element, and the oxide of the element imparting luminescence to obtain a slurry. As a dispersion medium, what was mentioned as an example of the liquid medium used in said manufacturing process A is mentioned. The grinding conditions of the 2nd step include those exemplified in the 5th step. The powder obtained in the 2D process is granulated and dried in the 3D process to obtain a granulated product. The operation contents such as granulation and drying are the same as the operation contents of step 6A of the manufacturing method A described above.

And, in the 4D step, a corrosion-resistant material containing a rare earth element aluminum oxide containing a luminescent ability imparting element is obtained by firing the granulated product obtained in the 3D step. The firing atmosphere may be an oxygen-containing atmosphere such as an atmospheric atmosphere or an inert atmosphere such as nitrogen or argon, and an oxygen-containing atmosphere is preferable from the viewpoint of obtaining the target composition with high efficiency. When the firing temperature is 1800°C or less, a corrosion-resistant material suitable for preventing contamination of impurities from the furnace material is obtained, and it is more preferably 1600°C or less, and even more preferably 1500°C or less. Moreover, it is easy to obtain a desired corrosion-resistant material that a firing temperature is 1000 degreeC or more, and it is more preferable that it is 1200 degreeC or more. 3 hours or more and 10 hours or less are preferable at the point which baking can be performed uniformly, and, as for the baking time in the said temperature range, 4 hours or more and 8 hours or less are more preferable.

Next, when the base material is a silicon oxide containing a rare earth element, it is preferable to carry out the following.

(Method E)

A method for producing a corrosion-resistant material for a semiconductor manufacturing apparatus, comprising a base material having dry etching resistance and an element that imparts to the base material the ability to emit visible light by ultraviolet irradiation, wherein the base material is silicon oxide containing rare earth elements,

1E step of mixing an oxide of a rare earth element, an oxide of the luminescent ability imparting element, and a silicon oxide;

a second step of pulverizing the mixture obtained in the first step;

A 3E step of granulating and drying the powder obtained in the 2E step;

step 4E of calcining the granulated product obtained in step 3E to obtain a silicon oxide containing rare earth element containing a luminescent ability imparting element;

A method for manufacturing a corrosion-resistant material having

A suitable example of the said manufacturing method E is demonstrated.

In the first step E, silicon oxide is used instead of the aluminum oxide used in the above-mentioned production method D. Silicon oxide includes silicon dioxide (SiO ₂ ) and silicon monoxide (SiO), but in general, silicon dioxide (silica) is produced in the form of quartz, silica sand, silica stone, or the like, and its powder or the like is often used. As the oxide of the rare earth element and the oxide of the element for imparting luminescence, the oxides exemplified in the production method A can be used.

In the first E step and the second E step, the silicon oxide, the rare earth element oxide, and the luminescent ability imparting element oxide are mixed in a desired ratio, and mixed and pulverized. The 1st E process and the 2nd E process may be performed simultaneously. The pulverization in step 2E may be dry pulverization or wet pulverization. In the case of wet grinding, a dispersion medium is added to the silicon oxide, the oxide of the rare earth element, and the oxide of the element imparting luminescence to obtain a slurry, and grinding is performed. As a dispersion medium, what was mentioned as an example of the dispersion medium of the wet grinding used in the said manufacturing process A is mentioned. The grinding conditions of the grinding|pulverization of the 2nd E process are those exemplified in the 5th process. The powder obtained in step 2E is granulated and dried in step 3E to obtain a granulated product. The operation contents such as granulation and drying are the same as the operation contents of step 6A of the manufacturing method A described above.

Then, in the step 4E, by firing the granulated product obtained in the step 3E, a corrosion-resistant material containing a rare earth element silicon oxide containing a light-emitting ability imparting element is obtained. The firing atmosphere may be an oxygen-containing atmosphere such as an air atmosphere or an inert atmosphere such as nitrogen or argon, and an oxygen-containing atmosphere is preferable from the viewpoint of obtaining the target composition with high efficiency. When the firing temperature is 1800°C or less, a corrosion-resistant material suitable for suppressing impurity contamination from the furnace material is obtained, and it is more preferably 1600°C or less, and even more preferably 1500°C or less. Moreover, it is easy to obtain a desired corrosion-resistant material that a firing temperature is 1000 degreeC or more, and it is more preferable that it is 1200 degreeC or more. 5 hours or more and 30 hours or less are preferable at the point which performs baking uniformly, and, as for the baking time in the said temperature range, 10 hours or more and 25 hours or less are more preferable.

Next, the method of using the obtained corrosion-resistant material according to the present invention will be described.

It is preferable that the corrosion-resistant material which concerns on this invention be used as a film which coat|covers the surface of a semiconductor manufacturing apparatus, a container etc. which is its structural member, or these. In order to use it for a semiconductor manufacturing apparatus or its structural member, it can shape|mold the corrosion-resistant material which concerns on this invention to form a compact, or it can sinter and manufacture as a sintered compact. Alternatively, in order to cover the surface of the semiconductor manufacturing apparatus or its constituent member, it can be obtained by forming a film on the above-described surface with the corrosion-resistant material according to the present invention.

First, the manufacturing method of the molded object or sintered compact using the corrosion-resistant material which concerns on this invention is demonstrated.

In order to manufacture a molded object, the metal mold|die press method, the rubber press (hydrostatic press) method, the sheet|seat shaping|molding method, the extrusion molding method, the injection molding method, etc. can be used. And in order to sinter the obtained molded object, the pressure sintering method is used. As a specific pressure sintering method, hot press, pulse energization pressurization (SPS), and hot isostatic pressurization (HIP) can be used. By these methods, the powder (granule) of the corrosion-resistant material according to the present invention can be used as a compact or sintered compact.

Further, a method for forming a film of the corrosion-resistant material powder according to the present invention on a semiconductor manufacturing apparatus or a constituent member thereof will be described. As a main film-forming method, a thermal spraying method, AD (aerosol deposition) method, a physical vapor deposition (PVD) method, etc. are mentioned. As the thermal spraying method, frame thermal spraying, high-speed frame thermal spraying, explosion thermal spraying, laser thermal spraying, plasma thermal spraying, laser-plasma composite thermal spraying, etc. are applicable. AD method is a technique for forming a film on the surface of a substrate by mixing a film-forming powder with a gas at room temperature to form an aerosol state, and then spraying it at high speed through a nozzle to collide with the substrate. The PVD method is largely divided into a sputtering method, a vacuum deposition method, and an ion plating method. For example, the vacuum vapor deposition method is a method of forming a film by evaporating or sublimating a material for film formation in a vacuum, and depositing the vapor onto a substrate to be formed into a film. As the vacuum vapor deposition method, an electron beam method or a laser vapor deposition method is preferable because it has a sufficiently large energy to vaporize a powder such as an oxide of a rare earth element. In addition, the ion plating method is a film formation method on the same principle as the vapor deposition method, but in the other part, by passing the evaporating particles through the plasma, the ion plating method has a positive charge, and a negative charge is applied to the substrate to attract the evaporating particles. It is deposited to form a film.

Next, in the semiconductor manufacturing apparatus using the corrosion-resistant material which concerns on this invention, the method of detecting the location deteriorated by the dry etching gas is demonstrated.

In the semiconductor manufacturing apparatus, what is deteriorated by the dry etching gas is that the surface of the container of the semiconductor manufacturing apparatus is contaminated and deteriorated by the dry etching by the halogen gas or the like in the dry etching process at the time of manufacturing the semiconductor. Because. When the surface deteriorates, it is necessary to repair or change the location, and if the location can be determined and specified, repair and replacement work will be efficient, and it will become very advantageous also in the point of maintenance. Therefore, the corrosion-resistant material according to the present invention in which a rare-earth element-containing oxide as a base material is mixed with an element for imparting luminescence is used as a molded body, a sintered body, or a film formed on the surface of a container of a semiconductor manufacturing apparatus. Determination of deterioration by

The reason which makes deterioration determination possible is as follows.

When dry etching is performed, the surface of a container etc. becomes ravaged by an etching gas, and surface roughness becomes large. The more severe the contamination by the etching gas, the greater the surface roughness. When the surface is irradiated with ultraviolet light, visible light is emitted from a light-emitting ability-imparting element such as europium present in the material on the surface. As the surface roughness increases, the specific surface area increases. As the specific surface area increases, the emission intensity of visible light also increases. Therefore, by observing the emission degree, for example, the peak height of the emission intensity, the degree of deterioration due to etching gas is determined. can do. Therefore, when the light emission degree is investigated before and after dry etching, the degree of deterioration due to the etching process becomes clear.

Ultraviolet is an electromagnetic wave of invisible light having a wavelength of 10 nm or more and 400 nm or less, that is, shorter than visible light and longer than soft X-rays. The wavelength of the ultraviolet-ray used for deterioration determination is preferable at the point which shows high luminous efficiency of 200 nm or more and 400 nm or less.

From the above, the molded body or the sintered body made of the corrosion-resistant material according to the present invention is a semiconductor manufacturing apparatus or a container as a constituent member thereof, specifically, a container such as a vacuum chamber in an etching apparatus, and a sample stand, chuck, and wafer in the container. By manufacturing a holding material (ring plate), a discharge substrate (etching plate), a focus ring, an etching gas supply port, or the like, or by forming a corrosion resistant material according to the present invention on the surface of a semiconductor manufacturing apparatus or a component thereof, a semiconductor A location of deterioration of dry etching in a manufacturing apparatus can be determined and detected. Before using the molded body or sintered body or film made of the corrosion-resistant material according to the present invention, it is preferable that the surface roughness Ra is 20 µm or less because it is easy to determine the degree of deterioration due to the etching process, and it is 10 µm or less more preferably. The surface roughness can be measured by the method described in Examples to be described later.

[Example]

Hereinafter, the present invention will be described in more detail by way of Examples. However, the scope of the present invention is not limited to these examples. In addition, in the following Examples and Comparative Examples, the characteristic specific surface area (SSA, m 2 /g) and the average particle diameter (D50, µm) of the obtained powder were measured as follows.

[Specific Surface Area]

It was measured by the BET one-point method using a fully automatic specific surface area meter Macsorb model-1201 manufactured by Muntech Corporation. The gas used was nitrogen-helium mixed gas (nitrogen 30 vol%).

[Average particle diameter]

Measured with Microtrac HRA manufactured by Nikkiso Co., Ltd. At the time of measurement, 0.2 mass % sodium hexametaphosphate aqueous solution was used as a dispersion medium, and the sample (granule) was added to the chamber of the sample circulator of Microtrac HRA until the apparatus determined that it was an appropriate concentration.

[Example 1]

70 L of pure water and 25 L of 80 mass % acetic acid aqueous solution were mixed, 99 kg of yttrium oxide and 1 kg of europium oxide were thrown in in the liquid mixture, it heated to 90 degreeC, and it was set as the solution. Thereafter, the solution was heated to 100°C and concentrated until the solution reached 65 L. After concentration, the solution was cooled to precipitate a mixed acetate comprising yttrium acetate and europium acetate. The precipitate was dehydrated in a centrifugal separator, and the dehydrated product was calcined in an atmospheric atmosphere at 600°C for 24 hours to obtain europium-containing yttrium oxide.

Pure water was added to the obtained oxide to make a slurry of 1400 g/L, and pulverization was performed using a ball mill until D50 was set to 0.1 µm to 1 µm. The obtained pulverized slurry was granulated and dried using a spray dryer (manufactured by Okawara Kagogi Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were made as follows.

·Slurry feed rate: 300mL/min

・Atomizer rotation speed: 20000min ^-1

·Inlet temperature: 250℃

The obtained granulated material was placed in an alumina container and baked in an electric furnace under an atmospheric atmosphere to obtain granulated granules. The calcination temperature was 1000°C, and the calcination time was 12 hours. In this way, the target corrosion-resistant material was obtained.

[Example 2]

70 L of pure water and 25 L of 80 mass % acetic acid aqueous solution were mixed, 97 kg of yttrium oxide and 3 kg of europium oxide were thrown in in the liquid mixture, it heated to 90 degreeC, and it was set as the solution. Thereafter, the solution was heated to 100°C and concentrated until the solution reached 65 L. After concentration, the solution was cooled to precipitate a mixed acetate comprising yttrium acetate and europium acetate. The precipitate was dehydrated in a centrifugal separator, and the dehydrated product was calcined in an atmospheric atmosphere at 600°C for 24 hours to obtain europium-containing yttrium oxide.

Pure water was added to the obtained oxide to make a slurry of 1400 g/L, and pulverization was performed using a ball mill until D50 was set to 0.1 µm to 1 µm. The obtained pulverized slurry was granulated and dried using a spray dryer (manufactured by Okawara Kagogi Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were made as follows.

·Slurry feed rate: 300mL/min

・Atomizer rotation speed: 20000min ^-1

·Inlet temperature: 250℃

The obtained granulated material was placed in an alumina container and baked in an electric furnace under an atmospheric atmosphere to obtain granulated granules. The calcination temperature was 1000°C, and the calcination time was 12 hours. In this way, the target corrosion-resistant material was obtained.

[Example 3]

70 L of pure water and 25 L of 80 mass % acetic acid aqueous solution were mixed, 99 kg of yttrium oxide and 1 kg of europium oxide were thrown in in the liquid mixture, it heated to 90 degreeC, and it was set as the solution. Thereafter, the solution was heated to 100°C and concentrated until the solution reached 65 L. After concentration, the solution was cooled to precipitate a mixed acetate comprising yttrium acetate and europium acetate. The precipitate was dehydrated in a centrifugal separator, and the dehydrated product was calcined in an atmospheric atmosphere at 600°C for 24 hours to obtain europium-containing yttrium oxide.

Pure water was added to the obtained oxide to make a slurry of 1400 g/L, and pulverization was performed using a ball mill until D50 was set to 0.1 µm to 1 µm. The obtained pulverized slurry was granulated and dried using a spray dryer (manufactured by Okawara Kagogi Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were made as follows.

·Slurry feed rate: 300mL/min

・Atomizer rotation speed: 20000min ^-1

·Inlet temperature: 250℃

The obtained granulated material was placed in an alumina container and baked in an electric furnace under an atmospheric atmosphere to obtain granulated granules. The calcination temperature was 1600°C, and the calcination time was 12 hours. In this way, the target corrosion-resistant material was obtained.

[Example 4]

70 L of pure water and 25 L of 80 mass % acetic acid aqueous solution were mixed, 95.5 kg of yttrium oxide and 4.5 kg of europium oxide were thrown in in the liquid mixture, it heated to 90 degreeC, and it was set as the solution. Thereafter, the solution was heated to 100°C and concentrated until the solution reached 65 L. After concentration, the solution was cooled to precipitate a mixed acetate comprising yttrium acetate and europium acetate. The precipitate was dehydrated in a centrifugal separator, and the dehydrated product was calcined in an atmospheric atmosphere at 600°C for 24 hours to obtain europium-containing yttrium oxide.

Pure water was added to the obtained oxide to make a slurry of 1400 g/L, and pulverization was performed using a ball mill until D50 was set to 0.1 µm to 1 µm. The obtained pulverized slurry was granulated and dried using a spray dryer (manufactured by Okawara Kagogi Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were made as follows.

·Slurry feed rate: 300mL/min

・Atomizer rotation speed: 20000min ^-1

·Inlet temperature: 250℃

The obtained granulated material was placed in an alumina container and baked in an electric furnace under an atmospheric atmosphere to obtain granulated granules. The calcination temperature was 1400°C, and the calcination time was 12 hours. In this way, the target corrosion-resistant material was obtained.

[Example 5]

70 L of pure water and 25 L of 80 mass % acetic acid aqueous solution were mixed, 99 kg of yttrium oxide and 1 kg of europium oxide were thrown in in the liquid mixture, it heated to 90 degreeC, and it was set as the solution. Thereafter, the solution was heated to 100°C and concentrated until the solution reached 65 L. After concentration, the solution was cooled to precipitate a mixed acetate comprising yttrium acetate and europium acetate. The precipitate was dehydrated in a centrifugal separator, and the dehydrated product was calcined in an atmospheric atmosphere at 600°C for 24 hours to obtain europium-containing yttrium oxide.

Pure water was added to the obtained oxide to make a slurry of 1400 g/L, and pulverization was performed using a ball mill until D50 was set to 0.1 µm to 1 µm. The obtained pulverized slurry was granulated and dried using a spray dryer (manufactured by Okawara Kagogi Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were made as follows.

·Slurry feed rate: 300mL/min

・Atomizer rotation speed: 10000min ^-1

·Inlet temperature: 250℃

The obtained granulated material was placed in an alumina container and baked in an electric furnace under an atmospheric atmosphere to obtain granulated granules. The calcination temperature was set to 800°C, and the calcination time was set to 12 hours. In this way, the target corrosion-resistant material was obtained.

[Example 6]

99 kg of yttrium oxide powder and 1 kg of europium oxide powder were dissolved in 333 L of a concentration 60 mass % nitric acid aqueous solution, and it was set as the solution with a density|concentration of 300 g/L. 105 kg of hydrofluoric acid aqueous solution having a concentration of 50% was added to the obtained solution to obtain a precipitate. Thereafter, pure water was washed and dehydrated using a gravity filter, and then dried at 150° C. for 24 hours. The obtained dried product was calcined at 900 DEG C for 24 hours in an air atmosphere to obtain europium-containing yttrium fluoride.

Pure water was added to the obtained fluoride to make a slurry of 1400 g/L, and pulverization was performed using a ball mill until D50 became 0.1 µm to 1 µm. The obtained pulverized slurry was granulated and dried using a spray dryer (manufactured by Okawara Kagogi Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were made as follows.

·Slurry feed rate: 300mL/min

・Atomizer rotation speed: 20000min ^-1

·Inlet temperature: 250℃

The obtained granulated material was placed in an alumina container and baked in an electric furnace under an atmospheric atmosphere to obtain granulated granules. The calcination temperature was 550°C, and the calcination time was 12 hours. In this way, the target corrosion-resistant material was obtained.

[Example 7]

70 L of pure water and 25 L of 80 mass % acetic acid aqueous solution were mixed, 99 kg of yttrium oxide and 1 kg of europium oxide were thrown in in the liquid mixture, it heated to 90 degreeC, and it was set as the solution. Thereafter, the solution was heated to 100°C and concentrated until the solution reached 65 L. After concentration, the solution was cooled to precipitate a mixed acetate comprising yttrium acetate and europium acetate. The precipitate was dehydrated in a centrifugal separator, and the dehydrated product was calcined in an atmospheric atmosphere at 600°C for 24 hours to obtain europium-containing yttrium oxide.

Pure water was added to the obtained oxide, it was set as 70 g/L suspension, and 35 kg of 50 mass % hydrofluoric acid aqueous solution was added, stirring at the speed|rate of 60 rpm. After stirring at 30 to 40 DEG C for 24 hours, dehydration was performed using a gravity filter, and the obtained dehydrated product was calcined in an atmospheric atmosphere at 600 DEG C for 24 hours to obtain yttrium oxyfluoride containing yttrium and europium.

Pure water was added to the obtained oxyfluoride to make a slurry of 1400 g/L, and pulverization was performed using a ball mill until D50 was set to 0.1 µm to 1 µm. The obtained pulverized slurry was granulated and dried using a spray dryer (manufactured by Okawara Kagogi Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were made as follows.

·Slurry feed rate: 300mL/min

・Atomizer rotation speed: 20000min ^-1

·Inlet temperature: 250℃

The obtained granulated material was placed in an alumina container and baked in an electric furnace under an atmospheric atmosphere to obtain granulated granules. The calcination temperature was 700°C, and the calcination time was 12 hours. In this way, the target corrosion-resistant material was obtained.

[Example 8]

56.5 kg of yttrium oxide powder, 0.6 kg of europium oxide powder, and 43.0 kg of aluminum oxide powder were mixed, 100 kg of pure water was added, and it was set as the slurry with a density|concentration of 50 mass %. The obtained slurry was wet-pulverized until it became 0.3 micrometer using Dynomyl KD-45H by the Willy A Bacofen company. The slurry containing the pulverized particles was granulated and dried using a spray dryer (manufactured by Okawara Kagogi Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were made as follows.

·Slurry feed rate: 300mL/min

・Atomizer rotation speed: 10000min ^-1

·Inlet temperature: 250℃

The obtained granulated material was placed in an alumina container and baked in an electric furnace under an atmospheric atmosphere to obtain granulated granules. The calcination temperature was 1400°C, and the calcination time was 5 hours. In this way, the target corrosion-resistant material was obtained.

[Example 9]

64.6 kg of yttrium oxide powder, 0.65 kg of europium oxide powder, and 34.7 kg of silicon dioxide powder were mixed, 100 kg of pure water was added, and it was set as the slurry with a density|concentration of 50 mass %. The obtained slurry was wet-pulverized until it became 0.3 micrometer using Dynomyl KD-20L by the Willy A Bacofen company. The slurry containing the pulverized particles was granulated and dried using a spray dryer (manufactured by Okawara Kagogi Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were made as follows.

·Slurry feed rate: 300mL/min

・Atomizer rotation speed: 10000min ^-1

·Inlet temperature: 250℃

The obtained granulated material was placed in an alumina container and baked in an electric furnace under an atmospheric atmosphere to obtain granulated granules. The calcination temperature was 1400°C, and the calcination time was 12 hours. In this way, the target corrosion-resistant material was obtained.

[Example 10]

70 L of pure water and 25 L of 80 mass % acetic acid aqueous solution were mixed, 99 kg of yttrium oxide and 1 kg of terbium oxide were thrown in in the liquid mixture, it heated to 90 degreeC, and it was set as the solution. Thereafter, the solution was heated to 100°C and concentrated until the solution reached 65 L. After concentration, the solution was cooled to precipitate a mixed acetate consisting of yttrium acetate and terbium acetate. The precipitate was dehydrated in a centrifugal separator, and the dehydrated product was calcined in an atmospheric atmosphere at 600° C. for 24 hours to obtain terbium-containing yttrium oxide.

Pure water was added to the obtained oxide to make a slurry of 1400 g/L, and pulverization was performed using a ball mill until D50 was set to 0.1 µm to 1 µm. The obtained pulverized slurry was granulated and dried using a spray dryer (manufactured by Okawara Kagogi Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were made as follows.

·Slurry feed rate: 300mL/min

・Atomizer rotation speed: 17500min ^-1

·Inlet temperature: 250℃

The obtained granulated material was placed in an alumina container and baked in an electric furnace under an atmospheric atmosphere to obtain granulated granules. The calcination temperature was 1400°C, and the calcination time was 12 hours. In this way, the target corrosion-resistant material was obtained.

[Example 11]

70 L of pure water and 25 L of 80 mass % acetic acid aqueous solution were mixed, 99.98 kg of yttrium oxide and 0.02 kg of europium oxide were thrown in in the liquid mixture, it heated to 90 degreeC, and it was set as the solution. Thereafter, the solution was heated to 100°C and concentrated until the solution reached 65 L. After concentration, the solution was cooled to precipitate a mixed acetate comprising yttrium acetate and europium acetate. The precipitate was dehydrated in a centrifugal separator, and the dehydrated product was calcined in an atmospheric atmosphere at 600°C for 24 hours to obtain europium-containing yttrium oxide.

Pure water was added to the obtained oxide to make a slurry of 1400 g/L, and pulverization was performed using a ball mill until D50 was set to 0.1 µm to 1 µm. The obtained pulverized slurry was granulated and dried using a spray dryer (manufactured by Okawara Kagogi Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were made as follows.

·Slurry feed rate: 300mL/min

・Atomizer rotation speed: 20000min ^-1

·Inlet temperature: 250℃

The obtained granulated material was placed in an alumina container and baked in an electric furnace under an atmospheric atmosphere to obtain granulated granules. The calcination temperature was 1000°C, and the calcination time was 12 hours. In this way, the target corrosion-resistant material was obtained.

[Example 12]

70 L of pure water and 25 L of 80 mass % acetic acid aqueous solution were mixed, 99 kg of yttrium oxide and 1 kg of europium oxide were thrown in in the liquid mixture, it heated to 90 degreeC, and it was set as the solution. Thereafter, the solution was heated to 100°C and concentrated until the solution reached 65 L. After concentration, the solution was cooled to precipitate a mixed acetate comprising yttrium acetate and europium acetate. The precipitate was dehydrated in a centrifugal separator, and the dehydrated product was calcined in an atmospheric atmosphere at 600°C for 24 hours to obtain europium-containing yttrium oxide.

Pure water was added to the obtained oxide to make a slurry of 1400 g/L, and pulverization was performed using a ball mill until D50 was set to 0.1 µm to 1 µm. The obtained pulverized slurry was granulated and dried using a spray dryer (manufactured by Okawara Kagogi Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were made as follows.

·Slurry feed rate: 300mL/min

・Atomizer rotation speed: 20000min ^-1

·Inlet temperature: 250℃

The obtained granulated material was placed in an alumina container and baked in an electric furnace under an atmospheric atmosphere to obtain granulated granules. The calcination temperature was 600°C, and the calcination time was 12 hours. In this way, the target corrosion-resistant material was obtained.

[Comparative Example 1]

70 L of pure water and 25 L of 80 mass % acetic acid aqueous solution were mixed, 100 kg of yttrium oxide was thrown into the liquid mixture, it heated to 90 degreeC, and it was set as the solution. Thereafter, the solution was heated to 100°C and concentrated until the solution reached 65 L. After concentration, the solution was cooled to precipitate an acetate consisting of yttrium acetate. The precipitate was dehydrated in a centrifugal separator, and the dehydrated product was calcined in an atmospheric atmosphere at 600°C for 24 hours to obtain yttrium oxide.

Pure water was added to the obtained oxide to make a slurry of 1400 g/L, and pulverization was performed using a ball mill until D50 was set to 0.1 µm to 1 µm. The obtained pulverized slurry was granulated and dried using a spray dryer (manufactured by Okawara Kagogi Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were made as follows.

·Slurry feed rate: 300mL/min

・Atomizer rotation speed: 20000min ^-1

·Inlet temperature: 250℃

The obtained granulated material was placed in an alumina container and baked in an electric furnace under an atmospheric atmosphere to obtain granulated granules. The calcination temperature was 1000°C, and the calcination time was 12 hours. In this way, the target corrosion-resistant material was obtained.

[Comparative Example 2]

70 L of pure water and 25 L of 80 mass % acetic acid aqueous solution were mixed, 100 kg of europium oxide was thrown in in the liquid mixture, it heated to 90 degreeC, and it was set as the solution. Thereafter, the solution was heated to 100°C and concentrated until the solution reached 65 L. After concentration, the solution was cooled, and acetate composed of europium acetate was deposited. The precipitate was dehydrated in a centrifugal separator, and the dehydrated product was calcined in an atmospheric atmosphere at 600° C. for 24 hours to obtain europium oxide.

Pure water was added to the obtained oxide to make a slurry of 1400 g/L, and pulverization was performed using a ball mill until D50 was set to 0.1 µm to 1 µm. The obtained pulverized slurry was granulated and dried using a spray dryer (manufactured by Okawara Kagogi Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were made as follows.

·Slurry feed rate: 300mL/min

・Atomizer rotation speed: 20000min ^-1

·Inlet temperature: 250℃

The obtained granulated material was placed in an alumina container and baked in an electric furnace under an atmospheric atmosphere to obtain granulated granules. The calcination temperature was 1000°C, and the calcination time was 12 hours. In this way, the target corrosion-resistant material was obtained.

[Composition of base material and content rate of luminescent ability-imparting elements]

For the powdery corrosion-resistant material obtained in each Example and Comparative Example, 50 g is taken, put in an agate mortar, ethanol in an amount to completely immerse the powder is added dropwise, and pulverized by hand with a pestle for 10 minutes, then dried, and the size of the eye The under sieve of 250 μm or less was subjected to X-ray diffraction measurement and fluorescence X-ray analysis.

The composition of the base material described in each Example and Comparative Example was analyzed under the following conditions using an X-ray diffraction apparatus Ultima IV manufactured by Rigaku Corporation.

(X-ray diffraction measurement conditions)

Source: CuKα radiation

Tube voltage: 40kV

Tube current: 40mA

Scan speed: 2 degrees/min

Step: 0.02 degrees

Scan range: 2θ = 10 degrees to 90 degrees

A wavelength dispersion type fluorescent X-ray analyzer ZSX Primus II manufactured by Rigaku Corporation was used for analysis of the content of the luminescent ability-imparting element of the powder described in each Example. The measurement was carried out under the following conditions, and the obtained data was subjected to Scan Quant X analysis to obtain the content of the luminescent ability-imparting element contained in the powder.

For the powder described in Comparative Example 1, a luminescent ability imparting element (rare earth element contributing to luminescence) was analyzed under the following measurement conditions, and it was confirmed that it was less than the lower limit of detection.

For the powder described in Comparative Example 2, rare earth elements excluding the base material were analyzed under the following measurement conditions, and after confirming that it was less than the lower limit of detection, the ratio of the luminescent ability imparting element was calculated from the composition identified by X-ray diffraction measurement.

(Fluorescent X-ray measurement conditions)

[Conditions here]

Target: Rh

Tube voltage: 50kV

Tube current: 60mA

[Scan Conditions]

Start Angle: 5.000deg

End angle: 90.000deg

Step: 0.02deg

Speed: 30deg/min

[Optical Conditions]

Attenuator: 1/1

Slit: S2

Spectral Crystal: LiF (200)

Detector: SC

For the corrosion-resistant materials obtained in each Example, when X-ray diffraction measurement using Cu-Kα rays was performed, the peak of the maximum intensity observed at 2θ = 10 degrees to 90 degrees was the compound described in the “base material” section of Table 1 was confirmed to be of In the X-ray diffraction measurement using Cu-Kα ray, the corrosion-resistant material obtained in each Example was confirmed to be a single phase of the compound described in the section of "Base material" in Table 1.

[Powder luminescence properties]

In addition, the powdery corrosion-resistant materials obtained in Examples and Comparative Examples except for Example 10 were irradiated with powder emission wavelength and intensity by the following method, and evaluated according to the following evaluation criteria.

Measuring method of powder emission wavelength: Powder was uniformly filled in a powder measuring cell dedicated to a fluorescence spectrophotometer F-7000 manufactured by Hitachi High Technologies, and the emission wavelength was evaluated under the conditions described below. For the emission wavelength, the wavelength of the peak of the observed waveform was read among the following observation wavelengths. In the evaluation of the emission characteristics, in order to prevent secondary light of excitation light from entering the detector, a long-pass filter for cutting a wavelength of 300 nm or less was provided between the sample and the second diffraction grating.

[Light Emitting Characteristics]

・Apparatus: F-7000 fluorescence spectrophotometer manufactured by Hitachi High-Technologies

・Excitation wavelength: 254nm

Observation wavelength: 600nm to 630nm

·Photoreal voltage: 400 volts

Measuring method of powder emission intensity: In a dark room completely blocked from light from the outside, with respect to the cell filled with the powder provided for the above-mentioned wavelength measurement, using an iuch HANDY UV LAMP, the distance between the cell-lamp is 50 mm, , UV rays having a wavelength of 254 nm were irradiated with an illuminance of 614 μw/cm 2 , and the degree of luminescence confirmed visually was classified according to the following criteria.

(double-circle): strong light emission was confirmed.

(circle): Weak light emission was confirmed.

(triangle|delta): Although light emission was confirmed, it was very weak.

x: Light emission could not be confirmed at all.

About Example 10, the powder emission wavelength and intensity were investigated by the following method, and the following evaluation criteria evaluated.

Measuring method of powder emission wavelength: Powder was uniformly filled in a powder measuring cell dedicated to a fluorescence spectrophotometer F-7000 manufactured by Hitachi High Technologies, and the emission wavelength was evaluated under the conditions described below. For the emission wavelength, the wavelength of the peak of the observed waveform was read among the following observation wavelengths. In the evaluation of the emission characteristics, in order to prevent secondary light of excitation light from entering the detector, a long-pass filter for cutting a wavelength of 300 nm or less was provided between the sample and the second diffraction grating.

[Light Emitting Characteristics]

・Apparatus: F-7000 fluorescence spectrophotometer manufactured by Hitachi High-Technologies

・Excitation wavelength: 254nm

Observation wavelength: 520nm to 560nm

·Photoreal voltage: 400 volts

Measuring method of powder emission intensity: In a dark room completely blocked from light from the outside, with respect to the cell filled with the powder provided for the above-mentioned wavelength measurement, using an iuch HANDY UV LAMP, the distance between the cell-lamp is 50 mm, , UV rays having a wavelength of 254 nm were irradiated with an illuminance of 614 μw/cm 2 , and the degree of luminescence confirmed visually was classified according to the following criteria.

(double-circle): strong light emission was confirmed.

(circle): Weak light emission was confirmed.

(triangle|delta): Although light emission was confirmed, it was very weak.

x: Light emission could not be confirmed at all.

[Light emission characteristics before and after acid exposure]

[Example 1] to [Example 9], [Example 11], [Example 12], [Comparative Example 1] and [Comparative Example 2] for the corrosion-resistant material obtained by the method described in the following procedure Accordingly, as a model test for evaluation of deterioration due to etching gas in the dry etching process, the acid exposure method immersed in an aqueous hydrofluoric acid solution was used to evaluate whether corrosion resistance deterioration caused by halogen elements was identified by light emission.

The powder was put into a molding die having a diameter of φ20 mm, and was formed into a molded body by uniaxial molding by pressurization of 3 tons for 20 seconds, and then fired at 1500°C in an atmospheric atmosphere. The surface of the fired molded body was smoothed until Ra was 0.1 µm or less using a single-sided polishing machine equipped with a high-precision mirror polishing machine 15B facing device manufactured by Nanotech Machines. About the smoothed surface, Ra was measured using Mitsutoyo's stylus type surface roughness meter SJ-210, and luminescence properties were evaluated under the conditions described below using a fluorescence spectrophotometer F-7000 manufactured by Hitachi High-Technologies. In addition, when evaluating the emission characteristics, in order to prevent secondary light of excitation light from entering the detector, a long-pass filter that cuts a wavelength of 300 nm or less was installed between the sample and the second diffraction grating. Then, the molded object was immersed in 48 mass % hydrofluoric acid aqueous solution for 168 hours, and the corrosion resistance treatment by a halogen element was performed. After immersion, the molded article was dried, and Ra and luminescence properties were measured by the same evaluation method as before immersion.

[Light Emitting Characteristics]

The emission wavelength and the height of the emission peak were measured under the following conditions.

・Apparatus: F-7000 fluorescence spectrophotometer manufactured by Hitachi High-Technologies

・Excitation wavelength: 254nm

Observation wavelength: 600nm to 630nm

·Photoreal voltage: 275 volts

Acid exposure method in which the corrosion-resistant material obtained by the method described in the above-mentioned [Example 10] is immersed in an aqueous hydrofluoric acid solution as a model of deterioration of contamination by etching gas in the dry etching process by following the procedure shown below By this, the discrimination by light emission of corrosion resistance deterioration by a halogen element was evaluated.

The powder was put into a molding die having a diameter of φ20 mm, and was formed into a molded body by uniaxial molding by pressurization of 3 tons for 20 seconds, and then fired at 1500°C in an atmospheric atmosphere. The surface of the fired molded body was smoothed using a single-sided polishing machine equipped with a high-precision mirror polishing machine 15B facing device manufactured by Nanotech Machines. About the smoothed surface, Ra was measured using the Mitsutoyo stylus type surface roughness meter SJ-210, and the luminescent property was evaluated under the conditions demonstrated below using the Hitachi High-Technologies fluorescence spectrophotometer F-7000. In the evaluation of the emission characteristics, in order to prevent secondary light of excitation light from entering the detector, a long-pass filter for cutting a wavelength of 300 nm or less was provided between the sample and the second diffraction grating. Then, the molded object was immersed in 48 mass % hydrofluoric acid aqueous solution for 168 hours, and the corrosion resistance treatment by a halogen element was performed. After immersion, the molded article was dried, and Ra and luminescence properties were measured by the same evaluation method as before immersion.

[Light Emitting Characteristics]

The emission wavelength and the height of the emission peak were measured under the following conditions.

・Apparatus: F-7000 fluorescence spectrophotometer manufactured by Hitachi High-Technologies

・Excitation wavelength: 254nm

Observation wavelength: 520nm to 560nm

·Photoreal voltage: 275 volts

As described above, in the corrosion-resistant materials of the present invention obtained in Examples 1 to 12, light emission of visible light by ultraviolet irradiation was confirmed, and before and after the acid exposure test, the peak height of the emission intensity increased, and the halogen element deterioration was detected. However, since Comparative Example 1 did not contain a luminescent ability imparting element, there was no visible light emission by ultraviolet irradiation, and the acid exposure test could not be evaluated. In Comparative Example 2, since the base material itself was europium oxide and europium was not activated, the visible light emission by ultraviolet irradiation was weak, and the acid exposure test could not be evaluated. Thus, it turned out that the corrosion-resistant material which concerns on this invention is a material excellent in detecting the state of deterioration in an etching process.

Claims (16)

A corrosion-resistant material for semiconductor manufacturing devices, comprising: a base material having dry etching resistance; and an element that imparts to the base material the ability to emit visible light by irradiation with ultraviolet light. The corrosion-resistant material for a semiconductor manufacturing apparatus according to claim 1, wherein the base material is an oxide, halide or oxyhalide containing a rare earth element. The corrosion-resistant material for a semiconductor manufacturing apparatus according to claim 2, wherein the rare earth element comprises yttrium or gadolinium. The corrosion-resistant material for a semiconductor manufacturing apparatus according to claim 3, wherein the oxide containing a rare earth element is at least one selected from yttria, yttrium aluminate, gadolinium aluminate, yttrium silicate and gadolinium silicate. The corrosion-resistant material for a semiconductor manufacturing apparatus according to claim 3, wherein the halide containing a rare earth element is at least one selected from the group consisting of yttrium fluoride, gadolinium fluoride, yttrium chloride and gadolinium chloride. The corrosion-resistant material for a semiconductor manufacturing device according to claim 3, wherein the oxyhalide containing a rare earth element is at least one selected from the group consisting of yttrium oxyfluoride, gadolinium oxyfluoride, yttrium oxychloride and gadolinium oxychloride. The semiconductor manufacturing apparatus according to any one of claims 1 to 6, wherein the element that gives the base material the ability to emit visible light by irradiation with ultraviolet light is contained in an amount of 0.05% by mass or more and 10% by mass or less in the corrosion-resistant material. For corrosion-resistant materials. 8. The element according to any one of claims 1 to 7, wherein the element imparting the luminous ability of visible light by the ultraviolet irradiation to the base material is europium, terbium, neodymium, erbium, dysprosium, samarium, thulium, praseodymium and ytterbium The corrosion-resistant material for semiconductor manufacturing apparatuses which is at least 1 sort(s) selected. The corrosion-resistant material for a semiconductor manufacturing apparatus according to claim 8, wherein the element that imparts to the base material the ability to emit visible light by the ultraviolet irradiation is europium or terbium. The corrosion-resistant material for a semiconductor manufacturing apparatus according to any one of claims 1 to 9, wherein the corrosion-resistant material is a powder. 10. The corrosion-resistant material for a semiconductor manufacturing apparatus according to any one of claims 1 to 9, wherein the corrosion-resistant material is a powdered compact or sintered compact or film. The corrosion-resistant material for a semiconductor manufacturing apparatus according to claim 10, wherein the powder has a specific surface area of 0.1 m 2 /g or more and 30 m 2 /g or less. The corrosion-resistant material for a semiconductor manufacturing apparatus according to claim 10 or 12, wherein the powder has an average particle diameter of 10 µm or more and 100 µm or less. The corrosion-resistant material for a semiconductor manufacturing apparatus according to any one of claims 1 to 13, which is used for a dry etching apparatus for a semiconductor, a constituent member thereof, or a film constituting a surface thereof. A method for manufacturing a semiconductor manufacturing apparatus or a component thereof,
By molding or sintering a base material having dry etching resistance and a corrosion-resistant material containing an element that imparts visible light emitting ability to the base material by ultraviolet irradiation, a semiconductor manufacturing apparatus or a component thereof is manufactured, or a semiconductor manufacturing apparatus or A manufacturing method of forming the corrosion-resistant material into a film on the surface of a base material of the constituent member. A method for detecting a location deteriorated by an etching gas in a semiconductor manufacturing apparatus,
By molding or sintering a base material having dry etching resistance and a corrosion-resistant material containing an element that imparts visible light emitting ability to the base material by ultraviolet irradiation, a semiconductor manufacturing apparatus or a component thereof is manufactured, or a semiconductor manufacturing apparatus or Forming the corrosion-resistant material into a film on the surface of the base material of the constituent member,
After dry etching of a semiconductor using a semiconductor manufacturing apparatus or its structural member, the said semiconductor manufacturing apparatus or its structural member is irradiated with an ultraviolet-ray, The detection method of determining the location where visible light emits light.