JP2021102546A - Corrosion-resistant material for semiconductor-fabricating apparatus - Google Patents

Abstract

To provide a material suitable for detecting a damaged spot on a surface of a semiconductor-fabricating apparatus or its component member, the damaged spot being caused due to dry etching, a method for producing the material, and a method for detecting the damaged spot.SOLUTION: 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, wherein: 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 its component member by being formed into a molded body or a sintered body, thereby detecting a damaged spot due to dry etching.SELECTED DRAWING: None

Description

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

In the dry etching step of a semiconductor element, a circuit is usually formed on a semiconductor wafer by plasma discharge while inflowing a corrosive gas such as a halogen-containing gas. At that time, the corrosive gas is not limited to the wafer, but the container (chamber) of the semiconductor manufacturing equipment, the wafer holding material (ring plate), the discharge substrate (etching plate), etc. (hereinafter referred to as “container, etc.”), etching is not desired. It also damages the members and deteriorates the surface of those members to produce floating particles called particles. The particles eventually accumulate on the wafer, causing a short circuit in the circuit and poor etching, which reduces the productivity of the semiconductor device.

Rare earth elements are highly resistant to halogen-containing gases, so high corrosion resistance can be achieved by applying this to the surface of semiconductor etching equipment or by using molded or sintered bodies containing rare earth elements in semiconductor etching equipment. It is known that it can be etched (Patent Documents 1 and 2).

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

JP-A-2002-332559 Japanese Unexamined Patent Publication No. 2003-063883 JP-A-2002-38150 Japanese Unexamined Patent Publication No. 2008-174690

When the conventional corrosion-resistant members described in Patent Documents 1 and 2 are 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 place where the particles are generated and the degree of deterioration, and the deterioration is caused. All potential components had to be replaced on a regular basis. Since the degree of damage differs depending on the member even in the container of the semiconductor manufacturing equipment, if the location where particles are generated and the degree of deterioration can be determined, only the deteriorated member can be replaced without replacing all the members, so that the life of the member can be extended. , It is possible to reduce the replacement cost of members.

Further, Patent Documents 3 and 4 merely describe a light emitting element, which is a phosphor composed of an oxide containing europium and yttrium, and is used as a corrosion resistant material in a container or the like for a semiconductor manufacturing apparatus. No consideration has been given to its use.

As a result of diligent studies to solve the above problems, the present inventor has found that a specific corrosion-resistant material is corroded by halogen-based components to increase the emission intensity. Based on this knowledge, we have found a method that can easily determine the state of deterioration and the location of deterioration of a member by using this corrosion-resistant material in a container or the like of a semiconductor manufacturing apparatus.

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

The present invention is a method for manufacturing a semiconductor manufacturing apparatus or its constituent members.
A semiconductor manufacturing apparatus or a component thereof is manufactured by molding or sintering a corrosion-resistant material containing a base material having dry etching resistance and an element that imparts the ability to emit visible light by ultraviolet irradiation to the base material. Alternatively, the present invention relates to a manufacturing method for forming the corrosion-resistant material on the surface of a base material of a semiconductor manufacturing apparatus or its constituent members.

Further, the present invention is a method for detecting a portion deteriorated by an etching gas in a semiconductor manufacturing apparatus.
A semiconductor manufacturing apparatus or a component thereof can be manufactured by molding or sintering a corrosion-resistant material containing a base material having dry etching resistance and an element that imparts the ability to emit visible light by ultraviolet irradiation to the base material. Alternatively, the corrosion-resistant material is formed on the surface of the base material of the semiconductor manufacturing apparatus or its constituent members.
The present invention relates to a detection method for determining a portion where visible light is emitted by irradiating the semiconductor manufacturing apparatus or its constituent members with ultraviolet rays after performing dry etching of a semiconductor using the semiconductor manufacturing apparatus or its constituent members.

The corrosion-resistant material according to the present invention has a surface roughness that is etched by contacting with an etching gas in a dry etching step to etch a container or the like which is a component of a semiconductor manufacturing apparatus made of the corrosion-resistant material or formed into a film. By increasing the size and thereby increasing the emission intensity from the corrosion-resistant material according to the present invention, it is possible to easily identify the particle generation location. Since the corrosion-resistant material according to the present invention is a material that emits light in the wavelength region of visible light when irradiated with ultraviolet rays, the presence of particles can be easily detected even if the presence of particles is small.

Hereinafter, preferred embodiments of the present invention will be 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 the light emitting ability of visible light to the base material by ultraviolet irradiation.
Here, the base material is a material that is a main material or a base material such as a composite material. The base material according to the present specification preferably means a compound constituting the main phase of the corrosion resistant material.

In the present specification, the base material having dry etching resistance refers to a material that can withstand corrosion by an etching gas containing a halogen element or the like, which is used in a dry etching step in manufacturing 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, and among them, oxides, halides, oxyhalides and the like containing rare earth elements are used. Suitable.

As the rare earth element, yttrium or gadolinium is particularly preferable from the viewpoint of improving dry etching resistance. Here, the dry etching resistance can be evaluated by using the acid exposure method with a halogen acid or the like described in Examples described later.

Examples of the above-mentioned oxide containing a rare earth element include an oxide of a rare earth element and a composite oxide of a rare earth element and another metal element. The oxide containing a 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 viewpoint, the oxide containing a rare earth element _{is particularly preferably at least one selected from yttrium (Y 2} O ₃ ), yttrium aluminate, gadolinium aluminate, yttrium silicate and gadolinium silicate. Examples of yttrium aluminate include Y ₃ Al ₅ O ₁₂ , Y ₄ Al ₂ O _{9 , and Y AlO 3} . Examples of gadolinium aluminate include Gd ₃ Al ₅ O ₁₂ , Gd ₄ Al ₂ O _{9 , and Gd AlO 3} . Examples of yttrium silicate include Y ₂ Si ₂ O ₇ and Y ₂ SiO ₅ . Examples of gadolinium silicate include Gd ₂ Si ₂ O ₇ and Gd ₂ SiO ₅ .

Examples of the halide containing the rare earth element include compounds composed of the rare earth element (Ln) and halogen, and specific examples thereof are fluoride (fluoride) and chloride (chloride) of the rare earth element. From the viewpoint of corrosion resistance, the halide containing a rare earth element is at least one selected from _{yttrium fluoride (YF 3} ), gadolinium fluoride (GdF ₃ ), yttrium chloride (YCl ₃ ) and gadolinium chloride (GdCl _3). Is particularly preferred.

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-O-X may be represented by LnO a} X _b (0.3 ≦ a ≦ 1.7, 0.1 ≦ b ≦ 1.9) from the viewpoint of corrosion resistance and availability. preferable. In particular, from the above viewpoint, in the above formula, 0.35 ≦ a ≦ 1.65 is more preferable, and 0.4 ≦ a ≦ 1.6 is further preferable. Further, 0.2 ≦ b ≦ 1.8 is more preferable, and 0.5 ≦ b ≦ 1.5 is further preferable. Further, from the viewpoint of availability and the like, in the above formula, those satisfying 2.3 ≦ 2a + b ≦ 5.3, particularly 2.35 ≦ 2a + b ≦ 5.1 are preferable, and those satisfying 2a + b = 3 are particularly preferable.

Further, as the oxyhalide containing a rare earth element, from the viewpoint of corrosion resistance, yttrium oxyfluoride (hereinafter, also referred to as “YOF”) and gadolinium oxyfluoride (hereinafter, also referred to as “Gd-OF”). It is at least one selected from yttrium oxychloride (hereinafter also referred to as "YO-Cl") and gadolinium oxychloride (hereinafter also referred to as "Gd-O-Cl"). Especially preferable. Examples of 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 . Examples of yttrium oxychloride include YOCl. Examples of gadolinium oxychloride include GdOCl.

Further, as the base material having dry etching resistance, a compound containing yttrium and fluorine and / or oxygen is preferable from the viewpoint of corrosion resistance, and in particular, yttrium, yttrium aluminate, yttrium silicate, yttrium fluoride and oxyfluoride of yttrium are used. It is even more preferable that it is at least one selected, and above all, 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. It is preferable to have.

The fact that the base material having dry etching resistance is contained in the corrosion-resistant material means that, for example, when the base material is composed of a rare earth element-containing compound, the corrosion-resistant material contains a predetermined amount of the rare earth element. It can be identified by measuring with a line analyzer 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, preferably occupies 35% by mass or more, and occupies 60% by mass or more, as the amount of the rare earth element from the viewpoint of corrosion resistance stability. Is more preferable, and it is more preferable to occupy 65% by mass or more, and it is particularly preferable to occupy 70% by mass or more. Further, in the corrosion-resistant material, the content of the rare earth element, preferably yttrium or gadolinium, preferably occupies 70% by mass or more, preferably 80% by mass or more, as the amount of the rare earth element-containing compound from the viewpoint of corrosion resistance stability. It is particularly preferable to occupy. The upper limit of the content of yttrium or gadolinium in the corrosion-resistant material may be an amount that secures the amount of the luminescent ability-imparting element described later. From the viewpoint of enhancing corrosion resistance, the corrosion-resistant material of the present invention has the maximum intensity peak observed at 2θ = 10 to 90 degrees in yttrium or gadolinium in X-ray diffraction measurement using _{Cu-Kα ray or Cu-Kα 1-ray.} It is preferably an oxide, a halide or an oxyhalide of.

Next, a base material having dry etching resistance of the corrosion-resistant material according to the present invention and an element contained therein that imparts the light emitting ability of visible light by ultraviolet irradiation to the base material will be described.

Examples of the luminescent ability-imparting element include elements that are different from the rare earth elements constituting the base material and belong to lanthanoids among the rare earth elements. Specifically, europium (Eu), terbium (Tb), neodymium (Nd), erbium (Er), dysprosium (Dy), dysprosium (Sm), thulium (Tm), placeodim (Pr) and ytterbium (Yb). ) Is preferred because it is difficult to reduce the corrosion resistance of the base metal. Of these, europium (Eu) or terbium (Tb), which have a high emission intensity, are particularly preferable because they have a high ability to impart light emission to the base material.

It is preferable that the corrosion-resistant material according to the present invention contains the above-mentioned luminescent element-imparting element in an amount of 0.05% by mass or more and 10% by mass or less. When it is set to 0.05% by mass or more, the light emission intensity is increased, and deterioration of the container or the like of the semiconductor manufacturing apparatus described later can be efficiently detected. From this point of view, the amount of the light emitting ability-imparting element in the corrosion-resistant material is more preferably 0.1% by mass or more, and particularly preferably 0.5% by mass or more. In addition, since the element that imparts light emission ability is inferior in dry etching resistance to the base material that has resistance to dry etching, adding the element that imparts light emission ability causes impurity contamination. It is preferable that the luminescent ability-imparting element is 10% by mass or less because it is possible to effectively prevent a decrease in impurity contamination of the container or the like of the semiconductor manufacturing apparatus. From this point of view, it is more preferably 8% by mass or less, and particularly preferably 5% by mass or less. The amount of luminescent element in the corrosion resistant material can be measured by a wavelength dispersive fluorescent X-ray analyzer.

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

In the corrosion-resistant material according to the present invention, it is preferable that the base material and the luminescent element-imparting element are in a solid solution state. For example, when the base material is an oxide, halide, or oxyhalide containing yttrium or gadolinium, a part of yttrium or gadolinium in the base material is replaced with europium in the form of a solid solution. The luminescent element does not emit visible light sufficiently even when irradiated with ultraviolet rays in the form of itself or its single oxide, but is added to the base material, and the ions of the luminescent element are appropriately contained in the base material. By dispersing at a high concentration, it emits strong light when irradiated with ultraviolet rays. For example, in the base material such as yttrium oxide whose luminescent ability is imparted by the addition of europium, its Eu ³⁺ ions emit red light. This is because when the europium element is added to the base material containing yttrium such as yttrium oxide, the europium element is replaced with a part of the yttrium element and activated as ^{Eu 3+ ions.} When it is irradiated with ultraviolet rays, visible light is emitted from ^{Eu 3+ ions.} In the base material to which the luminescent ability is imparted by the 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 irradiation with ultraviolet rays is preferably, for example, 600 nm or more and 620 nm or less, and more preferably 605 nm or more and 615 nm or less. When the corrosion-resistant material of the present invention contains terbium, the wavelength of light emitted by irradiation with ultraviolet rays 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.

Further, the corrosion-resistant material according to the present invention may contain unavoidable impurities in addition to the base material and the luminescent element. Inevitable impurities include impurities contained in oxides, halides or oxyhalides containing rare earth elements as raw materials, compounds containing luminescent elements, and the like, which are mixed in during the production of the corrosion-resistant material. Impurities and the like can be mentioned.

Next, the form of the corrosion-resistant material according to the present invention will be described.
Examples of the form of the corrosion-resistant material according to the present invention include powder. Further, a molded product or a sintered body of the powder, or a film formed by the powder thereof is also mentioned.

The specific surface area of the powdered corrosion-resistant material ^{is preferably 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. Further, when the specific surface area of the corrosion-resistant material is 30 m ² / g or less, the light-emitting intensity of the corrosion-resistant material tends to be high, and the degree of improvement in the light-emitting intensity of the corrosion-resistant material when particles are generated is increased, so that the deteriorated part is further deteriorated. It has the advantage of being able to detect efficiently. 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, and particularly preferably 0.5 m ² / g or more and 18 m ² / g or less. It is preferably 0.5 m ² / g or more and 15 m ² / g or less. The specific surface area is measured by the BET 1-point method, and specifically, it can be measured by the method described in Examples described later. The powder having the above specific surface area may be in the form of granules.

The corrosion-resistant material, which is a powder, preferably has an average particle size of 10 μm or more and 100 μm or less, and more preferably 15 μm or more and 80 μm or less, from the viewpoints of ease of manufacture, fluidity, uniformity at the time of filling, and the like. , 20 μm or more and 60 μm or less is particularly preferable. The average particle size is the integrated volume particle size (D50) at an integrated volume of 50% by volume by a laser diffraction / scattering type particle size distribution measurement 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 corrosion-resistant material, which is a powder, is granules, it is preferable that the average particle size is in the above range because effects such as ease of production, fluidity, and uniformity during filling can be obtained.

Subsequently, a suitable method for producing the corrosion-resistant material according to the present invention will be described.
First, when the base material is a rare earth element-containing oxide, it is preferable to do as follows.

(Manufacturing method A)
A method for producing a corrosion-resistant material for a semiconductor manufacturing apparatus, which comprises a base material having dry etching resistance and an element that imparts visible light emission ability by ultraviolet irradiation to the base material, and the base material is a rare earth element-containing oxide. hand,
The first step A of mixing an aqueous solution containing a weak acid, an oxide of a rare earth element, and an oxide of the luminescent element to prepare a solution.
In the second A step of concentrating the solution obtained in the first A step,
In the third A step, the concentrated solution obtained in the second A step is cooled to precipitate a mixed weak acid salt of a rare earth element and the luminescent element.
A production 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 element.
The present production method further preferably has a fifth A step of pulverizing the oxide obtained in the fourth A step, and further granulates and dries the powder obtained in the fifth A step to obtain a granulated product. 6th A step to obtain and
It is more preferable to have a seventh A step of calcining the granulated product obtained in the sixth A step.

A suitable example of the manufacturing method A will be described.
In the first step A, the weak acid in the aqueous solution containing a weak acid means an acid having a small acid dissociation constant, preferably an acid having a pKa of 1.0 or more at 25 ° C. Here, pKa refers to _{pKa 1.} The pKa is preferably 3.0 or higher. Acids with a pKa of 1.0 or higher include 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, and malein. In addition to organic acids having a carboxylic acid group such as acid and tartaric acid, inorganic acids such as boric acid, hypochlorous acid, hydrogen fluoride and hydrosulfuric acid can be mentioned. Of these, an organic acid having a carboxylic acid group is preferable, and acetic acid is particularly preferable from the viewpoints of both suppressing the manufacturing cost and easily obtaining a corrosion-resistant material having desired physical properties. These can be used alone or in combination of two or more.

The concentration of the weak acid in the mixture obtained in the first step A, which is a mixture of the weak acid, the oxide of the rare earth element, and the oxide of the luminescent element in the aqueous solution containing the weak acid, is 10% by mass or more and 30% by mass or less. This is preferable in that the oxide of the rare earth element and the oxide of the luminescent element are easily dissolved to easily obtain a corrosion-resistant material having desired physical properties and to improve the solubility of the raw material, which is preferably 10% by mass or more and 25% by mass. More preferably, it is less than%.
The amount of the oxide of the rare earth element and the weak acid used for dissolving the oxide of the luminescent element is 60 mol or more of the weak acid with respect to 100 mol of the total of the oxide of the rare earth element and the oxide of the luminescent element. This is preferable in that the oxide of the rare earth element and the oxide of the luminescent element are sufficiently dissolved in the weak acid aqueous solution to facilitate obtaining a corrosion-resistant material having desired physical properties, and the amount is preferably 70 mol or more. Further, 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 oxide of the luminescent element, because it can be produced at low cost.

At the time when the oxide of the rare earth element and the oxide of the luminescent element are dissolved in the weak acid aqueous solution, the weak acid aqueous solution may be heated to room temperature or higher. This is because it is preferable in that the oxide of the rare earth element and the oxide of the luminescent element are sufficiently dissolved in an aqueous solution containing a weak acid to facilitate obtaining a corrosion-resistant material having desired physical properties. The heating temperature at this time is preferably 70 ° C. or higher and 95 ° C. or lower, and more preferably 80 ° C. or higher and 90 ° C. or lower, from the viewpoint of suppressing dissolution efficiency and dissolution residue.

As the oxide of the rare earth element, yttrium oxide (Y ₂ O ₃ ) or gadolinium oxide (Gd ₂ O ₃ ) is preferable. Examples of the oxide of the luminescent ability-imparting element include europium oxide (Eu ₂ O ₃ , Eu O), terbium oxide (Tb ₂ O ₃ , Tb ₄ O ₇ ), neodymium oxide (Nd ₂ O ₃ ), and erbium oxide (Er _2). O ₃ ), _{disprosium oxide (Dy 2} O ₃ ), samarium oxide (Sm ₂ O ₃ , SmO), turium oxide (Tm ₂ O ₃ ), placeodym oxide (Pr ₆ O ₁₁ ) and itterbium oxide (Yb ₂ O) _At least one oxide selected from 3) is preferable. Of these, europium oxide or terbium oxide is more preferable.

Next, in the second A step, the solution obtained in the first A step is concentrated. The concentration method can be heating and / or depressurizing. The degree of concentration is preferably such that the amount of the liquid is 60% by volume to 80% by volume with respect to the initial solution, from the viewpoint of obtaining uniform crystal nuclei, and is 65% by volume to 75% by volume. This is more preferable in that the crystal nuclei become more uniform.

Subsequently, in the third A step, the concentrated solution obtained in the second A step 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 components. Here, when the concentrated solution is cooled, a mixed weak acid salt composed of a weak acid salt of a rare earth element and a weak acid salt of a luminescent ability-imparting element is precipitated.

Then, in the 4A step, when the precipitate obtained in the 3A step is calcined, the powder of the target corrosion resistant material 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 in that the amount of residual organic matter derived from a weak acid can be reduced.

When the firing temperature is 1800 ° C. or lower, a preferable corrosion-resistant material can be easily obtained in terms of production cost, and it is more preferably 1700 ° C. or lower, and further preferably 1600 ° C. or lower. Further, it is easy to obtain a powder of a corrosion-resistant material, which is preferable in terms of luminous efficiency when the firing temperature is 500 ° C. or higher, and more preferably 550 ° C. or higher. The firing time in the above temperature range is preferably 10 hours or more and 50 hours or less, and more preferably 20 hours or more and 40 hours or less from the viewpoint of reducing uneven firing.

The mixed weak acid salt of the precipitated rare earth element weak acid salt and the luminescent element weak acid salt is preferably dehydrated before firing because it can reduce firing unevenness in the firing step. Dehydration can be performed by a conventional method using a centrifuge or the like. Further, the mixed weak acid salt may be washed, dried or the like before firing.

Next, in the case of forming granules, it is preferable to pulverize the oxide powder obtained in the fourth A step in the fifth A step, which is a suitable manufacturing step, to obtain a desired particle size. The pulverization may be performed by either dry pulverization or wet pulverization. In the case of dry crushing, 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 pulverization, it is preferable to carry out by a wet pulverizer using a pulverizing medium such as a spherical shape or a cylindrical shape. Examples of such a crushing device include a ball mill, a vibration mill, and a bead mill, which are medium stirring mills. Examples of the material of the pulverizing medium include zirconia, alumina, silicon nitride, silicon carbide, tungsten carbide, wear-resistant steel and stainless steel. Zirconia may be stabilized by adding a metal oxide. Further, as the dispersion medium for wet pulverization, the same dispersion medium as those listed below can be used as an example of the dispersion medium for the slurry used at the time of granulation by the spray-drying method described later. In the case of wet pulverization, a liquid medium is added to the object to be pulverized before pulverization to obtain a slurry. As the liquid medium, water or various organic solvents can be used alone or in combination of two or more, and the same dispersion medium as in the sixth step 6A described later can be used. Above all, water is preferable in terms of production cost. The pulverization is preferably carried out until D50 is 0.01 μm or more and 2 μm or less in terms of film forming property and moldability, and more preferably 0.02 μm or more and 1.5 μm or less.

In the case of granules, the sixth A step, which is a granulation step, is performed. As the granulation method, a spray-drying method, an extrusion granulation method, a rolling granulation method, or the like can be used, but the spray-drying method has good fluidity of the obtained granulation powder and is applied to the substrate at high pressure. It is preferable because it has high film forming property when pressed. In the spray-drying method, a slurry obtained by dispersing the rare earth element oxide powder obtained above in a dispersion medium is applied to a spray dryer. As the dispersion medium, water or various organic solvents can be used alone or in combination of two or more. Above all, it is preferable to use water, an organic solvent having a solubility in water of 5% by mass or more, or a mixture of the organic solvent and water because a more dense and uniform film can be easily obtained. Here, the organic solvent having a solubility in water of 5% by mass or more includes a solvent that is freely mixed with water. Examples of organic solvents having a solubility in water of 5% by mass or more (including those that are freely mixed with water) include alcohols, ketones, cyclic ethers, formamides, sulfoxides, and the like. Further, the mixing ratio of the organic solvent and water in the mixture of the organic solvent and water having a solubility in water of 5% by mass or more is preferably within the range of the solubility of the organic solvent in water. As the 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 a slurry supply rate of 200 mL / min or more and 400 mL / min or less, preferably 250 mL. More preferably, it is at least / min and at least 350 mL / min. For a rotary atomizer method, it is preferred to terms obtained a uniform granule size with a spray dryer 7500Min ^-1 or more 25000Min ^-1 or less, and more preferably to 10000 min ^-1 or more 22000Min ^-1 or less. The inlet temperature is preferably 150 ° C. or higher and 300 ° C. or lower, and more preferably 180 ° C. or higher and 270 ° C. or lower in terms of obtaining a uniform granule diameter and bulk density.

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

When the firing temperature is 1800 ° C. or lower, a desired corrosion-resistant material powder can be obtained in that contamination of impurities derived from the furnace material can be suppressed, more preferably 1700 ° C. or lower, further preferably 1650 ° C. or lower. .. Further, the temperature of 800 ° C. or higher makes it easy to obtain a desired corrosion-resistant material powder in terms of maintaining the strength of the granules, more preferably 900 ° C. or higher, and further preferably 950 ° C. or higher. 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 in that uneven firing can be reduced.

Next, when the base material is a rare earth element-containing halide, it is preferable to do as follows.
(Manufacturing method B)
A method for producing a corrosion-resistant material for a semiconductor manufacturing apparatus, which comprises a base material having dry etching resistance and an element that imparts visible light emission ability by ultraviolet irradiation to the base material, and the base material is a halide containing a rare earth element. hand,
The first B step of mixing an aqueous solution containing an acid, an oxide of a rare earth element, and an oxide of the luminescent element to prepare a solution.
In the second B step, the hydrohalic acid is added to the solution obtained in the first B step and precipitated.
In the third B step of dehydrating and drying the precipitate obtained in the second B step,
A production 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.
The present production method preferably further includes a fifth B step of pulverizing the halide obtained in the fourth B step.
In the sixth B step, the powder obtained in the fifth B step is granulated and dried to obtain a granulated product.
It is more preferable to have a seventh B step of calcining the granulated product obtained in the sixth B step.

A suitable example of the production method B will be described.
Examples of the acid in the aqueous solution containing the acid in the first step B include nitric acid, oxalic acid, acetic acid, ammine complex, hydrochloric acid and the like. Above all, nitric acid is preferable because it is easily available and can be produced at low cost. Further, the concentration of the acid in the liquid obtained by mixing the aqueous solution containing the acid, the oxide of the rare earth element, and the oxide of the luminescent element is 30% by mass or more from the viewpoint of solubility and safety during handling. It is preferably 80% by mass or less, and more preferably 40% by mass or more and 60% by 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 such that the acid is 100 mol in total of the oxide of the rare earth element and the oxide of the luminescent element. It is preferable that the amount is 500 mol or more because the oxide of the rare earth element and the oxide of the luminescent element are sufficiently dissolved in an aqueous solution containing an acid to facilitate obtaining a corrosion-resistant material having desired physical properties. The above is preferable. Further, 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 oxide of the luminescent element, because 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 oxide described in the above-mentioned production method A.

Next, in the second B step, the hydrohalic acid aqueous solution to be added to the solution obtained in the first B step is used as an aqueous solution having a concentration of 40% by mass or more and 60% by mass or less. However, it is preferable in terms of reactivity with the solution and ensuring safety during handling, and it is preferable to use it as an aqueous solution having a concentration of 45% by mass or more and 55% by mass or less. The amount of the hydrohalic acid used is 2.4 mol or more with respect to 1 mol of the total of the rare earth element and the luminescent element in the solution, and the oxidation of the rare earth element and the luminescent element. It is preferable that a good corrosion-resistant material can be easily obtained by sufficiently reacting with an object to obtain a precipitate having a uniform size, and more preferably 2.7 mol or more. The amount of the hydrohalic acid used is preferably 3.6 mol or less with respect to 1 mol of the total of the rare earth element and the luminescent element in the solution, because the manufacturing cost can be reduced. More preferably, it is 3 mol or less.
The reaction between the solution and the hydrohalic acid is carried out at 30 ° C. or higher and 60 ° C. or lower in that a preferable corrosion-resistant material can be easily obtained in that a rare earth element can be sufficiently reacted to obtain a precipitate in a high yield. It is preferable to carry out at 35 ° C. or higher and 55 ° C. or lower.

The precipitate obtained in the second B step is dried in the third B step. The precipitate is preferably washed with a liquid medium such as water and then dried. The drying may be carried out in an inert atmosphere such as nitrogen or argon, and an oxygen-containing atmosphere is preferable in that the precipitate after washing is efficiently dried. When the drying temperature is 200 ° C. or lower, it is easy to obtain a preferable corrosion-resistant material in that uniform firing is possible in the subsequent firing step, more preferably 180 ° C. or lower, and further preferably 160 ° C. or lower. preferable. The drying temperature is preferably 100 ° C. or higher because it can suppress drying efficiency and residual water, and more preferably 120 ° C. or higher. The drying time in the above temperature range is preferably 10 hours or more and 30 hours or less, and more preferably 15 hours or more and 25 hours or less.

Subsequently, in the 4B step, the dried product obtained in the 3B step is calcined to obtain a powder of a corrosion-resistant material as a rare earth element halide containing a luminescent ability-imparting element. 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 in that the amount of residual organic matter derived from a weak acid can be reduced.

When the firing temperature is 1000 ° C. or lower, a preferable corrosion-resistant material can be obtained in that excessive oxidation can be suppressed, more preferably 980 ° C. or lower, and further preferably 950 ° C. or lower. Further, it is easy to obtain a corrosion-resistant material which is preferable in terms of increasing crystallinity when the firing temperature is 600 ° C. or higher, and more preferably 700 ° C. or higher. The firing time in the above temperature range is preferably 10 hours or more and 50 hours or less, and more preferably 20 hours or more and 40 hours or less.

Next, in the fifth B step, which is a suitable manufacturing step, it is preferable to crush the corrosion-resistant material powder obtained in the fourth B step, and to produce granules by the sixth B step and the seventh B step, if necessary. ..
The operation contents in the 5th to 7B steps described above are the same as the operation contents in the 5A to 7A steps of the manufacturing method A. However, the firing temperature in the 7A step is preferably 400 ° C. or higher and 800 ° C. or lower in terms of successfully obtaining a rare earth element halide containing a luminescent element, and more preferably 500 ° C. or higher and 700 ° C. or lower. ..

Further, when the base material is a rare earth element-containing oxyhalide, it is preferable to do as follows.
(Manufacturing method C)
A method for producing a corrosion-resistant material for a semiconductor manufacturing apparatus, which comprises a base material having dry etching resistance and an element that imparts visible light emission ability by ultraviolet irradiation to the base material, and the base material is a rare earth element-containing oxyhalide. There,
The first C step of mixing an aqueous solution containing a weak acid, an oxide of a rare earth element, and an oxide of the luminescent element to prepare a solution.
In the second C step of concentrating the solution obtained in the first C step,
In the third C step, the concentrated solution obtained in the second C step is cooled to precipitate a mixed weak acid salt of a rare earth element and the luminescent element.
In the 4C step, the precipitate obtained in the 3C step is calcined to obtain a rare earth element oxide containing a luminescent element.
The fifth C step of adding hydrohalic acid to the suspension obtained by adding a liquid medium to the oxide obtained in the fourth C step and then dehydrating the suspension.
A production method comprising a sixth C step of calcining the dehydrated product obtained in the fifth C step to obtain the corrosion resistant material as a rare earth element oxyhalide containing a luminescent ability-imparting element.
The present production method further comprises a 7C step of pulverizing the oxyhalide obtained in the 6th C step.
In the 8C step, the powder obtained in the 7C step is granulated and dried to obtain a granulated product.
It is preferable to have a ninth C step of calcining the granulated product obtained in the eighth C step.

A suitable example of the production method C will be described.
The operation contents in the first to fourth C steps described above are the same as the operation contents in the first A to fourth A steps of the manufacturing method A. Further, the operation contents in the 7th C to 9C steps, which are suitable manufacturing steps, are the same as the operation contents in the 5A to 7A steps of the manufacturing method A.
The steps peculiar to the present manufacturing method C are the fifth C step and the sixth C step, and the operation contents thereof will be described below.

In the fifth C step, a hydrohalic acid is added to a suspension obtained by adding a liquid medium to an oxide of a rare earth element containing a luminescent element obtained in the fourth C step, and dehydration is performed. It is a process.
In the present production method C, it is preferable to use an oxide of a rare earth element containing a 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 element are dissolved in a heated weak acid aqueous solution and then cooled to precipitate a mixture of the weak acid salt of the rare earth element and the weak acid salt of the luminescent element. It is preferable to use the luminescent element rare earth element oxide obtained by calcining the mixture of the weak salts (that is, by the steps 1A to 4A).

In the fifth C step, an oxide of a rare earth element containing a luminescent element and a hydrohalic acid are mixed to obtain a precursor of an oxyhalide of the rare earth element containing a luminescent element. Examples of the hydrohalic acid include hydrofluoric acid (HF) and hydrochloric acid (HCl). The mixing is preferably carried out in water from the viewpoint of efficiently obtaining a corrosion-resistant material having preferable physical characteristics and from the viewpoint of being able to carry out the reaction uniformly. From the same viewpoint, the temperature of the mixture of the rare earth element oxide powder containing the luminescent element and the hydrohalic acid is 20 ° C. or higher and 50 ° C. or lower from the viewpoint of efficiently promoting the reaction. It is preferably 30 ° C. or higher and 40 ° C. or lower, more preferably. When mixed with hydrohalic acid, the powder of the rare earth element oxide containing the luminescent element is at a concentration of 50 g / L or more and 90 g / L or less in water in terms of the oxide of the rare earth element containing the luminescent element. Dispersion is preferable from the viewpoint that the oxyhalogenation reaction proceeds efficiently, and it is more preferable to disperse at a concentration of 60 g / L or more and 80 g / L or less.

The amount of hydrohalic acid used is 10 parts by mass or more and 50 parts by mass with respect to 100 parts by mass of the oxide of a rare earth element containing a luminescent element, from the viewpoint that a composition showing excellent corrosion resistance can be obtained. It is preferably 15 parts by mass or more and 40 parts by mass or less. Mixing of the rare earth element oxide powder containing the luminescent element and the hydrohalic acid is preferably performed with stirring, and the stirring time is set from the viewpoint of successfully obtaining the target product and shortening the production time. Is preferably, for example, 10 hours or more and 50 hours or less, and more preferably 15 hours or more and 40 hours or less.

Next, in the 6th C step, the precursor of the oxyhalide of a rare earth element containing the luminescent ability-imparting element obtained in the 5th C step is fired to emit light, which is suitable for the corrosion-resistant material according to the present invention. An oxyhalide powder of a rare earth element containing a function-imparting element can be obtained. It is preferable that the firing is performed in an oxygen-containing atmosphere such as an atmospheric atmosphere because an oxyhalide containing a rare earth element containing a luminescent ability-imparting element can be easily obtained.
Further, the firing temperature is preferably 500 ° C. or higher, more preferably 550 ° C. or higher, because it is easy to obtain a preferable corrosion-resistant material in terms of having the above-mentioned high crystallinity. Further, the firing temperature is preferably 800 ° C. or lower, and more preferably 700 ° C. or lower in terms of suppressing excessive oxidation. The firing time in the above temperature range is preferably 10 hours or more and 50 hours or less, and more preferably 20 hours or more and 40 hours or less.
From the viewpoint of efficiently obtaining an oxyhalide powder of a rare earth element containing a luminescent element, it is preferable to dry the precursor of the oxyhalide of a rare earth element before firing. For example, the drying temperature is 100 ° C. or higher and 200 ° C. or lower. Is preferable, and 120 ° C. or higher and 180 ° C. or lower is more preferable.
By the above firing, a corrosion resistant material containing an oxyhalide of a rare earth element containing a luminescent element can be obtained. Further, it is preferable to carry out the 7th to 9th steps. The firing temperature in the ninth C step is preferably 500 ° C. or higher and 900 ° C. or lower in terms of successfully obtaining a rare earth element oxyhalide containing a luminescent element, and more preferably 600 ° C. or higher and 800 ° C. or lower.

Next, when the base material is a rare earth element-containing aluminum oxide, it is preferable to do as follows.
(Manufacturing method D)
A method for producing a corrosion-resistant material for a semiconductor manufacturing apparatus, which comprises a base material having dry etching resistance and an element that imparts visible light emission ability by ultraviolet irradiation to the base material, and the base material is a rare earth element-containing aluminum oxide. There,
A first D step of mixing an oxide of a rare earth element, an oxide of the luminescent element, and an aluminum oxide.
In the second D step of pulverizing the mixture obtained in the first D step, and
In the 3D step of granulating and drying the powder obtained in the 2D step,
In the 4D step, the granulated product obtained in the 3D step is calcined to obtain a calcined body of a rare earth element-containing aluminum oxide containing a luminescent element.
A method for producing a corrosion-resistant material having.

A suitable example of the manufacturing method D will be described.
In the first D step, as the aluminum oxide, a very common powder of aluminum oxide (alumina) or the like can be used. Aluminum oxide includes aluminum _{oxide (III) represented by the chemical formula of Al 2} O ₃ , aluminum (II) oxide represented by the chemical formula of Al O, _{and aluminum oxide represented by the chemical formula of Al 2 O (Aluminium oxide (III) represented by the chemical formula of Al 2 O.} I) exists. As the oxide of the rare earth element and the oxide of the luminescent ability-imparting element, the oxide mentioned in the production method A can be used.

In the first D step and the second D step, the aluminum oxide, the oxide of the rare earth element, and the oxide of the luminescent element are mixed and pulverized in a desired ratio. The first D step and the second D step may be performed at the same time. The pulverization in the second D step may be dry pulverization or wet pulverization. In the case of wet pulverization, a dispersion medium is added to an aluminum oxide, an oxide of a rare earth element, and an oxide of a luminescent element to prepare a slurry. Examples of the dispersion medium include those mentioned as examples of the liquid medium used in the above-mentioned production step A. Examples of the crushing conditions in the second D step include those mentioned in the fifth A step. The powder obtained in the second D step is granulated and dried in the third D step to obtain a granulated product. The operation contents such as granulation and drying are the same as the operation contents of the sixth A step of the above-mentioned manufacturing method A.
Then, in the 4D step, the granulated product obtained in the 3D step is calcined to obtain a corrosion-resistant material containing a rare earth element aluminum oxide containing a luminescent element. 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 in that the target composition can be obtained with high efficiency. When the firing temperature is 1800 ° C. or lower, a preferable corrosion-resistant material can be obtained from the viewpoint of preventing impurity contamination from the furnace material, more preferably 1600 ° C. or lower, and further preferably 1500 ° C. or lower. Further, it is easy to obtain a desired corrosion-resistant material when the firing temperature is 1000 ° C. or higher, and it is more preferable that the firing temperature is 1200 ° C. or higher. The firing time in the above temperature range is preferably 3 hours or more and 10 hours or less, and more preferably 4 hours or more and 8 hours or less in terms of uniform firing.

Next, when the base material is a rare earth element-containing silicon oxide, it is preferable to do as follows.
(Manufacturing method E)
A method for producing a corrosion-resistant material for a semiconductor manufacturing apparatus, which comprises a base material having dry etching resistance and an element that imparts visible light emission ability by ultraviolet irradiation to the base material, and the base material is a rare earth element-containing silicon oxide. There,
The first step of mixing the oxide of the rare earth element, the oxide of the luminescent element, and the silicon oxide, and the first step.
In the second E step of pulverizing the mixture obtained in the first E step,
In the third E step of granulating and drying the powder obtained in the second E step,
In the 4E step, the granulated product obtained in the 3E step is calcined to obtain a rare earth element-containing silicon oxide containing a luminescent element.
A method for producing a corrosion-resistant material having.

A suitable example of the manufacturing method E will be described.
In the first step E, a silicon oxide is used instead of the aluminum oxide used in the above-mentioned production method D. Silicon oxides include 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, etc., and its powder is often used. Used. As the oxide of the rare earth element and the oxide of the luminescent ability-imparting element, the oxide mentioned in the production method A can be used.

In the first step and the second step, the silicon oxide, the oxide of the rare earth element, and the oxide of the luminescent element are mixed in a desired ratio, and the desired mixing and pulverization are performed. The first E step and the second E step may be performed at the same time. The pulverization in the second step E may be dry pulverization or wet pulverization. In the case of wet pulverization, a dispersion medium is added to a silicon oxide, an oxide of a rare earth element, and an oxide of a luminescent element to give a dispersion medium, and pulverization is performed. Examples of the dispersion medium include those mentioned as examples of the wet pulverization dispersion medium used in the above-mentioned production step A. Examples of the crushing conditions for crushing in the second E step include those mentioned in the fifth A step. The powder obtained in the second E step is then granulated and dried in the third E step to obtain a granulated product. The operation contents such as granulation and drying are the same as the operation contents of the sixth A step of the above-mentioned manufacturing method A.
Then, in the 4E step, the granulated product obtained in the 3E step is calcined to obtain a corrosion resistant material containing a rare earth element silicon oxide containing a light emitting ability-imparting element. 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 in that the target composition can be obtained with high efficiency. When the firing temperature is 1800 ° C. or lower, a preferable corrosion-resistant material can be obtained from the viewpoint of suppressing impurity contamination from the furnace material, more preferably 1600 ° C. or lower, further preferably 1500 ° C. or lower. Further, it is easy to obtain a desired corrosion-resistant material when the firing temperature is 1000 ° C. or higher, and it is more preferable that the firing temperature is 1200 ° C. or higher. The firing time in the above temperature range is preferably 5 hours or more and 30 hours or less, and more preferably 10 hours or more and 25 hours or less in terms of uniform firing.

Next, a method of using the obtained corrosion-resistant material according to the present invention will be described.
The corrosion-resistant material according to the present invention is preferably used as a semiconductor manufacturing apparatus, a container as a constituent member thereof, or a film covering the surface thereof. For use in a semiconductor manufacturing apparatus or its constituent members, the corrosion-resistant material according to the present invention can be molded into a molded product, or sintered to produce a sintered body. Alternatively, in order to coat the surface of the semiconductor manufacturing apparatus or its constituent members, it can be obtained by forming a film on the surface with the corrosion resistant material according to the present invention.

First, a method for producing a molded product or a sintered body using the corrosion-resistant material according to the present invention will be described.
In order to manufacture the molded product, a mold pressing method, a rubber press (hydrostatic pressure pressing) method, a sheet molding method, an extrusion molding method, a casting molding method and the like can be used. Then, in order to sinter the obtained molded product, a pressure sintering method is used. As a specific pressure sintering method, hot press, pulse energization pressurization (SPS), and hot isotropic 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 molded product or a sintered body.

Further, a method of forming a film of the corrosion-resistant material powder according to the present invention on the semiconductor manufacturing apparatus or its constituent members will be described. Examples of the main film forming method include a thermal spraying method, an AD (aerosol deposition) method, and a physical vapor deposition (PVD) method. As the thermal spraying method, frame thermal spraying, high-speed frame thermal spraying, explosive thermal spraying, laser thermal spraying, plasma thermal spraying, laser / plasma combined thermal spraying, and the like can be applied. The AD method is a technique for forming a film on the surface of a base material by mixing the film-forming powder with a gas at room temperature to make it into an aerosol state, and injecting it at high speed through a nozzle to cause it to collide with the base material. The PVD method is roughly classified into a sputtering method, a vacuum deposition method, and an ion plating method. For example, the vacuum vapor deposition method is a method in which a material for film formation is evaporated or sublimated in a vacuum, and the vapor reaches a substrate to be formed and is deposited to form a film. As the vacuum vapor deposition method, the electron beam method and the laser vapor deposition method are preferable because they have sufficiently large energy to vaporize powders such as rare earth element oxides. The ion plating method is a film forming method based on almost the same principle as the vapor deposition method, except that the evaporated particles are allowed to pass through the plasma to be positively charged and the substrate is negatively charged. The point is that an electric charge is applied to attract and deposit the evaporated particles to form a film.

Next, in the semiconductor manufacturing apparatus using the corrosion-resistant material according to the present invention, a method for detecting a portion deteriorated by the dry etching gas will be described.
The reason why the semiconductor manufacturing equipment is deteriorated by the dry etching gas is that the surface of the container or the like of the semiconductor manufacturing equipment is contaminated and deteriorated by the dry etching with the halogen gas or the like in the dry etching process when manufacturing the semiconductor. .. When the surface deteriorates, it is necessary to repair or replace the part, and if the part can be determined and identified, the repair and replacement work will be efficient and it is very advantageous in terms of maintenance. It becomes. Therefore, a corrosion-resistant material according to the present invention, which is a mixture of a rare earth element-containing oxide or the like as a base material and a light-emitting element-imparting element, is applied to a molded body, a sintered body, or a film formed on the surface of a container or the like of a semiconductor manufacturing apparatus. By using it as a film, it is possible to easily determine deterioration due to dry etching.

The reason for enabling the deterioration determination is as follows.
When dry etching is performed, the surface of the container or the like is roughened by the etching gas, and the 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 rays, visible light is emitted from a luminescent element such as europium existing in the surface material. The larger the surface roughness, the larger the specific surface area, and the larger the specific surface area, the higher the emission intensity of visible light. Therefore, if the degree of emission, for example, the peak height of the emission intensity is observed, etching is performed. The degree of deterioration due to gas can be determined. Therefore, if the degree of light emission is examined before and after the dry etching, the degree of deterioration due to the etching process can be determined.
Ultraviolet rays are electromagnetic waves 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 ultraviolet rays used for determining deterioration is preferably 200 nm or more and 400 nm or less because it exhibits high luminous efficiency.

From the above, in the molded body or sintered body made of the corrosion-resistant material according to the present invention, the semiconductor manufacturing apparatus or the container which is a constituent member thereof, specifically, the container such as the vacuum chamber in the etching apparatus and the inside of the container. A sample table, chuck, wafer holding material (ring plate), discharge substrate (etching plate), focus ring, etching gas supply port, etc. are manufactured, or the corrosion-resistant material according to the present invention is used for a semiconductor manufacturing apparatus or its constituent members. By forming a film on the surface, it is possible to determine and detect the deteriorated portion of dry etching in the semiconductor manufacturing apparatus. It is preferable that the molded product, sintered body, or film made of the corrosion-resistant material according to the present invention has a surface roughness Ra of 20 μm or less before being used in the etching process because it is easy to determine the degree of deterioration due to the etching process. It is more preferably 10 μm or less. The surface roughness can be measured by the method described in Examples described later.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the scope of the invention is not limited to such examples. In the following Examples and Comparative Examples, the specific surface area (SSA, m ² / g) and the average particle size (D50, μm) of the characteristics of the obtained powder were measured as follows.
[Specific surface area]
It was measured by the BET 1-point method using a fully automatic specific surface area meter Maxorb model-1201 manufactured by Mountech. The gas used was a nitrogen-helium mixed gas (nitrogen 30 vol%).
[Average particle size]
Measured with a micro truck HRA manufactured by Nikkiso Co., Ltd. At the time of measurement, a 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 the concentration was appropriate.

[Example 1]
70 L of pure water and 25 L of an 80 mass% acetic acid aqueous solution were mixed, and 99 kg of yttrium oxide and 1 kg of europium oxide were added to the mixed solution and heated to 90 ° C. to prepare a solution. Then, 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 of yttrium acetate and europium acetate. The precipitate was dehydrated with a centrifuge, and the dehydrated product was fired in an air atmosphere at 600 ° C. for 24 hours to obtain a europium-containing yttrium oxide.
Pure water was added to the obtained oxide to prepare a slurry of 1400 g / L, and pulverization was carried out 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 Ogawara Processing Machine Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were as follows.
・ Slurry supply rate: 300 mL / min
・ Atomizer rotation speed: 20000 min ^-1
・ Inlet temperature: 250 ℃
The obtained granules were placed in an alumina container and fired in an electric furnace in an air atmosphere to obtain granulated granules. The firing temperature was 1000 ° C. and the firing time was 12 hours. In this way, the desired corrosion resistant material was obtained.

[Example 2]
70 L of pure water and 25 L of an 80 mass% acetic acid aqueous solution were mixed, 97 kg of yttrium oxide and 3 kg of europium oxide were added to the mixed solution, and the mixture was heated to 90 ° C. to prepare a solution. Then, 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 of yttrium acetate and europium acetate. The precipitate was dehydrated with a centrifuge, and the dehydrated product was fired in an air atmosphere at 600 ° C. for 24 hours to obtain a europium-containing yttrium oxide.
Pure water was added to the obtained oxide to prepare a slurry of 1400 g / L, and pulverization was carried out 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 Ogawara Processing Machine Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were as follows.
・ Slurry supply rate: 300 mL / min
・ Atomizer rotation speed: 20000 min ^-1
・ Inlet temperature: 250 ℃
The obtained granules were placed in an alumina container and fired in an electric furnace in an air atmosphere to obtain granulated granules. The firing temperature was 1000 ° C. and the firing time was 12 hours. In this way, the desired corrosion resistant material was obtained.

[Example 3]
70 L of pure water and 25 L of an 80 mass% acetic acid aqueous solution were mixed, and 99 kg of yttrium oxide and 1 kg of europium oxide were added to the mixed solution and heated to 90 ° C. to prepare a solution. Then, 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 of yttrium acetate and europium acetate. The precipitate was dehydrated with a centrifuge, and the dehydrated product was fired in an air atmosphere at 600 ° C. for 24 hours to obtain a europium-containing yttrium oxide.
Pure water was added to the obtained oxide to prepare a slurry of 1400 g / L, and pulverization was carried out 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 Ogawara Processing Machine Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were as follows.
・ Slurry supply rate: 300 mL / min
・ Atomizer rotation speed: 20000 min ^-1
・ Inlet temperature: 250 ℃
The obtained granules were placed in an alumina container and fired in an electric furnace in an air atmosphere to obtain granulated granules. The firing temperature was 1600 ° C. and the firing time was 12 hours. In this way, the desired corrosion resistant material was obtained.

[Example 4]
70 L of pure water and 25 L of an 80 mass% acetic acid aqueous solution were mixed, and 95.5 kg of yttrium oxide and 4.5 kg of europium oxide were added to the mixed solution and heated to 90 ° C. to prepare a solution. Then, 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 of yttrium acetate and europium acetate. The precipitate was dehydrated with a centrifuge, and the dehydrated product was fired in an air atmosphere at 600 ° C. for 24 hours to obtain a europium-containing yttrium oxide.
Pure water was added to the obtained oxide to prepare a slurry of 1400 g / L, and pulverization was carried out 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 Ogawara Processing Machine Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were as follows.
・ Slurry supply rate: 300 mL / min
・ Atomizer rotation speed: 20000 min ^-1
・ Inlet temperature: 250 ℃
The obtained granules were placed in an alumina container and fired in an electric furnace in an air atmosphere to obtain granulated granules. The firing temperature was 1400 ° C. and the firing time was 12 hours. In this way, the desired corrosion resistant material was obtained.

[Example 5]
70 L of pure water and 25 L of an 80 mass% acetic acid aqueous solution were mixed, and 99 kg of yttrium oxide and 1 kg of europium oxide were added to the mixed solution and heated to 90 ° C. to prepare a solution. Then, 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 of yttrium acetate and europium acetate. The precipitate was dehydrated with a centrifuge, and the dehydrated product was fired in an air atmosphere at 600 ° C. for 24 hours to obtain a europium-containing yttrium oxide.
Pure water was added to the obtained oxide to prepare a slurry of 1400 g / L, and pulverization was carried out 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 Ogawara Processing Machine Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were as follows.
・ Slurry supply rate: 300 mL / min
・ Atomizer rotation speed: 10000min ^-1
・ Inlet temperature: 250 ℃
The obtained granules were placed in an alumina container and fired in an electric furnace in an air atmosphere to obtain granulated granules. The firing temperature was 800 ° C. and the firing time was 12 hours. In this way, the desired 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 60 mass% nitric acid aqueous solution to prepare a solution having a concentration of 300 g / L. 105 kg of a hydrofluoric acid aqueous solution having a concentration of 50% was added to the obtained solution to obtain a precipitate. Then, it was washed with pure water and dehydrated using a gravity filter, and then dried at 150 ° C. for 24 hours. The obtained dried product was calcined at 900 ° C. for 24 hours in an air atmosphere to obtain europium-containing yttrium fluoride.
Pure water was added to the obtained fluoride to prepare a slurry of 1400 g / L, and pulverization was carried out 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 Ogawara Processing Machine Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were as follows.
・ Slurry supply rate: 300 mL / min
・ Atomizer rotation speed: 20000 min ^-1
・ Inlet temperature: 250 ℃
The obtained granules were placed in an alumina container and fired in an electric furnace in an air atmosphere to obtain granulated granules. The firing temperature was 550 ° C. and the firing time was 12 hours. In this way, the desired corrosion resistant material was obtained.

[Example 7]
70 L of pure water and 25 L of an 80 mass% acetic acid aqueous solution were mixed, and 99 kg of yttrium oxide and 1 kg of europium oxide were added to the mixed solution and heated to 90 ° C. to prepare a solution. Then, 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 of yttrium acetate and europium acetate. The precipitate was dehydrated with a centrifuge, and the dehydrated product was fired in an air atmosphere at 600 ° C. for 24 hours to obtain a europium-containing yttrium oxide.
Pure water was added to the obtained oxide to prepare a suspension of 70 g / L, and 35 kg of a 50 mass% hydrofluoric acid aqueous solution was added while stirring at a speed of 60 rpm. After stirring at 30 to 40 ° C. for 24 hours, dehydration was performed using a gravity filter, and the obtained dehydrated product was fired in an atmospheric atmosphere at 600 ° C. for 24 hours to obtain yttrium and europium-containing yttrium oxyfluoride.
Pure water was added to the obtained oxyfluoride to prepare a slurry of 1400 g / L, and pulverization was carried out 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 Ogawara Processing Machine Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were as follows.
・ Slurry supply rate: 300 mL / min
・ Atomizer rotation speed: 20000 min ^-1
・ Inlet temperature: 250 ℃
The obtained granules were placed in an alumina container and fired in an electric furnace in an air atmosphere to obtain granulated granules. The firing temperature was 700 ° C. and the firing time was 12 hours. In this way, the desired 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, and 100 kg of pure water was added to prepare a slurry having a concentration of 50% by mass. The obtained slurry was wet-milled to 0.3 μm using a Dynomill KD-45H manufactured by Willie et Bacoffen. The slurry containing the crushed particles was granulated and dried using a spray dryer (manufactured by Okawara Processing Machine Co., Ltd.) to obtain granulated products. The operating conditions of the spray dryer were as follows.
・ Slurry supply rate: 300 mL / min
・ Atomizer rotation speed: 10000min ^-1
・ Inlet temperature: 250 ℃
The obtained granules were placed in an alumina container and fired in an electric furnace in an air atmosphere to obtain granulated granules. The firing temperature was 1400 ° C. and the firing time was 5 hours. In this way, the desired 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, and 100 kg of pure water was added to prepare a slurry having a concentration of 50% by mass. The obtained slurry was wet-milled to 0.3 μm using a Dynomill KD-20L manufactured by Willie et Bacoffen. The slurry containing the crushed particles was granulated and dried using a spray dryer (manufactured by Okawara Processing Machine Co., Ltd.) to obtain granulated products. The operating conditions of the spray dryer were as follows.
・ Slurry supply rate: 300 mL / min
・ Atomizer rotation speed: 10000min ^-1
・ Inlet temperature: 250 ℃
The obtained granules were placed in an alumina container and fired in an electric furnace in an air atmosphere to obtain granulated granules. The firing temperature was 1400 ° C. and the firing time was 12 hours. In this way, the desired corrosion resistant material was obtained.

[Example 10]
70 L of pure water and 25 L of an 80 mass% acetic acid aqueous solution were mixed, and 99 kg of yttrium oxide and 1 kg of terbium oxide were added to the mixed solution and heated to 90 ° C. to prepare a solution. Then, 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 with a centrifuge, and the dehydrated product was fired in an air atmosphere at 600 ° C. for 24 hours to obtain a terbium-containing yttrium oxide.
Pure water was added to the obtained oxide to prepare a slurry of 1400 g / L, and pulverization was carried out 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 Ogawara Processing Machine Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were as follows.
・ Slurry supply rate: 300 mL / min
・ Atomizer rotation speed: 17500min ^-1
・ Inlet temperature: 250 ℃
The obtained granules were placed in an alumina container and fired in an electric furnace in an air atmosphere to obtain granulated granules. The firing temperature was 1400 ° C. and the firing time was 12 hours. In this way, the desired corrosion resistant material was obtained.

[Example 11]
70 L of pure water and 25 L of 80 mass% acetic acid aqueous solution are mixed, and yttrium oxide 99 is contained in the mixed solution.
.. 98 kg and 0.02 kg of europium oxide were added and heated to 90 ° C. to prepare a solution. Then, 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 of yttrium acetate and europium acetate. The precipitate was dehydrated with a centrifuge, and the dehydrated product was fired in an air atmosphere at 600 ° C. for 24 hours to obtain a europium-containing yttrium oxide.
Pure water was added to the obtained oxide to prepare a slurry of 1400 g / L, and pulverization was carried out 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 Ogawara Processing Machine Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were as follows.
・ Slurry supply rate: 300 mL / min
・ Atomizer rotation speed: 20000 min ^-1
・ Inlet temperature: 250 ℃
The obtained granules were placed in an alumina container and fired in an electric furnace in an air atmosphere to obtain granulated granules. The firing temperature was 1000 ° C. and the firing time was 12 hours. In this way, the desired corrosion resistant material was obtained.

[Example 12]
70 L of pure water and 25 L of an 80 mass% acetic acid aqueous solution were mixed, and 99 kg of yttrium oxide and 1 kg of europium oxide were added to the mixed solution and heated to 90 ° C. to prepare a solution. Then, 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 of yttrium acetate and europium acetate. The precipitate was dehydrated with a centrifuge, and the dehydrated product was fired in an air atmosphere at 600 ° C. for 24 hours to obtain a europium-containing yttrium oxide.
Pure water was added to the obtained oxide to prepare a slurry of 1400 g / L, and pulverization was carried out 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 Ogawara Processing Machine Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were as follows.
・ Slurry supply rate: 300 mL / min
・ Atomizer rotation speed: 20000 min ^-1
・ Inlet temperature: 250 ℃
The obtained granules were placed in an alumina container and fired in an electric furnace in an air atmosphere to obtain granulated granules. The firing temperature was 600 ° C. and the firing time was 12 hours. In this way, the desired corrosion resistant material was obtained.

[Comparative Example 1]
70 L of pure water and 25 L of an 80 mass% acetic acid aqueous solution were mixed, 100 kg of yttrium oxide was added into the mixed solution, and the mixture was heated to 90 ° C. to prepare a solution. Then, 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 salt consisting of yttrium acetate. The precipitate was dehydrated with a centrifuge, and the dehydrated product was calcined in an air atmosphere at 600 ° C. for 24 hours to obtain an yttrium oxide.
Pure water was added to the obtained oxide to prepare a slurry of 1400 g / L, and pulverization was carried out 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 Ogawara Processing Machine Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were as follows.
・ Slurry supply rate: 300 mL / min
・ Atomizer rotation speed: 20000 min ^-1
・ Inlet temperature: 250 ℃
The obtained granules were placed in an alumina container and fired in an electric furnace in an air atmosphere to obtain granulated granules. The firing temperature was 1000 ° C. and the firing time was 12 hours. In this way, the desired corrosion resistant material was obtained.

[Comparative Example 2]
70 L of pure water and 25 L of an 80 mass% acetic acid aqueous solution were mixed, 100 kg of europium oxide was added into the mixed solution, and the mixture was heated to 90 ° C. to prepare a solution. Then, 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 of europium acetate. The precipitate was dehydrated with a centrifuge, and the dehydrated product was fired in an air atmosphere at 600 ° C. for 24 hours to obtain a europium oxide.
Pure water was added to the obtained oxide to prepare a slurry of 1400 g / L, and pulverization was carried out 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 Ogawara Processing Machine Co., Ltd.) to obtain a granulated product. The operating conditions of the spray dryer were as follows.
・ Slurry supply rate: 300 mL / min
・ Atomizer rotation speed: 20000 min ^-1
・ Inlet temperature: 250 ℃
The obtained granules were placed in an alumina container and fired in an electric furnace in an air atmosphere to obtain granulated granules. The firing temperature was 1000 ° C. and the firing time was 12 hours. In this way, the desired corrosion resistant material was obtained.

[Composition of base material and content of luminescent element]
50 g of the powdery corrosion-resistant material obtained in each Example and Comparative Example was collected, placed in a sieve mortar, and ethanol was added dropwise in an amount so that the powder was completely immersed, and the powder was hand-ground with a dusting wood for 10 minutes. It was dried and subjected to X-ray diffraction measurement and fluorescent X-ray analysis under a sieve having an opening of 250 μm or less.

The composition of the base material described in each Example and Comparative Example was analyzed under the following conditions using an X-ray diffractometer Ultima IV manufactured by Rigaku Corporation.
(X-ray diffraction measurement conditions)
Radioactive source: CuKα wire 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 dispersive fluorescent X-ray analyzer ZSX Primus II manufactured by Rigaku Co., Ltd. was used for the analysis of the content of the luminescent element in the powder described in each example. The measurement was carried out under the following conditions, and the obtained data was donated to the ScanQuant X analysis to obtain the content of the luminescent element contained in the powder.
Regarding the powder described in Comparative Example 1, the luminescent ability-imparting element (rare earth element that contributes to luminescence) was analyzed under the following measurement conditions, and it was confirmed that the powder was below the lower limit of detection.
Regarding the powder described in Comparative Example 2, the rare earth elements excluding the base material were analyzed under the following measurement conditions, and after confirming that the powder was below the lower limit of detection, the luminescence ability was imparted from the composition identified by the X-ray diffraction measurement. The ratio of elements was calculated.

(Fluorescent X-ray measurement conditions)
[Excited conditions]
Target: Rh
Tube voltage: 50 kV
Tube current: 60mA
[Scan conditions]
Starting angle: 5.000deg
End angle: 90.000 deg
Step: 0.02 deg
Speed: 30 deg / min
[Optical conditions]
Attenuator: 1/1
Slit: S2
Spectral crystal: LiF (200)
Detector: SC

When the corrosion-resistant material obtained in each example was subjected to X-ray diffraction measurement using Cu-Kα rays, the peak of the maximum intensity observed at 2θ = 10 to 90 degrees was the "base material" in Table 1. It was confirmed that it was the compound described in the section of. The corrosion-resistant material obtained in each example was confirmed to be a single phase of the compound described in the "base material" section of Table 1 by X-ray diffraction measurement using Cu-Kα rays.

[Powder emission characteristics]
Further, the powdery corrosion-resistant materials obtained in each Example and Comparative Example except Example 10 were examined by the following method for powder emission wavelength and intensity, and evaluated according to the following evaluation criteria.
Measurement method of powder emission wavelength: The powder was uniformly filled in a powder measurement cell dedicated to the fluorescence spectrophotometer F-7000 manufactured by Hitachi High-Technologies Corporation, and the emission wavelength was evaluated under the conditions described below. As the emission wavelength, the wavelength of the apex of the waveform observed in the following observation wavelengths was read. When evaluating the emission characteristics, a long-pass filter that cuts wavelengths of 300 nm or less was installed between the sample and the second diffraction grating in order to prevent the secondary light of the excitation light from entering the detector.
[Light emission characteristics]
・ Equipment: Hitachi High-Technologies Fluorescence Spectrophotometer F-7000
-Excitation wavelength: 254 nm
-Observation wavelength: 600 nm to 630 nm
・ Photomal voltage: 400 volt Measurement method of powder emission intensity: In a dark room where light from the outside is completely blocked, iuch HANDY UV LAMP is used for the cell filled with the powder used for the above wavelength measurement. The distance between the cell and the lamp was set to 50 mm, ultraviolet rays having a wavelength of 254 nm were irradiated with an illuminance of 614 μw / cm ² , and the degree of light emission visually confirmed was classified according to the following criteria.
⊚: Strong light emission was confirmed.
〇: Weak light emission was confirmed.
Δ: Light emission was confirmed, but it was extremely weak.
X: No light emission could be confirmed.

Regarding Example 10, the powder emission wavelength and the intensity were examined by the following method, and evaluated according to the following evaluation criteria.
Measurement method of powder emission wavelength: The powder was uniformly filled in a powder measurement cell dedicated to the fluorescence spectrophotometer F-7000 manufactured by Hitachi High-Technologies Corporation, and the emission wavelength was evaluated under the conditions described below. As the emission wavelength, the wavelength of the apex of the waveform observed in the following observation wavelengths was read. When evaluating the emission characteristics, a long-pass filter that cuts wavelengths of 300 nm or less was installed between the sample and the second diffraction grating in order to prevent the secondary light of the excitation light from entering the detector.
[Light emission characteristics]
・ Equipment: Hitachi High-Technologies Fluorescence Spectrophotometer F-7000
-Excitation wavelength: 254 nm
-Observation wavelength: 520 nm to 560 nm
・ Photomal voltage: 400 volt Measurement method of powder emission intensity: In a dark room where light from the outside is completely blocked, iuch HANDY UV LAMP is used for the cell filled with the powder used for the above wavelength measurement. The distance between the cell and the lamp was set to 50 mm, ultraviolet rays having a wavelength of 254 nm were irradiated with an illuminance of 614 μw / cm ² , and the degree of light emission visually confirmed was classified according to the following criteria.
⊚: Strong light emission was confirmed.
〇: Weak light emission was confirmed.
Δ: Light emission was confirmed, but it was extremely weak.
X: No light emission could be confirmed.

[Emission characteristics before and after acid exposure]
With respect to the corrosion-resistant material obtained by the methods described in [Example 1] to [Example 9], [Example 11], [Example 12], [Comparative Example 1] and [Comparative Example 2], the following As a model test for evaluation of deterioration due to etching gas in the dry etching process, whether or not corrosion resistance due to halogen elements can be identified by light emission was evaluated by an acid exposure method immersed in an aqueous hydrofluoric acid solution according to the procedure shown in (1).
The powder was put into a molding die having a diameter of 20 mm, and the molded product was formed by uniaxial molding by applying a pressure of 3 tons for 20 seconds, and then fired at 1500 ° C. in an air atmosphere. The surface of the fired molded product was smoothed using a high-precision mirror surface polishing machine 15B single-sided polishing machine with a facing device manufactured by Nanotech Machines until Ra became 0.1 μm or less. Ra was measured on the smoothed surface using the Mitutoyo stylus type surface roughness measuring instrument SJ-210, and the emission characteristics were measured using the Hitachi High-Technologies Fluorometer F-7000 under the conditions described below. Was evaluated. When evaluating the emission characteristics, a long-pass filter that cuts wavelengths of 300 nm or less was installed between the sample and the second diffraction grating in order to prevent the secondary light of the excitation light from entering the detector. Then, the molded product was immersed in a 48 mass% hydrofluoric acid aqueous solution for 168 hours to be subjected to corrosion resistance treatment with a halogen element. After the immersion, the molded product was dried, and Ra and light emission characteristics were measured by the same evaluation method as before the immersion.

[Light emission characteristics]
The emission wavelength and the height of the emission peak were measured under the following conditions.
・ Equipment: Hitachi High-Technologies Fluorescence Spectrophotometer F-7000
-Excitation wavelength: 254 nm
-Observation wavelength: 600 nm to 630 nm
・ Photomal voltage: 275 volts

The corrosion-resistant material obtained by the method described in [Example 10] above is immersed in a hydrofluoric acid aqueous solution as a model of deterioration of contamination by etching gas in the dry etching step according to the following procedure. It was evaluated whether or not the corrosion resistance deterioration due to the halogen element could be identified by the light emission by the acid exposure method.
The powder was put into a molding die having a diameter of 20 mm, and the molded product was formed by uniaxial molding by applying a pressure of 3 tons for 20 seconds, and then fired at 1500 ° C. in an air atmosphere. The surface of the fired molded product was smoothed using a high-precision mirror surface polishing machine 15B single-sided polishing machine with a facing device manufactured by Nanotech Machines. Ra was measured on the smoothed surface using the Mitutoyo stylus type surface roughness measuring instrument SJ-210, and the emission characteristics were measured using the Hitachi High-Technologies Fluorometer F-7000 under the conditions described below. Was evaluated. When evaluating the emission characteristics, a long-pass filter that cuts wavelengths of 300 nm or less was installed between the sample and the second diffraction grating in order to prevent the secondary light of the excitation light from entering the detector. Then, the molded product was immersed in a 48 mass% hydrofluoric acid aqueous solution for 168 hours to be subjected to corrosion resistance treatment with a halogen element. After the immersion, the molded product was dried, and Ra and light emission characteristics were measured by the same evaluation method as before the immersion.

[Light emission characteristics]
The emission wavelength and the height of the emission peak were measured under the following conditions.
・ Equipment: Hitachi High-Technologies Fluorescence Spectrophotometer F-7000
-Excitation wavelength: 254 nm
-Observation wavelength: 520 nm to 560 nm
・ Photomal voltage: 275 volts

As described above, the corrosion-resistant material according to the present invention obtained in Examples 1 to 12 was found to emit visible light by ultraviolet irradiation, and the peak height of the emission intensity increased before and after the acid exposure test. Deterioration due to halogen elements was detected. However, since Comparative Example 1 did not contain a luminescent element, it did not emit visible light due to ultraviolet irradiation, and the acid exposure test could not be evaluated. Further, in Comparative Example 2, since the base material itself was a europium oxide and europium was not activated, the emission of visible light by ultraviolet irradiation was weak, and the acid exposure test could not be evaluated. As described above, it was found that the corrosion-resistant material according to the present invention is an excellent material for detecting the state of deterioration in the etching process.

Claims (16)

A corrosion-resistant material for semiconductor manufacturing equipment, which comprises a base material having dry etching resistance and an element that imparts the ability to emit visible light by ultraviolet irradiation to the base material. The corrosion-resistant material for a semiconductor manufacturing apparatus according to claim 1, wherein the base material is an oxide, a halide or an oxyhalide containing a rare earth element. The corrosion-resistant material for a semiconductor manufacturing apparatus according to claim 2, wherein the rare earth element contains yttrium or gadolinium. The corrosion-resistant material for semiconductor manufacturing equipment 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 yttrium fluoride, gadolinium fluoride, yttrium chloride and gadolinium chloride. The corrosion-resistant material for semiconductor manufacturing equipment according to claim 3, wherein the oxyhalide containing a rare earth element is at least one selected from yttrium oxyfluoride, gadolinium oxyfluoride, yttrium oxychloride and gadolinium oxychloride. .. The item according to any one of claims 1 to 6, wherein the corrosion-resistant material contains 0.05% by mass or more and 10% by mass or less of an element that imparts the light emitting ability of visible light by ultraviolet irradiation to the base material. Corrosion resistant material for semiconductor manufacturing equipment. Claims 1 to 7 in which the element that imparts the ability to emit visible light by irradiation with ultraviolet rays to the base material is at least one selected from europium, terbium, neodymium, erbium, dysprosium, samarium, thulium, praseodymium, and ytterbium. The corrosion-resistant material for a semiconductor manufacturing apparatus according to any one of the above items. The corrosion-resistant material for a semiconductor manufacturing apparatus according to claim 8, wherein the element that imparts the light emitting ability of visible light by the ultraviolet irradiation to the base material 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 powder. 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 molded body, a sintered body, or a film. The corrosion-resistant material for a semiconductor manufacturing apparatus according to claim 10, wherein the specific surface area of the powder is 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 size 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 semiconductor dry etching apparatus, its constituent members, or a film constituting the surface thereof. A method for manufacturing a semiconductor manufacturing device or its constituent members.
A semiconductor manufacturing apparatus or a component thereof is manufactured by molding or sintering a corrosion-resistant material containing a base material having dry etching resistance and an element that imparts the ability to emit visible light by ultraviolet irradiation to the base material. Alternatively, a manufacturing method for forming the corrosion-resistant material on the surface of the base material of the semiconductor manufacturing apparatus or its constituent members. This is a method for detecting parts that have deteriorated due to etching gas in semiconductor manufacturing equipment.
A semiconductor manufacturing apparatus or a component thereof can be manufactured by molding or sintering a corrosion-resistant material containing a base material having dry etching resistance and an element that imparts the ability to emit visible light by ultraviolet irradiation to the base material. Alternatively, the corrosion-resistant material is formed on the surface of the base material of the semiconductor manufacturing apparatus or its constituent members.
A detection method for determining a portion where visible light is emitted by irradiating the semiconductor manufacturing apparatus or its constituent members with ultraviolet rays after performing dry etching of a semiconductor using the semiconductor manufacturing apparatus or its constituent members.