JP2020180963A - Laminate and indicator - Google Patents

Abstract

To provide a laminate and an indicator the color tone of which changes upon detecting at least one substance selected from the group consisting of plasma, ozone, ultraviolet light and a radical-containing gas.SOLUTION: The present invention includes a step for providing a laminate comprising a detection layer 4 the color tone of which changes upon detecting at least one substance selected from the group consisting of plasma, ozone, ultraviolet light and a radical-containing gas and a substrate layer 3. The detection layer includes a structure 1 having an internal space communicated with an open hole part on the surface, with a detection agent included in the internal space that includes at least one detection component the color tone of which changes upon detecting at least one substance selected from the group consisting of plasma, ozone, ultraviolet light and a radical-containing gas, the content of each metal atom in the laminate being less than 5.0 mass% or a laminate where the detection component contains a dye compound that does not contain atoms other than carbon, hydrogen and nitrogen.SELECTED DRAWING: Figure 1

Description

The present invention relates to laminates and indicators.

As a method for treating various articles, a method using at least one selected from the group consisting of plasma, ozone, ultraviolet rays and radical-containing gas (hereinafter, may be referred to as "plasma or the like") is widely known. For example, plasma is generated in a gas atmosphere for plasma generation, and the plasma treatment is performed by irradiating various articles, substrates, and the like with the plasma.
Processing by plasma or the like is also performed when manufacturing electronic devices (semiconductor chips, light emitting diodes (LEDs), solar cells, liquid crystal displays, organic EL (Electro-Luminescence) displays, semiconductor lasers, power devices, etc.).
For example, in semiconductor chip manufacturing, film formation (CVD, sputtering, etc.) on a semiconductor wafer (wafer), resist pattern formation (plasma dry etching, ion beam etching, etc.), film etching using a resist pattern, and resist in the previous step. In each step such as pattern removal and cleaning, treatment with plasma or the like is performed.

When manufacturing an electronic device, it is necessary that the treatment with plasma or the like is uniformly performed.
For example, it is important that the treatment with plasma or the like in the pre-process of semiconductor chip manufacturing is uniformly performed in the wafer surface and has in-plane uniformity. When the in-plane uniformity is impaired, the performance of each semiconductor chip formed on the semiconductor wafer varies, which affects the yield.
Therefore, confirmation of the uniformity of processing by plasma or the like is indispensable when designing each electronic device manufacturing apparatus and controlling in the manufacturing process using the apparatus.

The uniformity of the treatment can be confirmed by using a method of measuring the film characteristics, processing accuracy, etc. of the manufactured electronic device, a method of individually performing each of the above treatments, and evaluating the in-plane uniformity. ..
For example, as a method for evaluating the uniformity of the plasma itself, a method of measuring the physical constant of the plasma with a Langmuir probe installed in the manufacturing equipment or a method of analyzing the emission of the plasma with a spectroscopic device is performed to evaluate the distribution in space. The method of doing is known.
However, the method using the Langmuir probe may require work such as opening the manufacturing apparatus to the atmosphere and removing the probe during the manufacturing work, which requires a lot of labor and time. Since the measurement range of the method using a spectroscope is limited, it may not be possible to measure the entire plasma in the device. In addition, the method using a Langmuir probe or a spectroscopic device does not directly indicate the in-plane distribution of each process, and involves analysis work from the measurement results.

Patent Document 1 and Patent Document 2 describe indicators for detecting the presence or absence of ozone or the like.
In Patent Document 3, an ink containing a dye, a specific surfactant, and a nonionic surfactant is applied onto a substrate and placed in a reaction chamber or the like as an indicator to detect the end point of plasma treatment. It is stated that.
Patent Document 4 describes that the uniformity of processing of plasma or the like is confirmed by using an indicator for detecting plasma or the like, which has the same shape as the substrate used in the electronic device manufacturing apparatus. The indicator includes a discoloration layer formed by an ink that discolors or decolorizes by reacting with plasma or the like.
Patent Document 5 describes that a plasma indicator containing a dye in pores formed by an anodic oxidation treatment is used to prevent contamination caused by an ink composition or the like.

The indicators described in Patent Documents 3 to 5 can visually confirm the progress of plasma treatment and the like in the reaction chamber, but the sensitivity and the like must be adjusted appropriately.
In addition, depending on the treatment conditions and the like, some of the constituent components of the indicator placed in the chamber may be gasified, which may contaminate the object to be treated such as plasma treatment and the inside of the chamber. For example, ink often contains substances containing metal atoms and halogen atoms, and it is expected that contamination of components containing metal atoms due to dispersed media or the like may occur during preparation.
In particular, in the pre-process of the manufacturing process of a semiconductor device, the presence of metal atoms is disliked, and an indicator for avoiding contamination has been required.

Japanese Patent No. 4382816 Special Table 2013-537978 Japanese Unexamined Patent Publication No. 2015-013982 International Publication No. 2015/025699 International Publication No. 2018/128123

INDUSTRIAL APPLICABILITY According to the present invention, the sensitivity of a detection layer whose color tone changes by detecting at least one selected from the group consisting of plasma, ozone, ultraviolet rays and radical-containing gas can be easily adjusted. It is an object of the present invention to provide a laminate and an indicator capable of reliably detecting the progress and end point of treatment by at least one selected from the group consisting of ultraviolet rays and radical-containing gases.
The present invention can easily detect whether or not the treatment by at least one selected from the group consisting of plasma, ozone, ultraviolet rays and radical-containing gas is uniformly performed on the entire object to be treated. It is an object of the present invention to provide a laminate and an indicator capable of avoiding contamination of an object to be treated or the inside of a chamber by a pollutant generated by the treatment of the above.

As a result of studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by constructing a laminated body having a specific structure and using this as an indicator.
Specifically, it is as follows.
1: It has a detection layer that detects at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and radical-containing gas and changes the color tone, and a base material layer.
The detection layer includes a structure having an internal space that communicates with an opening on the surface.
The internal space contains a detection agent containing at least one detection component that detects at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and radical-containing gas and changes the color tone.
A laminate in which the content of each metal atom in the laminate is less than 5.0 mass ppm.
2: It has a detection layer that detects at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and radical-containing gas to change the color tone, and a base material layer.
The detection layer includes a structure having an internal space that communicates with an opening on the surface.
The internal space contains a detection agent containing at least one detection component that detects at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and radical-containing gas and changes the color tone.
A laminate in which the detection agent contains a dye compound containing no atoms other than carbon, hydrogen, oxygen and nitrogen.
3: The laminate according to Item 1 above, wherein the detection component contains a dye compound containing no atoms other than carbon, hydrogen, oxygen and nitrogen.
4: At least one resin selected from the group in which the structure comprises a polyimide resin, a polyamideimide resin, a polyamide resin, a polyolefin resin, a polyurethane resin, a melamine resin, a polyester resin, and a polycarbonate resin. Item 3. The laminate according to any one of Items 1 to 3, which is a structure containing.
5: The detection agent contains a resin and / or a resin precursor, and the resin and / or the resin precursor does not contain atoms other than carbon, hydrogen, oxygen and nitrogen atoms. The laminate according to any one of.
6: The laminate according to any one of Items 1 to 5, wherein the content of each halogen atom in the laminate is less than 30 mass ppm.
7: An indicator including the laminate according to any one of the above items 1 to 6.

According to the present invention, it is possible to easily adjust the sensitivity of the detection layer whose color tone changes by detecting at least one selected from the group consisting of plasma, ozone, ultraviolet rays and radical-containing gas, and plasma, ozone, Provided are a laminate and an indicator capable of reliably detecting the progress and end point of treatment by at least one selected from the group consisting of ultraviolet rays and radical-containing gases.
According to the present invention, it is possible to easily detect whether or not the treatment by at least one selected from the group consisting of plasma, ozone, ultraviolet rays and radical-containing gas is uniformly performed on the entire object to be treated. Laminates and indicators that can avoid contamination of the object to be treated and the inside of the chamber by the contaminants generated by the treatment of the above are provided.

The figure which shows the laminated body of this invention Electron micrograph of cross section of the laminate of the present invention

[Laminate]
The laminated body of the present invention has a detection layer whose color tone changes by detecting plasma or the like and a base material layer, and the detection layer includes a structure having an internal space communicating with an opening portion on the surface. The internal space contains at least one detection agent that detects plasma or the like and changes the color tone.

<Detection layer>
The change in the color tone of the detection layer occurs when the detection component comes into contact with plasma or the like and causes one or more color change of discoloration, decolorization, or color development. Here, plasma or the like is at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and radical-containing gas, as described above.
The detection layer of the present invention not only detects plasma or the like, but also can easily visually detect in-plane uniformity in processing by plasma or the like. In the present invention, it is considered that the detection agent can be uniformly present in the plane in the detection layer, so that the in-plane uniformity can be detected.
The thickness of the detection layer is not particularly limited as long as it exhibits the detection function, and can be appropriately optimized according to the application, desired characteristics, and the like. It can be 10 μm or more, preferably 15 to 100 μm, in order to reliably capture the change in color tone.

(plasma)
Plasma means plasma generated by applying an AC voltage, a DC voltage, a pulse voltage, a high frequency, a microwave, or the like using a plasma generating gas, and corresponds to both a reduced pressure plasma and an atmospheric pressure plasma.
The plasma generating gas is not particularly limited as long as it generates plasma by applying an AC voltage, a DC voltage, a pulse voltage, a high frequency, a microwave, or the like. For example, oxygen, nitrogen, hydrogen, fluorine, chlorine, helium, neon, argon, silane, ammonia, sulfur bromide, water vapor, nitrogen peroxide, tetraethoxysilane, carbon tetrafluoride, trifluoromethane, carbon tetrachloride, silicon tetrachloride. At least one selected from the group consisting of silicon, sulfur hexafluoride, titanium tetrachloride, dichlorosilane, trimethylgallium, trimethyldium, trimethylaluminum, air and carbon dioxide is used.

As for plasma, for example, in the manufacture of electronic devices, a plasma processing apparatus used in a film forming step, an etching step, an ashing step, an impurity addition step, a cleaning step, etc. (AC voltage under an atmosphere contained as a plasma generating gas). A device that performs plasma processing by applying a DC voltage, a pulse voltage, a high frequency, a microwave, or the like to generate a plasma).

(ozone)
Examples of ozone include those generated when oxygen is exposed to ultraviolet rays, those generated by discharging oxygen-containing gas such as dry air or oxygen gas, and those generated by electrolysis of dilute sulfuric acid. For example, ozone generated in an ozone treatment apparatus used in a film forming process, an ashing process, a cleaning process, etc. in the manufacture of an electronic device, ozone generated in the generation of photochemical smog, or the like may be used.

(Ultraviolet rays)
Ultraviolet rays refer to electromagnetic waves having a wavelength of about 1 to 400 nm, and include near ultraviolet rays, far ultraviolet rays or vacuum ultraviolet rays, and extreme ultraviolet rays or extreme ultraviolet rays. Examples thereof include ultraviolet rays generated from an ultraviolet irradiation device including a mercury lamp and an LED, and ultraviolet rays generated in an ultraviolet processing device used in a photolithography process, an ashing process, a cleaning process, etc. in manufacturing an electronic device.

(Radical-containing gas)
Radical-containing gas is generated by giving energy to the gas. For example, it can be produced by passing hydrogen through a thin tube made of Ta heated to 2100 K by an electron beam impact. In such an environment in which a radical-containing gas is used, it is preferable to control the flow rate of hydrogen to maintain the degree of vacuum at about 1.0 × 10 ^-4 Torr to 1.0 × 10 ^-6 Torr. For example, radical-containing gas generated in a radical-containing gas treatment apparatus used in a film forming step, an etching step, an ashing step, a cleaning step, etc. in the manufacture of an electronic device can be mentioned.

(Structure)
The structure constituting the detection layer of the present invention is composed of at least one selected from the group consisting of an organic material, an inorganic material and an organic-inorganic composite material, and has an internal space communicating with a hole on the surface. .. The color tone may be any as long as it can grasp the change in the color tone of the detection component, and is preferably transparent, colored transparent, white, light color, or the like.
As the structure, for example, a porous body having an internal space communicating with the opening portion on the surface, one or more of holes, recesses, protrusions and cracks are provided by a known appropriate means, and the opening portion on the surface is provided. It is possible to use a composition in which a material corresponding to an internal space communicating with the above is formed, a composition in which a porous substance is arranged on the surface, or the like. Of these, a porous body having an internal space communicating with the opening on the surface is preferably used.
The organic material, the inorganic material, and the organic-inorganic composite material constituting the structure are composed of at least one kind of compound. If necessary, a component such as a bulking agent may be contained. When the content of each metal atom in the laminate is less than 5.0 mass ppm, it is preferable to use a structure that does not contain metal atoms.
In the present invention, the structure has a function of hiding the color of the wafer and can greatly change the color tone. Further, by using the structure, the detection agent can cause a color tone change with time according to the penetrance of plasma or the like, or a color tone change proportional to the amount and intensity of exposure to plasma or the like.

The porous body having an internal space communicating with the pores on the surface may be, for example, an inorganic porous body, an organic porous body, or an organic-inorganic composite porous body.
Examples of the inorganic porous body include a metal porous body, a silica-based porous body (silica, aerosol, colloidal silica, etc.), an alumina-based porous body (active alumina, etc.), and a zeolite-based porous body (aluminosilicate zeolite). , Metallosilicate zeolite, aluminophosphate zeolite, etc.), silicate-based porous body (kaolinite, montmorillonite, mica, etc.), mesoporous-based porous body (mesoporous silica, etc.), glass porous body, ceramic porous body, At least one selected from the group consisting of porous materials such as pebbles, metal oxides and metal hydroxides (almite, hydroxyapatite, hydrotalcite, layered zirconium phosphate, heteropolyate, porous manganese oxide, etc.) However, it is not particularly limited.

The organic porous body is selected from the group consisting of, for example, resin porous bodies (porous films, porous polymer beads, etc.), non-woven fabrics, knitted fabrics, textiles, paper, wood, leather, activated carbon, fullerenes, carbon nanotubes, and the like. At least one of these can be mentioned, but is not particularly limited.

As the resin constituting the resin porous body, for example, known or commercially available ones can be used, for example, polyamide-based resin, polyamideimide-based resin, polyimide-based resin, amino-based resin (melamine-based resin / benzoguanamine-based resin). Resins, urea-based resins, etc.), acrylic resins ((meth) acrylic resins, poly (meth) acrylonitrile-based resins, poly (meth) acrylamide-based resins, etc.), polyvinylpyrrolidone-based resins, polyvinylimidazole-based resins, polyolefin-based resins (Polyethylene-based resin, polypropylene-based resin, etc.), Fluorine-based resin, vinyl chloride-based resin, vinyl acetate-based resin, polyvinyl acetal-based resin (polyvinyl butyral-based resin, etc.), polyvinyl alcohol-based resin, polystyrene-based resin (polystyrene-based resin, Styrene-maleic acid resin, styrene-acrylic acid resin, etc.), polyester resin (polyester resin, unsaturated polyester resin, alkyd resin, etc.), phenol resin (phenol resin, alkylphenol resin, terpenphenol, etc.) (Resin, rosin-modified phenol resin, etc.), polyether resin, epoxy resin, maleic acid resin, polyketone resin, polyethyleneimine resin, polyurethane resin, polysiloxane resin, acetal resin, block polymerization system At least one selected from the group consisting of resins, graft polymerization system resins, cellulose resins, rosin resins (rosin resins, rosin ester resins, etc.), rubber resins (natural rubber, diene rubber, SB rubber, etc.), etc. Seeds can be given, but are not particularly limited.

Of these resins, preferably polyimide resins, polyamideimide resins, polyamide resins, polyolefin resins, polyurethane resins, melamine resins, polyester resins and polycarbonate resins can be used. In particular, if a heat-resistant polymer such as a polyamide-imide resin, a polyimide resin, or a polyamide resin is used as the structure, the laminate has excellent heat resistance, so that it can be used under high temperature conditions and is strong. It is possible to construct an indicator having resistance to various plasma treatments.

Examples of the organic-inorganic composite porous body include, but are not limited to, at least one selected from the group consisting of a porous body of a resin composition containing an inorganic component, an organic metal-organic framework (MOF), and the like.
The organic component constituting the organic-inorganic composite porous body constitutes an organic component constituting the organic porous body, and the inorganic component constituting the organic-inorganic composite porous body constitutes an organic porous body. Inorganic components and well-known inorganic fillers can be used respectively.

In the structure, a structure having one or more holes, recesses, protrusions and cracks corresponding to an internal space by providing one or more of holes, recesses, protrusions and cracks by a known appropriate means is perforated by a needle, a laser or the like. Those with holes by spraying, those with holes or recesses by chemical treatment, those with recesses by embossing or grinding, those with protrusions by spraying convex-forming material, those with fine surface A resin composition containing a crack-forming agent such as an inorganic filler that forms cracks, a material in which cracks are provided by preparing using a paint, etc., a material in which a porous filler or the like is mixed with a binder such as resin, etc. Can be used.

In the present invention, when the content of each metal atom in the laminate is less than 5.0 mass ppm, it is preferable to use an organic porous body, particularly a resin porous body, as the structure constituting the detection layer. ..
Further, in order to prevent contamination of the electronic device manufacturing apparatus by metal atoms, it is preferable to use an organic porous body, particularly a resin porous body, as the structure constituting the detection layer.

As the resin porous body, a resin prepared by a known method can be used, and examples thereof include the following methods (1) to (4).
(1) Porousization by chemical means such as using a pore-forming agent (for example, perforation with a foaming agent, porosity using a gas generated during polymerization, modification or molding, after molding (after film formation) Porculation to remove porosity forming agent (removal of components, sublimation, etc.), porosity by phase separation (use of mixed solvent with different solubility, etc.), etc.)
(2) Porousization by stretching (3) Porousization by fusion of powders and granules (4) Porousization by mechanical means such as perforation

In the present invention, the resin porous body obtained by the method (1) above is preferable. In particular, a porous coating film obtained by applying a resin solution containing two or more kinds of solvents having different solubilities or boiling points is preferable as the resin porous body.
For example, by using a resin solution containing a polyimide resin or a polyamideimide resin, a good solvent for these resins, and a poor solvent for these resins, a polyimide resin porous body or a polyamide resin porous body can be obtained. Obtainable.
Examples of a good solvent for a polyimide resin or a polyamide-imide resin include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, and tetramethylurea. At least one solvent selected from the group consisting of dimethylethyleneurea, 1,3-dimethyl-2-imidazolidinone and the like is used.
As the poor solvent for the polyimide resin or the polyamideimide resin, a solvent having a solubility of less than 1% by mass can be used. For example, an ether solvent (tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tripropylene glycol) can be used. Dimethyl ether, dipropylene glycol dimethyl ether, tetrahydrofuran, dioxane, etc.), hydrocarbon solvents (n-hexane, cyclohexane, benzene, toluene, xylene, petroleum ether, etc.), ester solvents (ethylcarbitol acetate, butylcarbitol acetate, khaku) Selected from the group consisting of dimethyl acid acid, diethyl succinate, dimethyl glutarate, diethyl glutarate, dimethyl adipate, diethyl adipate, etc.), alcoholic solvents (triethylene glycol, diethylene glycol, ethylene glycol, methanol, ethanol, etc.), etc. At least one solvent is used.
Preferably, a polyamide-imide resin porous body obtained from a resin solution containing a polyamide-imide resin, N-methyl-2-pyrrolidone, and tetraethylene glycol dimethyl ether, a polyimide resin, and N, N-dimethylacetamide. And a polyimide-based resin porous body obtained from a resin solution containing tetraethylene glycol dimethyl ether.

(Detective agent)
The detection agent in the present invention contains at least one detection component whose color tone changes by detecting plasma or the like.
Further, the detection agent can contain various components as necessary for the purpose of adjusting the sensitivity and improving the visibility of the color difference before and after the detection within a range that does not impair the effect of the color tone change due to the detection component. ..
Such components include, for example, dyes that do not function as the detection component (those whose color tone does not change when exposed to the detection target), resins and / or resin precursors, reaction accelerators, and reaction delays. Contains additives such as agents, fillers and surfactants.

In the present invention, in order to make the content of each metal atom in the laminate less than 5.0 mass ppm, it is preferable that the detection agent containing the detection component does not contain the metal atom. As a result, when the laminate is used as an indicator for detecting plasma or the like in the manufacturing apparatus of the electronic device, contamination by metal atoms in the manufacturing apparatus of the electronic device can be effectively prevented.
In the present invention, it is preferable to use a detection agent containing a dye compound containing no atoms other than carbon, hydrogen, oxygen and nitrogen. As a result, when the laminate is used as an indicator for detecting plasma or the like, contamination in the manufacturing apparatus of the electronic device, particularly contamination by metal atoms or halogen atoms can be effectively prevented.
It is preferable that the detection agent is not contaminated with impurities such as metal atoms and halogen atoms by sufficiently purifying its constituent components and by not using a metal instrument for preparation.

-Detection component-
The compound used as a detection component in the present invention whose color tone changes by detecting plasma or the like is not particularly limited as long as it exhibits a behavior in which the color tone changes when exposed to plasma or the like.
Examples of such a compound include a dye known as a colorant, preferably a dye or a pigment whose color tone changes by detecting plasma or the like.

Examples of the dye include known or commercially available dyes. For example, anthraquinone dyes, benzoquinone dyes, perylene dyes, methine dyes, azo dyes (monoazo dyes, diazo dyes, triazo dyes, polyazo dyes, azoic dyes (diazo components, coupling components), etc. ), Phthalocyanine dyes, diarylmethane dyes, triarylmethane dyes, xanthene dyes, oxazine dyes, edible dyes, perinone dyes, diketopyrrolopyrrole dyes, quinacridone dyes, anthraquinone dyes, perinone dyes. Dyes, isoindolinone dyes, isoindoline dyes, indanslen dyes, coumarin dyes, quinacridone dyes, pyranthrene dyes, flavanthron dyes, nitroso dyes, nitro dyes, stilben dyes, carotenoid dyes Dyes, acridine dyes, quinoline dyes, thiazole dyes, naphthoquinone dyes, indamine dyes, indophenol dyes, azine dyes, thiazine dyes, sulfide dyes, lactone dyes, hydroxyketone dyes, aminoketone dyes. Dyes, indigoid dyes, thioindigo dyes, cationic dyes, cyanine dyes, squarylium dyes, croconium dyes, merocyanine dyes, fluorane dyes, spiropyran dyes, flugide dyes, azulene dyes, natural dyes, At least one selected from the group consisting of oxidizing dyes, metal complex dyes, and the like can be mentioned, but is not limited thereto.

Among the dyes, the dyes for detecting plasma include anthraquinone dyes, perylene dyes, methine dyes, azo dyes, phthalocyanine dyes, triarylmethane dyes, xanthene dyes, and indanthrone dyes. And at least one selected from the group consisting of food dyes is preferably used.
Among the dyes, it is preferable to use at least one selected from the group consisting of oxazine dyes, azo dyes, methine dyes, indanthrone dyes and anthraquinone dyes as the dye for detecting ozone. ..

Among the dyes, the dyes for detecting ultraviolet rays include azo dyes, anthraquinone dyes, triarylmethane dyes, phthalocyanine dyes, indigo dyes, diarylmethane dyes, triarylamine dyes and cyanine dyes. It is preferable to use at least one selected from the group consisting of dyes.
Further, a compound that changes the coloring mechanism of the dye by ultraviolet irradiation together with the dye for detecting the ultraviolet rays, and the compound itself changes to a compound that changes the coloring mechanism of the dye by ultraviolet irradiation. / Or, it is preferable to use a compound that generates a free group in which the compound changes the color development mechanism by irradiation with ultraviolet rays.
Examples of the compound that changes the color development mechanism of the dye by ultraviolet irradiation include an acetophenone type compound, a benzophenone type compound, a Michler ketone type compound, a benzyl type compound, a benzoin type compound, a benzoin ether type compound, a benzyl dimethyl ketal type compound, and a benzoin benzoate type. At least one selected from the group consisting of compounds, α-acoxime ester type compounds, tetramethyluram monosulfide type compounds, thioxanthone type compounds and acylphosphine oxide type compounds can be mentioned, but is not limited thereto.
In particular, it is preferable to use a compound that generates a free radical that changes the color development mechanism by irradiation with ultraviolet rays, and at least one selected from compounds having an absorption maximum at a wavelength of about 150 to 450 nm (more preferably 200 to 400 nm). Seeds are preferred.
The blending amount of the compound that changes the color development mechanism of the dye by ultraviolet irradiation can be determined according to the type of dye used and the like. The amount may be such that a sufficient discoloration effect that can be visually recognized can be obtained and the amount does not cause a problem in solubility in a solvent or the like. For example, it is usually about 0.1 to 20 mol, preferably about 0.1 to 20 mol, per 1 mol of the dye. 0.5 to 15 mol can be given.

When a benzophenone-type compound, a Michler-ketone-type compound, a benzyl-type compound, a thioxanthone-type compound or the like is used as a compound that changes the color development mechanism of the dye by irradiation with ultraviolet rays, an amine-based reaction accelerator such as ethanolamine (amine-based radical promotion) Agent) is preferably used in combination. In such a case, the blending amount of the amine reaction accelerator can be appropriately determined according to the above compound, dye and the like.
Examples of the combination of the dye and the compound that changes the color development mechanism of the dye by irradiation with ultraviolet rays include (1) the anthraquinone-based dye is a combination of a benzoin ether type compound, a benzyl dimethyl ketal type compound, or an acylphosphine oxide type compound. (2) The disazo dye is a combination with a benzoin ether type compound or an acylphosphine oxide type compound, (3) the phthalocyanine type dye is a combination with a benzoin ether type compound or an acylphosphine oxide type compound, and (4) the cyanine type dye is a benzophenone. Examples thereof include a combination with a type compound and (5) a combination with a benzophenone type compound or an acylphosphine oxide type compound as the azo dye.

Among the dyes, at least one selected from the group consisting of anthraquinone dyes, azo dyes and triarylmethane dyes is preferably used as the dye for detecting radical-containing gas.

In the present invention, among the dyes, anthraquinone dyes, perylene dyes, methine dyes, azo dyes (monoazo dyes, diazo dyes, triazo dyes, polyazo dyes, azoic dyes (diazo components), etc. At least one selected from the group consisting of azoic pigments (coupling components, etc.), phthalocyanine pigments, triarylmethane pigments, xanthene pigments, oxazine pigments, indanthrone pigments, food dyes and perinone pigments. It is preferable to use. Particularly preferred is at least one selected from the group consisting of anthraquinone dyes, perylene dyes, methine dyes, indanthrone dyes, and azo dyes.

Specific examples of these dyes include CIAcid Black 123 and CIAcid Blue 1,3,5,7,9,11,15,17,19,22,23,24,38,48,75,80. , 83,86,88,90,91,93,93: 1,100,103,104,108,109,110,119,123,147,213,269, CIAcid Green 16, CIAcid Red 52,81,83, CIAcid Violet 1,3,7,10,12,14,15,16, 17,19,20,21,23,25,30,38,39,43,48,49,72, CIAcid Yellow 11,12,13,14,21,22,23,24,74, CIAzoic Coupling Component 2,3,4,5,7,11,14,16,17,18,19,20,29,36, CIAzoic Diazo Component 1,5,8,12,13,20,24,34,41 , 48,109, CIAzoic Brown 11, CIBasic Blue 1,5,7,8,26,62,63,140, CIBasic Green 1,4, CIBasic Red 1,9,12,13,14,15,27,35 , 36,37,45,48, CIDeveloper 8,18,20,21,22, CIDirect Blue 41,86,87, CIDisperse Black 1,2,29, CIDisperse Blue 1,3,5,6, 7,26,27,44, CIDisperse Orange 1,3,5,11,13, CIDisperse Red 1,4,9,11,13,15,17,52,58,88,167: 1, CIDisperse Violet 1 , 4,8, CISisperse Yellow 1,3,4,5,7,8,23,31,60,61, CIMordant Blue 1, CIMordant Red 11,15,27, CIMordant Violet 1,25, CI Pigment Blue 15,15: 3,15: 4,15: 6,16, CIPigment Green 7,36, CIReactive Blue 4,19, CI Solvent B lack 3, CISolvent Brown 3,5, CISolvent Blue 11,14,35,63,70, CISolvent Green 3,5,15, CISolvent Orange 1,2,14,55,60,78,90, CI Solvent Red 1,3,18,23,24,25,27,49,52,114,135,162,179, CISolvent Violet 8,13,14,29, CISolvent Yellow 2,6,14,16,21,29,33,56, CIVat Black 8,9,25,27,29, CIVat Brown 1,3,25,44, CIVat Blue 1,4,12,20,21,30, CIVat Green 1,3,8,9, CIVat Orange 7,9,13,15, CIVat Red 10,13,15,19,28,29, CIVat Violet 13,15,17, CIVat Yellow 4,10,20, Lumogen FIR 788, Lumogen F Orange 240, Lumogen F Pink 285, Lumogen F Red 300,305,339, Lumogen F Violet 570, Lumogen F Yellow 083,170, Iketon Violet extra, Oil Peacock Blue, Oil Brown BG extra, Edible Red No. 1, Edible Red No. 3, Edible Red 102 No., Edible Red No. 104, Edible Red No. 105, Edible Red No. 106, Edible Yellow No. 4, Edible Yellow No. 5, Edible Green No. 3, Edible Blue No. 1, Edible Blue No. 2, etc. At least 1 selected from the group Seeds can be given.

For example, CIAcid Black 123, CIAzoic Brown 11, CIAzoic Coupling Component 2,3,4,5,7,11,14,16,17,18,19,20,29,36, CIAzoic Diazo Component 1, 5,8,12,13,20,24,34,41,48,109, CIBasic Green 4, CIDeveloper 8,18,20,21,22, CIDisperse Black 1,2,29, CIDisperse Blue 1,3 , 5,6,7,26,27, CIDisperse Orange 1,3,11,13, CIDisperse Red 1,4,9,11,15,17, CIDisperse Violet 1,4,8, CIDisperse Yellow 1 , 3,4,5,7,8,23,31,60,61, CIMordant Red 11,15,27, CISolvent Black 3, CISolvent Blue 11,35, CISolvent Brown 3,5, CISolvent Green 3, CISolvent Orange 1,2,14, CISolvent Red 1,3,18,23,24,25,27,49,52, CISolvent Violet 13,14, CISolvent Yellow 2,6,14,16, 21,29,33,56, CIVat Black 8,9,25,27,29, CIVat Blue 1,4,12,20, CIVat Brown 1,3,25,44, CIVat Green 1,3, 8,9, CIVat Orange 7,9,13,15, CIVat Red 10,13,15, CIVat Violet 13, CIVat Yellow 4,10,20, Lumogen FIR 788, Lumogen F Orange 240, Lumogen F Pink 285, Lumogen F Red 300,305,339, Lumogen F Violet 570, Lumogen F Yellow 083,170, Iketon Violet extra, Oil Peacock Blue, Oil B It is preferable to use at least one selected from the group consisting of rown BG extra and the like.

More preferably, CIAzoic Coupling Component 3,16, CIBasic Green 4, CIMordant Red 27, CISolvent Black 3, CISolvent Blue 35, CISolvent Red 18,24,27,49,52, CISolvent Violet 14, CISolvent Yellow 29, CIVat Black 8,9,25,27,29, CIVat Brown 1,3,25,44, CIVat Green 8, CIVat Orange 13,15, CIVat Red 10,13,15, From CIVat Yellow 10,20, Lumogen F IR 788, Lumogen F Orange 240, Lumogen F Pink 285, Lumogen F Red 300,305,339, Lumogen F Violet 570, Lumogen F Yellow 083,170, Iketon Violet extra, Oil Peacock Blue, Oil Brown BG extra At least one species selected from the group.

In the present invention, it is possible to control the detection sensitivity and control the coloration and color tone change of the detection layer by changing the type (molecular structure, etc.) of these dyes, using a plurality of dyes in combination, and the like. ..
The content of these dyes may be appropriately determined according to the type of dye, desired discoloration (detection sensitivity), product form, structure characteristics, and the like.
For example, the detection layer can contain 0.01 to 20% by mass, preferably 0.1 to 10% by mass of the dye. Further, for example, the detection agent can contain 0.01 to 100% by mass, preferably 0.1 to 100% by mass of the dye.

-Dyes that do not function as the detection component-
In the present invention, the detection agent may contain a dye that does not exhibit the function as the detection component.
By incorporating such a dye that does not exhibit the function as the detection component, the visual effect can be further enhanced by changing the color tone from one color to another.
Examples of the dye that does not exhibit the function as the detection component include at least one selected from the group consisting of dyes that do not change in color tone when exposed to the detection target, but are not particularly limited.
For example, select from a group consisting of a dye that does not change the color tone even if plasma or the like is detected, or a dye that does not change the hue depending on the detection target even if the dye that detects plasma or the like and causes a change in color tone. At least one of these can be used.
When the detection agent contains a dye that does not function as a detection component, the content thereof can be appropriately determined according to the type, visibility of the detection layer, desired color tone, etc., but is generally 0 in the detection agent. It is preferably about 99.99% by mass, particularly preferably 0 to 99.9% by mass.

-Resin and / or resin precursor-
In the present invention, the detection agent may contain a resin and / or a resin precursor that may function as a binder.
As the resin, either a natural resin or a synthetic resin may be used, or a commercially available resin may be used. Further, any molecular weight and molecular weight distribution can be used.
As the resin precursor, any resin precursor can be used as long as it can become a resin by reacting. For example, at least one selected from the group consisting of (meth) acrylate compounds, polyamic acids, polyurethane prepolymers and the like can be mentioned, but is not particularly limited.
The resin and / or the resin precursor is appropriately selected according to the components constituting the detection agent and the like.
By containing the resin and / or the resin precursor in the detection agent, for example, the fixability of the detection agent can be adjusted, the detection component can be prevented from being detached or peeled from the detection agent or the detection layer, and the detection component and the detection target can be separated from each other. Contact control, etc. ・ Sensitivity can be adjusted by BR>, and detectors can be protected.

As such a resin, known or commercially available ones can be used, for example, polyamide-based resin, polyamideimide-based resin, polyimide-based resin, amino-based resin (melamine-based resin / benzoguanamine-based resin, urea-based resin, etc.). ), Acrylic resin ((meth) acrylic resin, poly (meth) acrylonitrile resin, poly (meth) acrylamide resin, etc.), polyvinylpyrrolidone resin, polyvinylimidazole resin, polyolefin resin (polyethylene resin, polypropylene) (Resin, etc.), Fluorine resin, Vinyl chloride resin, Vinyl acetate resin, Polyvinyl acetal resin (Polyvinyl butyral resin, etc.), Polyvinyl alcohol resin, Polystyrene resin (Polystyrene resin, Styrene-maleic acid resin, etc.) , Styrene-acrylic acid resin, etc.), polyester resin (polyester resin, unsaturated polyester resin, alkyd resin, etc.), phenol resin (phenol resin, alkylphenol resin, terpenphenol resin, rosin modified phenol) (Resin etc.), polyether resin, epoxy resin, maleic acid resin, polyketone resin, polyethyleneimine resin, polyurethane resin, polysiloxane resin, acetal resin, block polymerization system resin, graft polymerization system resin , Cellulous resin, rosin resin (rosin resin, rosin ester resin, etc.), rubber resin (natural rubber, diene rubber, SB rubber, etc.), etc. At least one selected from the group can be mentioned. Not limited.
When the resin and / or the resin precursor is contained in the detection agent, the content thereof can be appropriately determined according to the type of the resin and / or the resin precursor, the type of the detection component to be used, and the like. For example, in general, it can be used in an amount of about 50% by mass or less, preferably 5 to 35% by mass, in the detection agent.

-Surfactant-
In the present invention, the surfactant may be contained in the detection agent.
Examples of the surfactant include, but are not limited to, at least one selected from the group consisting of nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants. Of these, particularly when detecting plasma, it is preferable to use at least one selected from the group consisting of nonionic surfactants and cationic surfactants. As a result, it is possible to promote discoloration of the detection component and improve the detection sensitivity of the detection component.

Examples of the nonionic surfactant include the following (1) to (4) (1) alkylene glycol derivatives (for example, polyethylene glycol (for example, trade name "PEG2000" manufactured by Sanyo Kasei Kogyo Co., Ltd.), polyethylene glycol-polypropylene). Glycol copolymer (for example, trade name "Epan 710" manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.), polyoxyalkylene alkyl ether (for example, trade name "Emargen 109P" manufactured by Kao Co., Ltd.), polyalkylene glycol monofatty acid ester, etc.) 2) Polyglycerin derivative, (3) alkylene glycol glyceryl derivative (for example, fatty acid polyoxyalkylene glyceryl (for example, trade name "Uniox GM-30IS" manufactured by Nichiyu Co., Ltd.), and (4) acetylene glycol derivative (for example). , At least one selected from the group consisting of "Surfinol 104H" manufactured by Air Products Japan Co., Ltd., etc.), but is not particularly limited.
When the nonionic surfactant is contained in the detection agent, the content thereof can be appropriately determined according to the type of the nonionic surfactant, the type of the detection component to be used, and the like. For example, it can be about 0.1 to 10% by mass, preferably 0.5 to 5% by mass, in the detection agent in consideration of the storage stability and the discoloration promoting effect in the detection agent.

Examples of the cationic surfactant include the following (1) to (4) (1) tetraalkylammonium salts (for example, alkyltrimethylammonium salts (for example, behenyltrimethylammonium chloride, lauryltrimethylammonium chloride, etc.), dialkyldimethyl. Ammonium salt, etc.), (2) Isoquinolinium salt (eg, laurylisoquinolinium bromide, etc.), (3) Imidazolinium salt (eg, 2-chloro-1,3-dimethylimidazolinium chloride, etc.), and (4) At least one selected from the group consisting of pyridinium salts (for example, hexadecylpyridinium chloride, etc.) and the like can be mentioned, but is not particularly limited.
When the cationic surfactant is contained in the detection agent, the content thereof can be appropriately determined according to the type of the cationic surfactant, the type of the detection component to be used, and the like. For example, it can be about 0.1 to 10% by mass, preferably 0.5 to 5% by mass, in the detection agent in consideration of the storage stability and the discoloration promoting effect in the detection agent.

-Filler-
In the present invention, the filler may be contained in the detection agent. As the filler, known or commercially available ones can be used, and for example, at least selected from the group consisting of bentonite, clay, activated clay, talc, alumina, silica, silica gel, calcium carbonate, barium sulfate, resin beads and the like. One type can be mentioned, but it is not particularly limited.
For example, when the detection agent contains a resin, if silica or the like is contained, a plurality of fine cracks are generated on the surface of the detection agent, so that the detection sensitivity can be improved.
The content of the filler can be appropriately determined according to the type of the filler, the type of the detection component to be used, and the like, as long as the effect of the color tone change by the detection component is not significantly impaired. For example, it can be about 0.1 to 10% by mass, preferably 0.5 to 5% by mass, in the detection agent in consideration of the storage stability and the discoloration promoting effect in the detection agent.

-Color change retarder-
In the present invention, a color tone change delaying agent may be contained in the detection agent in order to delay the color tone change of the detection agent. As the color tone change delaying agent, for example, an agent having a function of inhibiting contact between plasma or the like and a detection component can be used.
Examples of the color tone change retarder include an absorbent that absorbs plasma and the like (for example, a known or commercially available ion absorber, radical absorber, ozone absorber, ultraviolet absorber, etc.), and shields the detection component from plasma and the like. At least one selected from the group consisting of a shielding agent (for example, the above-mentioned resin, filler, etc.) and the like can be mentioned, but is not particularly limited.
The content of the color tone change retarder can be appropriately determined according to the desired color tone change delay effect, the composition of the detection agent, and the like, as long as the effect of the color tone change by the detection component is not significantly impaired. For example, it can be about 0 to 10% by mass in the detection agent.

-Color change accelerator-
In the present invention, a known or commercially available color tone change accelerator may be contained in the detection agent in order to promote the color tone change of the detection agent.
Examples of such a color tone change accelerator include a resin having a function of enhancing the accuracy (sensitivity) of detection of plasma and the like (for example, a nitrogen-containing resin effective for enhancing plasma detection), the surfactant, and the filling. At least one selected from the group consisting of agents and the like can be mentioned, but is not particularly limited.
The content of the color tone change delaying agent can be appropriately determined according to the desired effect of promoting the color tone change, the composition of the detection agent, and the like within a range that does not significantly impair the effect of the color tone change by the detection component. For example, it can be about 0 to 10% by mass in the detection agent.

− Solvent −
In the present invention, a known or commercially available solvent may be contained in the detection agent.
The solvent is used when introducing and holding the detection component in the internal space of the structure having an internal space having an opening on the surface in the detection layer. Usually, it is removed by means such as drying, but a small amount may be present in the detection agent.
Examples of the solvent include water, hydrocarbon solvents (eg, hexane, cyclohexane, toluene, xylene, benzene, tetralin, mineral spirit, etc.), alcohol solvents (eg, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, etc.). Flufuryl alcohol, octyl alcohol, stearyl alcohol, oleyl alcohol, benzyl alcohol, cyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, glycerin, trimethylolethane, trimethylolpropane, etc. ), Ether solvents (eg, dimethyl ether, diethyl ether, phenyl ether, benzyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tetrahydrofuran, dioxane, morpholine, etc.) , Ester solvents (eg, methyl acetate, ethyl acetate, butyl acetate, amyl acetate, ethyl lactate, glycol diacetate, dimethyl carbonate, vegetable oil, γ-butyrolactone, ε-caprolactone, etc.), ketone solvents (eg, acetone, methyl ethyl ketone, etc.) , Cyclohexanone, diacetone alcohol, isophorone, acetophenone, etc.), phenolic solvent (eg, phenol, cresol, etc.), fatty acid solvent (eg, hexadecanoic acid, isopalmitic acid, oleic acid, isostearic acid, etc.), carbonate solvent (eg, hexadecanoic acid, isopalmitic acid, oleic acid, isostearic acid, etc.) For example, dimethyl carbonate, diethyl carbonate, propylene carbonate, ethylene carbonate, etc.), amine solvents (triethanolamine, tripropanolamine, tributanolamine, N, N-dimethyl-2-aminoethanol, N, N-diethyl-2) -Aminoethanol, etc.), amide solvents (eg, acetamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.), halogenated hydrocarbon solvents (eg, carbon tetrachloride) , Chlorroide, trichloroethane, fluorine-containing solvent) and the like, but the present invention is not particularly limited.

The solvent may be any solvent that can dissolve or disperse the detection component. Preferably, a solvent capable of dissolving the detection component is used. It is preferable that the solvent is highly purified to reduce the content of metal atoms and halogen atoms. As a result, the content of metal atoms and the content of halogen atoms in the laminate are reduced.
When the detection component is introduced and held in the internal space, the amount of the solvent used can be appropriately determined according to the type of the solvent, the composition of the detection agent, and the like. Preferably, when a solution or dispersion of the detection component is formed, the amount is such that the detection component does not precipitate. For example, when a solvent capable of dissolving the detection component is used, the concentration of the detection component is preferably 0.1 to 30% by mass, but is not particularly limited.
When the detection component contains a solvent even after being held in the internal space, the content of the solvent is within a range in which the detection agent does not easily flow and the effect of the color tone change by the detection component is not impaired. Although it depends on the composition of the detection agent and the like, for example, the detection agent may contain about 0 to 1% by mass of a solvent.

-Other additives-
In the present invention, other additives other than the above-mentioned components may be contained in the detection agent, if necessary. Examples of other additives that may be contained in the detection agent in the present invention include, but are not limited to, at least one selected from the group consisting of leveling agents, antifoaming agents, and surface conditioners.
The content of other additives can be appropriately determined depending on the composition of the detection agent and the like as long as the effect of the color tone change by the detection component is not impaired. For example, it can be about 0 to 5% by mass in the detection agent.

<Base layer>
The base material layer may be any one that can support the detection layer. In consideration of the characteristics and uses required for the laminate, at least one selected from the group consisting of inorganic materials, organic materials and composites thereof can be mentioned, but is not particularly limited.
The thickness of the base material layer is not particularly limited as long as it can reliably support the detection layer, and can be 0.01 to 10 mm, preferably 0.01 to 1 mm.
Examples of the inorganic material include, but are not limited to, at least one selected from the group consisting of metals or alloys, semiconductor materials, ceramics, glass, quartz, sapphire, concrete and the like.
Examples of the organic material include, but are not limited to, at least one selected from the group consisting of resin, paper, synthetic paper, wood and fibers (nonwoven fabric, knitted fabric, woven fabric, other fiber sheet), leather and the like.
Examples of the composite include, but are not limited to, a laminate and a composition obtained by using at least one material selected from the group consisting of the inorganic material and the organic material.
As the base material layer, it is preferable to use at least one selected from the group consisting of semiconductor materials, glass, sapphire, resin and paper.

Examples of the semiconductor material include silicon (Si), germanium (Ge), tellurium (Te), zinc oxide (ZnO), gallium arsenide (GaAs), gallium nitride (GaN), gallium oxide (Ga ₂ O ₃ ), and the like. Aluminum Nitride (AlN), Indium Nitride (InN), Silicon Carbide (SiC), Aluminum Gallium Nitride (AlGaN), Indium Gallium Nitride (InGaN), Indium Gallium Nitride (InAlGaN), Diamond, VDD Material (β-FeSi ₂ , At least one selected from the group consisting of MgSi ₂ , NiSi ₂ , BaSi ₂ , CrSi ₂ , CoSi ₂ , TaSi, etc.), metal oxides, metal oxynitrides, etc. can be mentioned, but is not particularly limited.

Here, examples of the metal oxide or metal oxynitride include In-Sn-Ga-Zn-O oxide, In-Hf-Ga-Zn-O oxide, and In-Al-Ga-Zn. -O oxides, In-Sn-Al-Zn-O oxides, In-Sn-Hf-Zn-O oxides, In-Hf-Al-Zn-O oxides, In-Ga-Zn -O-based oxides, In-Sn-Zn-O-based oxides, In-Al-Zn-O-based oxides, Sn-Ga-Zn-O-based oxides, Al-Ga-Zn-O-based oxides, Sn-Al-Zn-O oxides, In-Sn-Zn-O oxides, In-Hf-Zn-O oxides, In-La-Zn-O oxides, In-Ce-Zn- O-based oxides, In-Pr-Zn-O-based oxides, In-Nd-Zn-O-based oxides, In-Sm-Zn-O-based oxides, In-Eu-Zn-O-based oxides, In -Gd-Zn-O oxides, In-Tb-Zn-O oxides, In-Dy-Zn-O oxides, In-Ho-Zn-O oxides, In-Er-Zn-O In-Tm-Zn-O Oxide, In-Yb-Zn-O Oxide, In-Lu-Zn-O Oxide, In-Zn-O Oxide, Sn-Zn- O-based oxides, Al-Zn-O-based oxides, Zn-Mg-O-based oxides, Sn-Mg-O-based oxides, In-Mg-O-based oxides, In-Ga-O-based oxides, At least one selected from the group consisting of Zn-ON oxynitrides, In-O oxides (indium oxide), Sn-O oxides (tin oxide), Zn-O oxides (zinc oxide), etc. However, it is not particularly limited.
Here, for example, the In-Sn-Ga-Zn-O-based oxide is an oxide semiconductor having indium (In), tin (Sn), gallium (Ga), zinc (Zn) and oxygen (O). This means that the composition ratio of each atom is not particularly limited, and in some cases, an atom such as silicon (Si) may be contained.

As the resin, known or commercially available ones can be used, for example, polyolefin resins (polyethylene, polypropylene, polynorbornene, etc.), polyvinyl chloride resins, vinylidene chloride resins, fluororesins, polyester resins. (Polyethylene terephthalate, polyethylene naphthalate, etc.), polystyrene resin, polyimide resin, polyamide resin, polyamideimide resin, polysulfone resin, polysulfide resin, polyether ketone resin, polyether resin, polyurethane resin, At least one selected from the group consisting of polycarbonate-based resins, acrylic-based resins, ABS-based resins, and the like can be mentioned, but is not particularly limited.
Preferably, it is selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polyethylene resin, polypropylene resin, polynorbornene resin, polyamide resin, polyamideimide resin, polyimide resin, polycarbonate resin, acrylic resin and the like. At least one type can be mentioned.

For example, when the laminate is used as an indicator for an apparatus for manufacturing a semiconductor, the base material is preferably silicon, gallium arsenide, or silicon carbide.
For example, when the laminate is used as an indicator for an apparatus for manufacturing LEDs, the base material is preferably sapphire, gallium nitride, gallium arsenide, or the like.
For example, when the laminate is used as an indicator for an apparatus for manufacturing a semiconductor laser, the base material is preferably gallium arsenide, gallium nitride, sapphire, or the like.
For example, when the laminate is used as an indicator for an apparatus for manufacturing a power device, the base material is preferably silicon carbide, gallium nitride, silicon or the like.
For example, when the laminate is used as an indicator for an apparatus for manufacturing a solar cell, the base material is preferably silicon, glass, germanium or the like.
For example, when the laminate is used as an indicator for an apparatus for manufacturing a liquid crystal display, the base material is preferably silicon, glass, germanium or the like.
For example, when the laminate is used as an indicator for an apparatus for manufacturing an organic EL display, the base material is preferably glass or the like.
For example, when the laminate is an inexpensive or simple indicator, the base material is preferably resin, paper, glass or the like.

<Content of each metal atom>
In the present invention, the content of each metal atom in the laminate can be less than 5.0 mass ppm, for example, less than 1.0 mass ppm. It is preferably less than 0.5 mass ppm, more preferably less than 0.1 mass ppm, more preferably less than 1 mass ppt, and most preferably less than 0.5 mass ppt.
Here, the "metal atom" means an atom other than hydrogen, carbon, nitrogen, oxygen, silicon, fluorine, chlorine, bromine, iodine and a rare gas.
In order to make the content of each metal atom in the laminate less than 5.0 mass ppm, for example, less than 1.0 mass ppm, the detection layer and the base material layer are composed of those containing no metal atom. Further, all the components (including the solvent and the like) related to the laminate are made free of metal atoms, and further, the metal atom-containing substances contained as impurities are removed by purification. Further, in the manufacturing process, it is preferable not to use an instrument or the like in which metal atoms are mixed (contamination).
In the present invention, the content of each metal atom of each material and substrate layer constituting the detection layer is measured by ICP-MS (Inductively Coupled Plasma Mass Spectrometry) or the like, and each of them is 5. If it is less than 0 mass ppm, it is assumed that the content of each metal atom in the laminate is less than 5.0 mass ppm.
In addition, the indicator containing the laminate of the present invention is introduced into the processing apparatus together with the material to be processed, and processing such as plasma processing is performed. After that, each metal atom on the surface of the material to be treated introduced into the treatment apparatus was recovered with hydrofluoric acid or the like, and the content of each metal atom was measured by ICP-MS or the like, and each was less than 5.0 mass ppm. If so, each metal atom in the laminate may be less than 5.0 mass ppm.
By setting the content of each metal atom in the laminate to less than 5.0 mass ppm, for example, less than 1.0 mass ppm, when the laminate is used as an indicator used in an electronic device manufacturing apparatus, the object to be treated or the above. It is possible to prevent contamination of metal atoms in the manufacturing equipment.
This makes it possible to obtain an indicator that can be used even in a manufacturing process of a semiconductor electronic device that dislikes the presence of metal atoms (particularly, an etching process in the first half process).

<Content of each halogen atom>
In the present invention, the content of each halogen atom in the laminate can be less than 30 mass ppm, for example, less than 5 mass ppm. It is preferably less than 1 mass ppm, more preferably less than 0.5 mass ppm, and most preferably less than 1 ppt.
In order to make the content of each halogen atom in the laminate less than 30 mass ppm, for example, less than 5 mass ppm, it is preferable that the detection layer and the base material layer are composed of those containing no halogen atom. Further, it is preferable to use a halogen atom-free substance for all the components (including a solvent) related to the laminate and to remove the halogen atom-containing substance contained as an impurity by purification. Further, in the manufacturing process, it is preferable to use a method or the like that does not use an instrument or the like in which halogen atoms are mixed (contamination).
In the present invention, the content of each halogen atom is measured by combustion ion chromatography or ICP-MS (Inductively Coupled Plasma Mass Spectrometry) or the like for each material and base material layer constituting the detection layer. If each is less than 30 mass ppm, it is assumed that the content of each halogen atom in the laminate is less than 30 mass ppm.
In addition, the indicator containing the laminate of the present invention is introduced into the processing apparatus together with the material to be processed, and processing such as plasma processing is performed. After that, the halogen atoms on the surface of the material to be treated introduced into the processing apparatus are recovered and the content of each halogen atom is measured by combustion ion chromatography or ICP-MS. If each is less than 30 mass ppm, It is also possible that the content of each halogen atom in the laminate is less than 30 mass ppm.
By setting the content of each halogen atom in the laminate to less than 30 mass ppm, for example, less than 5 mass ppm, when the laminate is used as an indicator used in an electronic device manufacturing apparatus, it is present in the object to be processed or in the manufacturing apparatus. It is possible to prevent contamination of halogen atoms.
This makes it possible to obtain an indicator that can be used even in a manufacturing process of a semiconductor electronic device that dislikes the presence of halogen atoms (particularly, an etching process in the first half process).

<Layer structure>
The laminate of the present invention may have a non-detection layer in which the color tone does not change even if plasma or the like is detected, in addition to the detection layer and the base material layer in which the color tone changes by detecting plasma or the like.
The order of laminating the detection layer, the base material layer and the non-detection layer may be arbitrary.
The detection layer and the non-detection layer may be formed one layer each, or a plurality of layers may be formed respectively. Further, the discolored layers or the non-discolored layers may be laminated. In this case, the detection layers may have the same composition or different compositions, and the non-discoloring layers may have the same composition or different compositions.
The detection layer and the non-detection layer may be formed on the entire surface of the base material layer or each layer, or may be partially formed. In these cases, the detection layer and the non-detection layer can be formed so that at least a part or all of the detection layer is exposed to plasma or the like, particularly in order to secure a change in the color tone of the detection layer.

In the laminated body of the present invention, the discolored layer and the non-discolored layer may be combined in any way as long as the completion of each of the above treatments and the in-plane uniformity can be confirmed.
For example, the color tone of the detection layer before the color tone changes and the color tone of the non-detection layer are formed as the same, and the color tone of the detection layer changes due to plasma or the like so that the color difference between the detection layer and the non-detection layer can be identified. A detection layer and a non-detection layer can be formed.
Further, the color tone of the detection layer before the color tone is changed and the color tone of the non-detection layer are formed as different ones, and the color tone of the detection layer is changed by plasma or the like so that the color difference between the detection layer and the non-detection layer is eliminated. A detection layer and a non-detection layer can be formed.

In the laminated body of the present invention, it is particularly preferable to form the detection layer and the non-detection layer so that the color difference between the detection layer and the non-detection layer can be discriminated by changing the color tone of the detection layer due to plasma or the like.
For example, when the color difference of the discolored layer can be identified by changing the color tone of the detection layer due to plasma or the like, for example, the discolored layer and the non-discolored layer so that at least one kind of characters, patterns and symbols appears due to the discoloration of the discolored layer. A discolored layer can be formed.
The characters, patterns and symbols include all the information for notifying the discoloration, and these characters and the like can be appropriately designed according to the purpose of use and the like.

In the laminated body of the present invention, the detection layer and the non-detection layer can be prevented from overlapping, and the detection layer and the non-detection layer can be overlapped.
Further, in the laminated body of the present invention, a detection layer or a non-detection layer can be further formed on at least one of the detection layer and the non-detection layer.
For example, if a detection layer having a different design is formed on top of a layer in which the detection layer and the non-detection layer are formed so that the detection layer and the non-detection layer do not overlap (referred to as “detection-non-detection layer”), Since the boundary line between the detection layer and the non-detection layer in the detection-non-detection layer can be made substantially indistinguishable, better design can be achieved.
In the laminated body of the present invention, as a preferable aspect of the layer structure,
(1) A laminate in which the detection layer is formed adjacently on at least one main surface of the base material layer,
(2) A non-detection layer and a detection layer are sequentially formed on the base material layer, the non-detection layer is formed adjacent to the main surface of the base material layer, and the detection layer is the said. Laminates formed adjacently on the main surface of the non-detection layer,
Can be given. In the laminated body of the above (1), the non-detection layer may be a laminated body formed adjacent to the main surface of the detection layer.

<Shape>
The shape of the laminated body of the present invention can be any shape depending on the application and the like.
For example, it can be the same as the shape of the substrate used in the electronic device manufacturing apparatus.
As a result, the laminated body can be used as a so-called dummy substrate, and it is possible to easily detect whether or not the above processing is uniformly performed on the entire substrate.
Here, "the same as the shape of the substrate used in the electronic device manufacturing apparatus" is used in the electronic device manufacturing apparatus in addition to the case where it is completely the same as the shape of the substrate used in the electronic device manufacturing apparatus. It may be any case where the shape of the substrate is substantially the same so that it can be placed (fitted) at the installation location of the substrate in each electronic device device to be processed. Substantially the same means, for example, the length of the main surface of the laminate with respect to the length of the main surface of the substrate (diameter when the main surface shape is circular, vertical and horizontal length when the main surface shape is square or rectangular). The difference between the two is within ± 5.0 mm, and the difference in the thickness of the laminate with respect to the substrate is within ± 1000 μm.

<Manufacturing method of laminated body>
Examples of the method for producing the laminated body include the following methods (1) to (4), but the method is not particularly limited.
(1) After providing a structure having an internal space communicating with the opening on the surface by a known appropriate means on the base material layer, a detection agent or a detection agent solution is applied, impregnated, sprayed or the like. , A method of retaining a detection agent in the internal space.
(2) A structure having an internal space that communicates with the opening on the surface is formed by a known appropriate means, and a detection agent or a detection agent solution is applied, impregnated, sprayed, or the like to the structure in the internal space. A method in which the detection agent is retained and then fixed onto the base material layer by a known appropriate means.
(3) After providing a composition containing the component forming the structure, the component forming the internal space communicating with the opening on the surface of the structure in the structure, and the detection agent on the base material layer, A method of forming an internal space in a structure that communicates with an opening on the surface.
(4) A composition containing the component forming the structure, the component forming the internal space communicating with the opening on the surface of the structure, and the detection agent is prepared, and the opening on the surface of the structure is prepared. A method of forming an internal space communicating with a portion and holding a detection agent in the internal space, and then fixing the detection agent on the base material layer by a known appropriate means.
In the present invention, the method (1) or (2) is preferable, and the method (1) is more preferable, from the viewpoints of ease of manufacturing the laminate, prevention of impurities from being mixed into the laminate, and the like.

When mixing, dissolving or dispersing, a known stirrer can be used, if necessary. At this time, it is preferable not to mix the contaminated components caused by the stirrer.
Known methods can be used for mixing, dissolving or dispersing. For example, a method of adding the detection component to the solvent, a method of adding the solvent to the detection component, a method of adding each component constituting the detection agent to the solvent in order, and the like can be used.
When the detection component is retained in the internal space, the solvent can be removed by a known means such as drying, if necessary.

When the structure is provided on the base material layer, there is a possibility that the adhesiveness can be improved by performing a surface treatment on the base material layer as needed. Examples of the surface treatment include at least one selected from the group consisting of primer treatment, chemical conversion treatment, plasma treatment, corona treatment, flame treatment, sandblast treatment and the like, which are well-known means.
As a means for providing the structure on the base material layer, for example, the following methods (1) or (2) can be used, but are not particularly limited.
(1) A solution for preparing a structure is applied on the surface-treated base material layer.
(2) After preparing the structure in advance, it is adhered onto the base material layer using an adhesive or the like.
In the present invention, the method (1) can be preferably used from the viewpoints of ease of manufacturing the laminate, prevention of impurities from being mixed into the laminate due to the adhesive, and the like.

<Use of laminated body>
The laminate of the present invention can be used as an indicator not only for detecting plasma or the like but also for detecting the uniformity of processing of plasma or the like by measuring the color difference based on the color of the detection layer before the treatment.
For example, the laminate can be used as an indicator used in an apparatus for manufacturing electronic devices such as semiconductors, LEDs, semiconductor lasers, power devices, solar cells, liquid crystal displays, organic EL displays, and MEMS.

In the present invention, the L ^* a ^* b ^* color space (note that the L ^* a ^* b ^* color space is defined by measuring the color tone of the detection layer before and after detecting plasma or the like using a commercially available colorimeter. , A color system commonly used to express the color of an object, which was standardized by the International Commission on Illumination (CIE) in 1976, and is JIS Z 8781-4 or JIS Z 8781-5. It is possible to obtain the values of L ^* representing lightness and the chromaticities a ^* and b ^* representing hue and saturation in the color system used in (1). Using these values of L ^* , a ^* and b ^* , the following formula ΔE ^* = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2
The color difference ΔE is calculated by.
Based on the color difference ΔE, in addition to the detection layer measuring the detection of plasma or the like, it is possible to quantitatively obtain the in-plane uniformity or the like on the plane of the detection layer such as plasma.
In particular, the in-plane distribution of color difference (in-plane distribution of discoloration of the detection layer) has a correlation with the flow of plasma or the like. Therefore, by grasping the in-plane distribution of the color difference, it can be used as an indicator for grasping the flow of plasma or the like, which is important in manufacturing an electronic device, and evaluating the uniformity in the processed plane in a short time.
The laminate in the present invention preferably has a ΔE of 0.9 or more, preferably 3.0 or more when treated with plasma or the like for a predetermined time, because it can be accurately visually determined. Further, it is preferable that the color tone change after showing the maximum value of ΔE is less than 3.0 within a predetermined processing time. By forming such a laminated body showing ΔE, it is possible to accurately grasp the treatment by plasma or the like, and it becomes easy to grasp the in-plane uniformity and the like.

When using the indicator, the indicator of the present invention may be placed at a place where a substrate is installed in each electronic device manufacturing apparatus that performs the above processing when manufacturing an electronic device.
For example, it may be laid horizontally (horizontally) with respect to a wafer stage, a heater, a vacuum chuck table, or the like, or may be arranged vertically (vertically) using a wafer boat or the like.
When the indicator of the present invention has the same shape as the substrate used when manufacturing an electronic device, it can be handled and installed in the same manner as the substrate.
In such a case, the color tone of the indicator placed in the apparatus is changed by being exposed to the above treatment, and the in-plane uniformity of the above treatment can be easily detected.

Hereinafter, the laminate and the indicator of the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples.

(Example 1)
A silicon substrate used for manufacturing semiconductors was used as the base material layer.
After surface-treating the surface of the silicon substrate, a polyamide-imide-based resin solution for forming a porous body is applied and dried on the surface-treated surface, and a polyamide-imide-based resin having a thickness of about 20 μm is applied onto the surface-treated surface of the silicon substrate. A porous body (polyamide-imide resin porous film) was formed. It was confirmed by electron microscope observation that the polyamide-imide-based resin porous body had pores having pores on the surface.
A solution (concentration 2% by mass (Example 1)) of CI Solvent Violet 14, which is a dye containing no atoms other than carbon, hydrogen, oxygen and nitrogen, was prepared.
The prepared detection agent solution was applied to and impregnated with the polyamide-imide resin porous body, and then dried to prepare a laminated body.
The produced laminate was measured for each metal atom content, each halogen atom content, and performance evaluation as a plasma indicator as follows.
The results of each are shown in Table 1.

(Measurement of each metal atom content)
When the metal atom content of the silicon substrate, polyamideimide-based resin solution for forming a porous body, and detector solution was measured by ICP-MS (Inductively Coupled Plasma Mass Spectrometry), each metal atom was found. Was a detected amount of less than 0.5 mass ppm.
Therefore, the content of each metal atom in the laminate is less than 0.5 mass ppm.

(Measurement of each halogen atom content)
Halogen atom content was measured by combustion ion chromatography and ICP-MS (Inductively Coupled Plasma Mass Spectrometry) for a silicon substrate, a polyamide-imide resin solution for forming a porous body, and a detector solution. The amount of each halogen atom detected was less than 5 mass ppm.
Therefore, the content of each halogen atom in the laminate is less than 5 mass ppm.

(Performance evaluation)
Using a commercially available plasma irradiation device as a dummy substrate, plasma treatment was performed using CF ₄ gas under the conditions of gas flow rate: 10 cc / min, output 50 W, initial pressure 5 Pa, and processing pressure 20 Pa.
L ^* , a ^*, and b ^* were measured with a colorimeter for the laminate that had not been plasma-treated and the laminate that had been plasma-treated for a predetermined time, and the color difference ΔE before and after the plasma treatment was determined. The results are shown in Table 1.

(Examples 2 to 16)
Solutions of CISolvent Red 52, CISolvent Blue 35, CISolvent Violet 13, CISolvent Violet 14, CISolvent Green 3, and Lumogen F Red 305, all of which are dyes containing no atoms other than carbon, hydrogen, oxygen and nitrogen (concentrations are shown in the table). A laminate was prepared in the same manner as in Example 1 except that the detection agent solution was used as described in 1.).
The produced laminate was measured for each metal atom content, each halogen atom content, and performance evaluation as a plasma indicator in the same manner as in Example 1. The results are also shown in Table 1.

(Comparative Example 1)
A laminate was prepared in the same manner as in Example 1 except that the detection agent solution was not applied or impregnated into the polyamide-imide resin porous body.
The produced laminate was measured for each metal atom content, each halogen atom content, and performance evaluation as a plasma indicator in the same manner as in Example 1. The results are also shown in Table 1.

(Example 17)
A laminate was prepared in the same manner as in Example 1 except that the polyimide resin solution for forming a porous body was used instead of the polyamide-imide resin solution for forming a porous body. After that, the performance as a plasma indicator was evaluated in the same manner as in Example 1 except that the processing time was changed, and the color difference ΔE was obtained. Further, the contents of the metal atom and the halogen atom were measured in the same manner as in Example 1. The results are shown in Table 2.

(Example 18)
A laminate was prepared in the same manner as in Example 17 except that Lumogen F Red 305 was used instead of CISolvent Violet 14. Then, the color difference ΔE was determined in the same manner as in Example 17. The results are also shown in Table 2.

(Examples 19 and 20)
After surface-treating the surface of a silicon substrate used for manufacturing a semiconductor, a polyimide resin solution for forming a porous body was applied and dried on the surface-treated surface. As a result, a polyimide-based resin porous body (polyimide-based resin porous film) having a thickness of about 20 μm having pores having pores on the surface was formed on the surface-treated surface of the silicon substrate.
A 1.0% by mass solution (Example 19) and a 0.25% by mass solution (Example 20) of Lumogen F Red 305, which is a dye containing no atoms other than carbon, hydrogen, oxygen and nitrogen, were prepared and a detector was prepared. It was made into a solution.
The prepared detection agent solution was applied to and impregnated with the polyimide resin porous body and then dried to prepare a laminated body.
The produced laminate was measured for each metal atom content, each halogen atom content, and performance evaluation as a plasma indicator in the same manner as in Example 1.
The results of each are shown in Table 3.

From Tables 1 to 3, it takes time to start discoloration when the concentration of the dye in the detection agent solution is high, although it depends on the type of structure and dye that has an internal space that communicates with the pores on the surface (discoloration is required). It can be seen that the plasma irradiation amount is large) and the discoloration is small when the concentration is low.
Then, the indicator including the laminated body of the present invention can determine whether or not the treatment is appropriately performed based on the visual change in color tone. At this time, the sensitivity can be adjusted by adjusting the dye type and concentration in the detection agent solution, and it is possible to easily and visually detect whether or not the treatment is uniformly performed on the entire object to be treated.
Further, the indicator containing the laminate of the present invention has a low content of metal atoms and halogen atoms. As a result, it is possible to avoid contamination of the object to be treated and the inside of the chamber by the pollutants generated during the treatment with at least one selected from the group consisting of plasma, ozone, ultraviolet rays and radical-containing gas.

1 Structure 2 Detection agent 3 Base material layer 4 Detection layer

Claims (7)

It has a detection layer that detects at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and radical-containing gas to change the color tone, and a base material layer.
The detection layer includes a structure having an internal space that communicates with an opening on the surface.
The internal space contains a detection agent containing at least one detection component that detects at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and radical-containing gas and changes the color tone.
A laminate in which the content of each metal atom in the laminate is less than 5.0 mass ppm. It has a detection layer that detects at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and radical-containing gas to change the color tone, and a base material layer.
The detection layer includes a structure having an internal space that communicates with an opening on the surface.
The internal space contains a detection agent containing at least one detection component that detects at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and radical-containing gas and changes the color tone.
A laminate in which the detection agent contains a dye compound containing no atoms other than carbon, hydrogen, oxygen and nitrogen. The laminate according to claim 1, wherein the detection component contains a dye compound containing no atoms other than carbon, hydrogen, oxygen and nitrogen. The structure contains at least one resin selected from the group consisting of polyimide-based resins, polyamideimide-based resins, polyamide-based resins, polyolefin-based resins, polyurethane-based resins, melamine-based resins, polyester-based resins, and polycarbonate-based resins. The laminate according to any one of claims 1 to 3, which is a structure. Any of claims 1 to 4, wherein the detection agent contains a resin and / or a resin precursor, and the resin and / or the resin precursor does not contain atoms other than carbon, hydrogen, oxygen, and nitrogen atoms. The laminate described in Crab. The laminate according to any one of claims 1 to 5, wherein the content of each halogen atom in the laminate is less than 30 mass ppm. An indicator comprising the laminate according to any one of claims 1-6.