JP7464219B2 - Laminate and indicator - Google Patents

Description

The present invention relates to a laminate and an indicator.

As a method for treating various articles, a method using at least one selected from the group consisting of plasma, ozone, ultraviolet light, and a radical-containing gas (hereinafter, sometimes referred to as "plasma, etc.") is widely known. For example, plasma is generated in a plasma generating gas atmosphere, and the plasma is irradiated onto various articles, substrates, etc., to perform plasma treatment.
Treatments using plasma or the like are also carried out 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, plasma or other treatments are performed in each of the upstream processes, such as film formation (CVD, sputtering, etc.) on a semiconductor wafer, resist pattern formation (plasma dry etching, ion beam etching, etc.), film etching using the resist pattern, resist pattern removal, and cleaning.

When manufacturing electronic devices, processing using plasma or the like needs to be performed uniformly.
For example, it is important that plasma processing or the like in the front end process of semiconductor chip manufacturing is performed uniformly across the wafer surface, and that in-plane uniformity is maintained. If the in-plane uniformity is lost, the performance of each semiconductor chip formed on the semiconductor wafer will vary, affecting the yield.
For this reason, confirmation of the uniformity of processing by plasma or the like is essential when designing each electronic device manufacturing apparatus and when managing the manufacturing process using said apparatus.

The uniformity of the treatment can be confirmed by using a method of measuring the film characteristics and processing accuracy of a manufactured electronic device, or a method of performing each of the above treatments individually and evaluating the in-plane uniformity.
For example, known methods for evaluating the uniformity of the plasma itself include measuring the physical constants of the plasma using a Langmuir probe installed in the manufacturing equipment, and evaluating the spatial distribution by performing optical emission analysis of the plasma using a spectrometer.
However, the method using the Langmuir probe requires the manufacturing equipment to be vented to the atmosphere or the probe to be removed during manufacturing operations, which requires a lot of time and effort. The method using the spectrometer has a limited measurement range, so it may not be possible to measure the entire plasma inside the equipment. In addition, the method using the Langmuir probe or spectrometer does not directly show the in-plane distribution of each process, and requires analysis of the measurement results.

Patent Documents 1 and 2 describe indicators for detecting the presence or absence of ozone or the like.
Patent Document 3 describes a method in which an ink containing a dye, a specific surfactant, and a nonionic surfactant is applied to a substrate and placed in a reaction chamber or the like as an indicator to detect the end point of plasma treatment.
Patent Document 4 describes the use of an indicator for detecting plasma, etc., which has the same shape as the substrate used in the electronic device manufacturing equipment, to confirm the uniformity of the treatment of plasma, etc. The indicator includes a color-changing layer formed of ink that changes color or loses color by reacting with plasma, etc.
Patent Document 5 describes the use of a plasma indicator having a dye contained in pores formed by anodization treatment to prevent contamination caused by ink compositions and the like.

The indicators described in Patent Documents 3 to 5 allow the progress of plasma processing or the like to be visually confirmed in a reaction chamber, but the sensitivity and the like must be appropriately adjusted.
In addition, depending on the processing conditions, etc., some of the components of the indicator placed in the chamber may gasify and contaminate the object to be treated in the plasma treatment, etc., or the inside of the chamber. For example, ink often contains substances that contain metal atoms or halogen atoms, and contamination of components containing metal atoms due to the dispersion media, etc. during preparation is also expected.
In particular, the presence of metal atoms is undesirable in the pre-processing steps of semiconductor device manufacturing, and an indicator that can avoid contamination has been required.

Patent No. 4382816 JP 2013-537978 A JP 2015-013982 A International Publication No. 2015/025699 International Publication No. 2018/128123

An object of the present invention is to provide a laminate and an indicator which can easily adjust the sensitivity of a detection layer, the color of which changes upon detection of at least one selected from the group consisting of plasma, ozone, ultraviolet light, and a radical-containing gas, and which can reliably detect the progress and end point of a treatment with at least one selected from the group consisting of plasma, ozone, ultraviolet light, and a radical-containing gas.
The present invention aims to provide a laminate and an indicator that can easily detect whether treatment with at least one selected from the group consisting of plasma, ozone, ultraviolet light, and radical-containing gas is being performed uniformly over the entire workpiece, and that can avoid contamination of the workpiece or the inside of a chamber due to contaminants generated during these treatments.

As a result of investigations aimed at solving the above problems, the present inventors have found that the above problems can be solved by forming a laminate having a specific structure and using this as an indicator.
Specifically, the following are included:
1: A sensor having a detection layer that changes color upon detecting at least one selected from the group consisting of plasma, ozone, ultraviolet light, and radical-containing gas, and a substrate layer;
the detection layer has a structure having an internal space communicating with the openings on the surface;
the internal space contains a detecting agent including at least one detecting component that changes color upon detecting at least one selected from the group consisting of plasma, ozone, ultraviolet light, and a radical-containing gas;
A laminate, in which the content of each metal atom in the laminate is less than 5.0 ppm by mass.
2: A sensor having a detection layer that changes color upon detecting at least one selected from the group consisting of plasma, ozone, ultraviolet light, and a radical-containing gas, and a substrate layer;
the detection layer has a structure having an internal space communicating with the openings on the surface;
the internal space contains a detecting agent including at least one detecting component that changes color upon detecting at least one selected from the group consisting of plasma, ozone, ultraviolet light, and a radical-containing gas;
The sensing agent comprises a dye compound that does not contain atoms other than carbon, hydrogen, oxygen and nitrogen.
3. The laminate according to item 1, wherein the sensing component comprises a dye compound that does not contain atoms other than carbon, hydrogen, oxygen and nitrogen.
4. The laminate according to any one of items 1 to 3, wherein the structure is a structure containing 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.
5. The laminate according to any one of items 1 to 4, wherein the detecting agent contains a resin and/or a resin precursor, and the resin and/or resin precursor does not contain atoms other than carbon, hydrogen, oxygen, and nitrogen atoms.
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 ppm by mass.
7: An indicator comprising the laminate according to any one of items 1 to 6 above.

The present invention provides a laminate and an indicator which can easily adjust the sensitivity of a detection layer that changes color upon detection of at least one selected from the group consisting of plasma, ozone, ultraviolet light, and a radical-containing gas, and which can reliably detect the progress and end point of a treatment with at least one selected from the group consisting of plasma, ozone, ultraviolet light, and a radical-containing gas.
The present invention provides a laminate and an indicator that can easily detect whether treatment with at least one selected from the group consisting of plasma, ozone, ultraviolet light, and radical-containing gas is being performed uniformly over the entire workpiece, and that can avoid contamination of the workpiece or the inside of a chamber due to contaminants generated during these treatments.

FIG. 1 shows a laminate of the present invention. Electron microscope photograph of a cross section of the laminate of the present invention

[Laminate]
The laminate of the present invention comprises a detection layer that changes color upon detecting plasma or the like, and a base layer, wherein the detection layer is provided with a structure having an internal space that communicates with an opening on the surface, and the internal space contains a detection agent that includes at least one detection component that changes color upon detecting plasma or the like.

<Detection layer>
The change in color tone of the detection layer occurs when the detection component comes into contact with plasma or the like and undergoes one or more color changes, such as discoloration, decolorization, or color development. Here, the plasma or the like is, as described above, at least one type selected from the group consisting of plasma, ozone, ultraviolet light, and radical-containing gas.
The detection layer of the present invention not only detects plasma etc., but also allows easy visual detection of in-plane uniformity in treatment with plasma etc. In the present invention, it is possible to cause the detection agent to be uniformly present in the detection layer, which is believed to have made it possible to detect in-plane uniformity.
The thickness of the detection layer is not particularly limited as long as it exhibits a detection function, and can be appropriately optimized according to the application, desired characteristics, etc. In order to reliably detect the change in color tone, the thickness can be 10 μm or more, and is preferably 15 to 100 μm.

(plasma)
The plasma refers to plasma generated by applying an AC voltage, a DC voltage, a pulse voltage, high frequency, microwaves, or the like using a plasma generating gas, and includes both low-pressure plasma and 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, high frequency, microwaves, etc. For example, at least one gas selected from the group consisting of oxygen, nitrogen, hydrogen, fluorine, chlorine, helium, neon, argon, silane, ammonia, sulfur bromide, water vapor, nitrous oxide, tetraethoxysilane, carbon tetrafluoride, trifluoromethane, carbon tetrachloride, silicon tetrachloride, sulfur hexafluoride, titanium tetrachloride, dichlorosilane, trimethylgallium, trimethylindium, trimethylaluminum, air, and carbon dioxide is used.

Examples of plasma include plasma generated in plasma processing equipment (equipment that performs plasma processing by applying AC voltage, DC voltage, pulse voltage, high frequency, microwaves, etc. in an atmosphere containing a plasma generating gas to generate plasma) used in film formation, etching, ashing, impurity addition, cleaning, and other processes during the manufacture of electronic devices.

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

(Ultraviolet rays)
Ultraviolet rays refer to electromagnetic waves with wavelengths of about 1 to 400 nm, and include near ultraviolet rays, far ultraviolet rays, vacuum ultraviolet rays, and extreme ultraviolet rays. Examples of ultraviolet rays include ultraviolet rays generated from ultraviolet irradiation devices including mercury lamps and LEDs, and ultraviolet rays generated in ultraviolet treatment devices used in photolithography, ashing, cleaning, and other processes during the manufacture of electronic devices.

(Radical-containing gas)
The radical-containing gas is generated by giving energy to a gas. For example, it can be generated by passing hydrogen through a Ta thin tube heated to 2100 K by electron beam bombardment. In the environment in which such a radical-containing gas is used, it is preferable to control the flow rate of hydrogen and maintain the degree of vacuum at about 1.0×10 ⁻⁴ Torr to 1.0×10 ⁻⁶ Torr. For example, the radical-containing gas may be generated in a radical-containing gas treatment device used in a film-forming process, an etching process, an ashing process, a cleaning process, or the like during the manufacture of an electronic device.

(Structure)
The structure constituting the detection layer of the present invention is made of at least one material selected from the group consisting of organic materials, inorganic materials, and organic-inorganic composite materials, and has an internal space communicating with the openings on the surface. The color tone of the structure may be any color tone that allows the change in color tone of the detection component to be recognized, and is preferably transparent, colored transparent, white, light color, etc.
Examples of the structure that can be used include a porous body having an internal space communicating with the openings on the surface, a body in which one or more of holes, recesses, protrusions, and cracks are provided by a known appropriate means to form an internal space that communicates with the openings on the surface, a composition in which a porous substance is disposed on the surface, etc. Of these, a porous body having an internal space communicating with the openings on the surface is preferably used.
The organic material, inorganic material, and organic-inorganic composite material constituting the structure are composed of at least one or more compounds. If necessary, they may contain components such as extenders. In addition, 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 increase the color change. In addition, by using the structure, the color change of the detecting agent over time can be caused according to the penetration degree of the plasma or the like, or the color change can be caused in proportion to the amount or strength of exposure to the plasma or the like.

The porous body having an internal space communicating with the open pores on the surface may be, for example, any of an inorganic porous body, an organic porous body, and an organic-inorganic composite porous body.
Examples of inorganic porous bodies include, but are not limited to, at least one selected from the group consisting of metal porous bodies, silica porous bodies (silica gel, aerosol, colloidal silica, etc.), alumina porous bodies (activated alumina, etc.), zeolite porous bodies (aluminosilicate zeolite, metallosilicate zeolite, aluminophosphate zeolite, etc.), silicate porous bodies (kaolinite, montmorillonite, mica, etc.), mesoporous porous bodies (mesoporous silica, etc.), glass porous bodies, ceramic porous bodies, pumice, and porous bodies such as metal oxides and metal hydroxides (alumite, hydroxyapatite, hydrotalcite, layered zirconium phosphate, heteropolyacid salts, porous manganese oxide, etc.).

The organic porous body may be, but is not limited to, at least one selected from the group consisting of resin porous bodies (porous films, porous polymer beads, etc.), nonwoven fabrics, knitted fabrics, woven fabrics, paper, wood, leather, activated carbon, fullerenes, carbon nanotubes, etc.

As the resin constituting the resin porous body, for example, known or commercially available resins can be used, such as polyamide-based resins, polyamideimide-based resins, polyimide-based resins, amino-based resins (melamine-based resins, benzoguanamine-based resins, urea-based resins, etc.), acrylic-based resins ((meth)acrylic-based resins, poly(meth)acrylonitrile-based resins, poly(meth)acrylamide-based resins, etc.), polyvinylpyrrolidone-based resins, polyvinyl imidazole-based resins, polyolefin-based resins (polyethylene-based resins, polypropylene-based resins, etc.), fluorine-based resins, vinyl chloride-based resins, vinyl acetate-based resins, polyvinyl acetal-based resins (polyvinyl butyral-based resins, etc.), polyvinyl alcohol-based resins, polystyrene-based resins (polystyrene-based resins, 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, terpene phenol resin, rosin-modified phenol resin, etc.), polyether resin, epoxy resin, maleic acid resin, polyketone resin, polyethyleneimine resin, polyurethane resin, polysiloxane resin, acetal resin, block polymer resin, graft polymer resin, cellulose resin, rosin resin (rosin resin, rosin ester resin, etc.), rubber resin (natural rubber, diene rubber, SB rubber, etc.), etc., but are not particularly limited thereto.

Of these resins, polyimide resins, polyamideimide resins, polyamide resins, polyolefin resins, polyurethane resins, melamine resins, polyester resins, and polycarbonate resins can be preferably used. In particular, when a heat-resistant polymer such as polyamideimide resin, polyimide resin, or polyamide resin is used as the structure, a laminate with excellent heat resistance is formed, so that an indicator can be constructed that can be used under high temperature conditions and has strong resistance to plasma treatment.

The organic-inorganic composite porous material may be, but is not limited to, at least one selected from the group consisting of a porous material of a resin composition containing an inorganic component, a metal-organic framework (MOF), and the like.
As the organic component constituting the organic-inorganic composite porous body, an organic component constituting an organic porous body can be used, and as the inorganic component constituting the organic-inorganic composite porous body, an inorganic component constituting an inorganic porous body or a well-known inorganic filler can be used.

In the above-mentioned structure, examples of structures having an internal space by providing one or more of holes, recesses, protrusions, and cracks by known suitable means include those having holes provided by drilling with a needle or laser, those having holes or recesses provided by chemical treatment, those having recesses provided by embossing or grinding, those having protrusions provided by spraying a protrusion-forming substance, those having cracks provided by preparation using a resin composition or paint containing a crack-forming agent such as an inorganic filler that forms fine cracks on the surface, and those having porous fillers blended with a binder such as a resin.

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

The resin porous body can be prepared by a known method, for example, the following methods (1) to (4).
(1) Porosification by chemical means such as using a pore-forming agent (for example, porosification using a foaming agent, porosification using gas generated during polymerization, modification, or molding, porosification by removing the porosity-forming agent after molding (after film formation) (removal of components or sublimation, etc.), porosification by phase separation (use of mixed solvents with different solubilities, etc.), etc.)
(2) Porosity due to stretching (3) Porosity due to fusion of powder particles (4) Porosity due to mechanical means such as perforation

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

(Detection agent)
The detecting agent in the present invention contains at least one detecting component that changes color upon detecting plasma or the like.
In addition, the detection agent may contain various components as necessary for the purpose of adjusting the sensitivity, improving the visibility of the color difference before and after detection, etc., within a range that does not impair the effect of the color change caused by the detection component.
Such components include, for example, pigments that do not function as the detection component (i.e., pigments that do not change color when exposed to the detection target), resins and/or resin precursors, reaction accelerators, reaction retarders, fillers, surfactants, and other additives.

In the present invention, in order to make the content of each metal atom in the laminate less than 5.0 ppm by mass, it is preferable that the detecting agent containing the detecting component does not contain metal atoms, whereby when the laminate is used as an indicator for detecting plasma or the like in an electronic device manufacturing apparatus, contamination by metal atoms in the electronic device manufacturing apparatus can be effectively prevented.
In the present invention, it is preferable to use a detecting agent containing a dye compound that does not contain atoms other than carbon, hydrogen, oxygen, and nitrogen, which can effectively prevent contamination, particularly contamination by metal atoms and halogen atoms, in electronic device manufacturing equipment when the laminate is used as an indicator for detecting plasma, etc.
It is preferable to thoroughly purify the components of the detecting agent and not use metal tools in the preparation of the detecting agent to prevent the inclusion of impurities such as metal atoms and halogen atoms.

-Detection component-
The compound used as the detection component in the present invention, which changes color upon detecting plasma or the like, is not particularly limited as long as it exhibits a behavior of changing color when exposed to plasma or the like.
Examples of such compounds include colorants known as colorants, preferably dyes and pigments, which change color upon 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, food dyes, perinone dyes, diketopyrrolopyrrole dyes , quinacridone dyes, anthanthrone dyes, isoindolinone dyes, isoindoline dyes, indanthrene dyes, coumarin dyes, pyranthrene dyes, flavanthrone dyes, nitroso ... Examples of the dyes include, but are not limited to, at least one selected from the group consisting of chlorine-based dyes, stilbene-based dyes, carotenoid-based dyes, acridine-based dyes, quinoline-based dyes, thiazole-based dyes, naphthoquinone-based dyes, indamine-based dyes, indophenol-based dyes, azine-based dyes, thiazine-based dyes, sulfide-based dyes, lactone-based dyes, hydroxyketone-based dyes, aminoketone-based dyes, indigoid-based dyes, thioindigo-based dyes, cationic dyes, cyanine-based dyes, squarylium-based dyes, croconium-based dyes, merocyanine-based dyes, fluoran-based dyes, spiropyran-based dyes, fulgide-based dyes, azulene-based dyes, natural dyes, oxidation-based dyes, and metal complex-based dyes.

Of the dyes, it is preferable to use, as the dye for detecting plasma, at least one selected from the group consisting of anthraquinone-based dyes, perylene-based dyes, methine-based dyes, azo-based dyes, phthalocyanine-based dyes, triarylmethane-based dyes, xanthene-based dyes, indanthrene-based dyes, and food dyes.
Of the dyes, it is preferable to use at least one dye selected from the group consisting of oxazine dyes, azo dyes, methine dyes, indanthrene dyes, and anthraquinone dyes as the dye for detecting ozone.

Of the dyes, as the dye for detecting ultraviolet light, it is preferable to use at least one dye selected from the group consisting of azo dyes, anthraquinone dyes, triarylmethane dyes, phthalocyanine dyes, indigo dyes, diarylmethane dyes, triarylamine dyes, and cyanine dyes.
Furthermore, it is preferable to use, together with the dye for detecting ultraviolet light, a compound which changes the color-developing mechanism of the dye when irradiated with ultraviolet light, the compound itself being transformed into a compound which changes the color-developing mechanism of the dye when irradiated with ultraviolet light and/or a compound which generates free radicals which change the color-developing mechanism when irradiated with ultraviolet light.
Examples of the compound that changes the color-developing mechanism of the dye upon irradiation with ultraviolet light include, but are not limited to, at least one selected from the group consisting of acetophenone-type compounds, benzophenone-type compounds, Michler's ketone-type compounds, benzyl-type compounds, benzoin-type compounds, benzoin ether-type compounds, benzyl dimethyl ketal-type compounds, benzoin benzoate-type compounds, α-acoxim ester- type compounds, tetramethylthiuram monosulfide-type compounds, thioxanthone-type compounds, and acylphosphine oxide-type compounds.
In particular, it is preferable to use a compound that generates free radicals that change the above-mentioned color-developing mechanism upon irradiation with ultraviolet light, and it is preferable to use at least one compound selected from compounds having an absorption maximum at wavelengths of about 150 to 450 nm (more preferably 200 to 400 nm).
The amount of the compound that changes the color-developing mechanism of the dye upon irradiation with ultraviolet light can be determined depending on the type of dye used, etc. Any amount may be used as long as it provides a sufficient color change effect that can be visually recognized and does not cause problems in terms of solubility in a solvent, etc. For example, the amount is usually about 0.1 to 20 mol, preferably 0.5 to 15 mol, per mol of the dye.

When a benzophenone type compound, a Michler's ketone type compound, a benzyl type compound, a thioxanthone type compound, or the like is used as a compound that changes the color-developing mechanism of the dye by ultraviolet irradiation, it is preferable to use an amine-based reaction accelerator (amine-based radical accelerator) such as ethanolamine in combination. In such a case, the amount of the amine-based reaction accelerator to be added can be appropriately determined depending on the compound, the dye, etc.
Examples of combinations of a dye and a compound that changes the color-developing mechanism of the dye upon exposure to ultraviolet light include: (1) a combination of an anthraquinone dye with a benzoin ether type compound, a benzyl dimethyl ketal type compound, or an acylphosphine oxide type compound; (2) a combination of a disazo dye with a benzoin ether type compound or an acylphosphine oxide type compound; (3) a combination of a phthalocyanine dye with a benzoin ether type compound or an acylphosphine oxide type compound; (4) a combination of a cyanine dye with a benzophenone type compound; and (5) a combination of an azo dye with a benzophenone type compound or an acylphosphine oxide type compound.

Of the above dyes, it is preferable to use at least one dye selected from the group consisting of anthraquinone dyes, azo dyes, and triarylmethane dyes as the dye for detecting radical-containing gases.

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

Specific examples of these dyes include C.I. Acid Black 123, C.I. Acid 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, C.I. Acid Green 16, C.I. Acid Red 52, 81, 83, C.I. Acid Violet 1, 3, 7, 10, 12, 14, 15, 16, 17, 19, 20, 21, 23, 25, 30, 38, 39, 43, 48, 49, 72, C.I. Acid Yellow 11,12,13,14,21,22,23,24,74,C.I.Azoic Coupling Component 2,3,4,5,7,11,14,16,17,18,19,20,29,36,C.I.Azoic Diazo Component 1,5,8,12,13,20,24,34,41,48,109,C.I.Azoic Brown 11,C.I.Basic Blue 1,5,7,8,26,62,63,140,C.I.Basic Green 1,4,C.I.Basic Red 1,9,12,13,14,15,27,35,36,37,45,48,C.I.Developer 8,18,20,21,22,C.I.Direct Blue 41,86,87,C.I.Disperse Black 1,2,29,C.I.Disperse Blue 1,3,5,6,7,26,27,44,C.I.Disperse Orange 1,3,5,11,13,C.I.Disperse Red 1,4,9,11,13,15,17,52,58,88,167:1,C.I.Disperse Violet 1,4,8,C.I.Disperse Yellow 1,3,4,5,7,8,23,31,60,61,C.I.Mordant Blue 1,C.I.Mordant Red 11,15,27,C.I.Mordant Violet 1,25,C.I.Pigment Blue 15,15:3,15:4,15:6,16,C.I.Pigment Green 7,36, C.I.Reactive Blue 4,19, C.I.Solvent Black 3, C.I.Solvent Brown 3,5, C.I.Solvent Blue 11,14,35,63,70, C.I.Solvent Green 3,5,15, C.I.Solvent Orange 1,2,14,55,60,78,90, C.I.Solvent Red 1,3,18,23,24,25,27,49,52,114,135,162,179, C.I.Solvent Violet 8,13,14,29, C.I.Solvent Yellow 2,6,14,16,21,29,33,56, C.I.Vat Black 8,9,25,27,29, C.I.Vat Brown 1,3,25,44, C.I.Vat Blue 1,4,12,20,21,30, C.I.Vat Green 1,3,8,9, C.I.Vat Orange 7,9,13,15, C.I.Vat Red 10,13,15,19,28,29, C.I.Vat Violet 13,15,17, C.I.Vat Yellow 4,10,20, 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 At least one selected from the group consisting of extra, Food Red No. 1, Food Red No. 3, Food Red No. 102, Food Red No. 104, Food Red No. 105, Food Red No. 106, Food Yellow No. 4, Food Yellow No. 5, Food Green No. 3, Food Blue No. 1, Food Blue No. 2, etc.

For example, C.I.Acid Black 123, C.I.Azoic Brown 11, C.I.Azoic Coupling Component 2,3,4,5,7,11,14,16,17,18,19,20,29,36, C.I.Azoic Diazo Component 1,5,8,12,13,20,24,34,41,48,109, C.I.Basic Green 4, C.I.Developer 8,18,20,21,22, C.I.Disperse Black 1,2,29, C.I.Disperse Blue 1,3,5,6,7,26,27, C.I.Disperse Orange 1,3,11,13, C.I.Disperse Red 1,4,9,11,15,17, C.I.Disperse Violet 1,4,8, C.I.Disperse Yellow 1,3,4,5,7,8,23,31,60,61, C.I.Mordant Red 11,15,27, C.I.Solvent Black 3, C.I.Solvent Blue 11,35, C.I.Solvent Brown 3,5, C.I.Solvent Green 3, C.I.Solvent Orange 1,2,14, C.I.Solvent Red 1,3,18,23,24,25,27,49,52, C.I.Solvent Violet 13,14, C.I.Solvent Yellow 2,6,14,16,21,29,33,56, C.I.Vat Black 8,9,25,27,29, C.I.Vat Blue 1,4,12,20, C.I.Vat It is preferable to use at least one selected from the group consisting of Brown 1,3,25,44, C.I.Vat Green 1,3,8,9, C.I.Vat Orange 7,9,13,15, C.I.Vat Red 10,13,15, C.I.Vat Violet 13, C.I.Vat Yellow 4,10,20, 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, etc.

More preferably, C.I.Azoic Coupling Component 3,16, C.I.Basic Green 4, C.I.Mordant Red 27, C.I.Solvent Black 3, C.I.Solvent Blue 35, C.I.Solvent Red 18,24,27,49,52, C.I.Solvent Violet 14, C.I.Solvent Yellow 29, C.I.Vat Black 8,9,25,27,29, C.I.Vat Brown 1,3,25,44, C.I.Vat Green 8, C.I.Vat Orange 13,15, C.I.Vat Red 10,13,15, C.I.Vat Yellow 10,20, Lumogen F IR 788, Lumogen F Orange 240, Lumogen F Pink 285, Lumogen F Red At least one selected from the group consisting of 300, 305, 339, Lumogen F Violet 570, Lumogen F Yellow 083, 170, Iketon Violet extra, Oil Peacock Blue, and Oil Brown BG extra.

In the present invention, the detection sensitivity and the color development and color tone change of the detection layer can be controlled by changing the type (molecular structure, etc.) of these dyes or by using a mixture of a plurality of dyes.
The content of these dyes may be appropriately determined depending on the type of dye, the desired color change (detection sensitivity), the product form, the properties of the structure, and the like.
For example, the detection layer may contain 0.01 to 20% by mass, preferably 0.1 to 10% by mass of the dye, and the detection agent may contain 0.01 to 100% by mass, preferably 0.1 to 100% by mass of the dye.

-Dye that does not function as a sensing component-
In the present invention, the detecting agent may contain a dye that does not function as a detecting component.
By incorporating such a dye that does not function as a detection component, the visibility can be further improved by changing the color tone from one color to another.
The dye that does not function as a detection component is, but is not particularly limited to, at least one selected from the group consisting of dyes that do not undergo a change in color when exposed to a detection target.
For example, at least one type selected from the group consisting of dyes that do not change color even when plasma or the like is detected, and dyes that change color when plasma or the like is detected but do not change hue depending on the detection target can be used.
When a dye that does not function as a detection component is contained in the detection agent, the content thereof can be appropriately determined depending on the type, visibility of the detection layer, desired color tone, etc., but it is generally preferable that the content be about 0 to 99.99 mass %, particularly 0 to 99.9 mass %, in the detection agent.

-Resin and/or resin precursor-
In the present invention, the detecting agent may contain a resin and/or a resin precursor which may function as a binder.
The resin may be either a natural resin or a synthetic resin, or may be a commercially available resin, and may have any molecular weight or molecular weight distribution.
Any resin precursor can be used as long as it can be converted into a resin by reaction, for example, at least one selected from the group consisting of (meth)acrylate compounds, polyamic acids, polyurethane prepolymers, etc., but is not particularly limited thereto.
The resin and/or resin precursor is appropriately selected depending on the components constituting the detecting agent.
By including a resin and/or a resin precursor in the detecting agent, it is possible to, for example, adjust the fixation property of the detecting agent, prevent detachment or peeling of the detecting component from the detecting agent or the detecting layer, adjust the sensitivity by controlling the contact between the detecting component and the detection target, and protect the detecting agent.

Such resins may be publicly known or commercially available, and examples of such resins include polyamide resins, polyamideimide resins, polyimide resins, amino resins (melamine resins, benzoguanamine resins, urea resins, etc.), acrylic resins ((meth)acrylic resins, poly(meth)acrylonitrile resins, poly(meth)acrylamide resins, etc.), polyvinylpyrrolidone resins, polyvinylimidazole resins, polyolefin resins (polyethylene resins, polypropylene resins, etc.), fluorine resins, vinyl chloride resins, vinyl acetate resins, polyvinyl acetal resins (polyvinyl butyral resins, etc.), polyvinyl alcohol resins, polystyrene resins (polystyrene resins, styrene-maleic acid resins, etc.), and the like. resins, styrene-acrylic acid resins, etc.), polyester resins (polyester resins, unsaturated polyester resins, alkyd resins, etc.), phenolic resins (phenolic resins, alkylphenol resins, terpene phenolic resins, rosin-modified phenolic resins, etc.), polyether resins, epoxy resins, maleic acid resins, polyketone resins, polyethyleneimine resins, polyurethane resins, polysiloxane resins, acetal resins, block polymer resins, graft polymer resins, cellulose resins, rosin resins (rosin resins, rosin ester resins, etc.), rubber resins (natural rubber, diene rubber, SB rubber, etc.), and the like, but are not particularly limited thereto.
When the resin and/or resin precursor is contained in the detecting agent, the content can be appropriately determined depending on the type of the resin and/or resin precursor, the type of the detecting component used, etc. For example, it can generally be used in an amount of about 50 mass % or less, preferably 5 to 35 mass %, in the detecting agent.

-Surfactants-
In the present invention, a surfactant may be contained in the sensing agent.
The surfactant may be at least one selected from the group consisting of nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants, but is not particularly limited thereto. Among these, it is preferable to use at least one selected from the group consisting of nonionic surfactants and cationic surfactants, particularly when detecting plasma. This can promote the discoloration of the detection component and improve the detection sensitivity of the detection component.

Examples of the nonionic surfactant include, but are not limited to, at least one selected from the group consisting of (1) to (4): (1) alkylene glycol derivatives (e.g., polyethylene glycol (e.g., trade name "PEG2000" manufactured by Sanyo Chemical Industries, Ltd.), polyethylene glycol-polypropylene glycol copolymers (e.g., trade name "Epane 710" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), polyoxyalkylene alkyl ethers (e.g., trade name "Emulgen 109P" manufactured by Kao Corporation), polyalkylene glycol mono fatty acid esters, etc.), (2) polyglycerin derivatives, (3) alkylene glycol glyceryl derivatives (e.g., fatty acid polyoxyalkylene glyceryl (e.g., trade name "UNIOX GM-30IS" manufactured by NOF Corporation), and (4) acetylene glycol derivatives (e.g., "Surfynol 104H" manufactured by Air Products Japan, Ltd.), etc.).
When a nonionic surfactant is contained in the detecting agent, the content can be appropriately determined depending on the type of nonionic surfactant and the type of detecting component used, etc. For example, taking into consideration the storage stability and discoloration promoting effect in the detecting agent, the content can be about 0.1 to 10 mass %, preferably 0.5 to 5 mass %, in the detecting agent.

Examples of the cationic surfactant include, but are not limited to, at least one selected from the group consisting of (1) to (4): (1) tetraalkylammonium salts (e.g., alkyltrimethylammonium salts (e.g., behenyltrimethylammonium chloride, lauryltrimethylammonium chloride, etc.), dialkyldimethylammonium salts, etc.), (2) isoquinolinium salts (e.g., laurylisoquinolinium bromide, etc.), (3) imidazolinium salts (e.g., 2-chloro-1,3-dimethylimidazolinium chloride, etc.), and (4) pyridinium salts (e.g., hexadecylpyridinium chloride, etc.).
When the cationic surfactant is contained in the detecting agent, the content can be appropriately determined depending on the type of cationic surfactant and the type of detecting component used, etc. For example, taking into consideration the storage stability and discoloration promoting effect in the detecting agent, the content can be about 0.1 to 10 mass %, preferably 0.5 to 5 mass %, in the detecting agent.

-filler-
In the present invention, the detection agent may contain a filler. As the filler, a known or commercially available one can be used, and examples thereof include at least one selected from the group consisting of bentonite, clay, activated clay, talc, alumina, silica, silica gel, calcium carbonate, barium sulfate, resin beads, etc., but are not particularly limited thereto.
For example, when the detecting agent contains a resin, if silica or the like is contained, a plurality of fine cracks will be generated on the surface of the detecting agent, thereby making it possible to increase the detection sensitivity.
The content of the filler can be appropriately determined according to the type of filler and the type of detection component used, within a range that does not significantly impair the effect of color change caused by the detection component. For example, taking into consideration the storage stability and color change promotion effect in the detection agent, the content can be about 0.1 to 10 mass %, preferably 0.5 to 5 mass %, in the detection agent.

- Color change retardant -
In the present invention, a color change retarder may be included in the detecting agent in order to retard the color change of the detecting agent. As the color change retarder, for example, a material having a function of inhibiting contact between the plasma or the like and the detecting component can be used.
Examples of the color change retarder include, but are not limited to, at least one selected from the group consisting of absorbents that absorb plasma, etc. (e.g., known or commercially available ion absorbents, radical absorbents, ozone absorbents, ultraviolet absorbents, etc.), and shielding agents that shield detection components from plasma, etc. (e.g., the above-mentioned resins and fillers, etc.).
The content of the color change retarder can be appropriately determined in a range that does not significantly impair the effect of the color change caused by the detection component depending on the desired delay effect of the color change and the composition of the detection agent, etc. For example, it can be about 0 to 10% by mass in the detection agent.

- Color change promoter -
In the present invention, the detecting agent may contain a known or commercially available color change promoter in order to promote the color change of the detecting agent.
Examples of such color change promoters include, but are not limited to, at least one selected from the group consisting of resins having a function of enhancing the accuracy (sensitivity) of detection of plasma, etc. (e.g., nitrogen-containing resins effective for enhancing plasma detection), the surfactants, the fillers, etc.
The content of the color change retarder can be appropriately determined in a range that does not significantly impair the effect of the color change caused by the detection component depending on the desired color change promotion effect, the composition of the detection agent, etc. For example, it can be about 0 to 10 mass % in the detection agent.

-solvent-
In the present invention, a known or commercially available solvent may be included in the sensing agent.
The solvent is used when introducing and retaining the sensing component in the internal space of the structure having an internal space with an opening on the surface of the sensing layer. The solvent is usually removed by a means such as drying, but may be present in a small amount in the sensing agent.
Examples of the solvent include water, hydrocarbon solvents (e.g., hexane, cyclohexane, toluene, xylene, benzene, tetralin, mineral spirits, etc.), alcohol solvents (e.g., methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, furfuryl 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 (e.g., 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.), and ester solvents (e.g., methyl acetate, ethyl acetate, butyl acetate, amyl acetate, ethyl lactate, glycol diacetate, dimethyl carbonate, vegetable oil, γ-butyrolactone, ε-caprolactone, etc.), ketone solvents (e.g., acetone, methyl ethyl ketone, cyclohexanone, diacetone alcohol, isophorone, acetophenone, etc.), phenol solvents (e.g., phenol, cresol, etc.), fatty acid solvents (e.g., hexadecanoic acid, isopalmitic acid, oleic acid, isostearic acid, etc.), carbonate solvents (e.g., dimethyl carbonate, diethyl carbonate, propylene carbonate, Examples of the solvent include, but are not limited to, at least one selected from the group consisting of: amine solvents (triethanolamine, tripropanolamine, tributanolamine, N,N-dimethyl-2-aminoethanol, N,N-diethyl-2-aminoethanol, etc.); amide solvents (for example, acetamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.); halogenated hydrocarbon solvents (for example, carbon tetrachloride, chloroform, trichloroethane, fluorine-containing solvents); and the like.

The solvent may be any solvent capable of dissolving or dispersing the sensing component. Preferably, a solvent capable of dissolving the sensing component is used. The solvent is preferably highly refined to reduce the content of metal atoms and halogen atoms. This reduces the content of metal atoms and halogen atoms in the laminate.
When the sensing component is introduced and held in the internal space, the amount of the solvent used can be appropriately determined depending on the type of solvent, the composition of the sensing agent, etc. It is preferably an amount that does not cause the sensing component to precipitate when a solution or dispersion of the sensing component is formed. For example, when a solvent capable of dissolving the sensing component is used, the concentration of the sensing component is preferably 0.1 to 30 mass %, but is not particularly limited.
In the case where the detection component contains a solvent even after being retained in the internal space, the content of the solvent is set to a range in which the detection agent does not easily flow and does not impair the effect of the color change caused by the detection component. Although it depends on the composition of the detection agent, for example, the detection agent may contain about 0 to 1 mass % of the solvent.

-Other additives-
In the present invention, other additives than the above-mentioned components may be contained in the detecting agent as necessary. Examples of other additives that may be contained in the detecting agent in the present invention include at least one selected from the group consisting of a leveling agent, a defoaming agent, and a surface conditioner, but are not particularly limited thereto.
The content of the other additives can be appropriately determined depending on the composition of the detecting agent, etc., within a range that does not impair the effect of the color change caused by the detecting component. For example, it can be about 0 to 5 mass % in the detecting agent.

<Base layer>
The base layer may be any material capable of supporting the detection layer, and may be at least one material selected from the group consisting of inorganic materials, organic materials, and composites thereof, taking into consideration the properties and applications required of the laminate, but is not particularly limited thereto.
The thickness of the substrate 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, and concrete.
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, fibers (nonwoven fabric, knitted fabric, woven fabric, other fiber sheets), leather, and the like.
Examples of the composite include, but are not limited to, laminates and compositions obtained using at least one material selected from the group consisting of the inorganic materials and the organic materials.
Of these, it is preferable to use at least one material selected from the group consisting of semiconductor materials, glass, sapphire, resin, and paper as the base material layer.

Examples of the semiconductor material include, but are not limited to, at least one selected from the group consisting of silicon (Si), germanium (Ge), tellurium (Te), zinc oxide (ZnO), gallium arsenide (GaAs), gallium nitride ( _GaN ), gallium oxide ( _Ga2O3 ), aluminum nitride (AlN), indium nitride (InN), silicon carbide (SiC), aluminum gallium nitride (AlGaN), indium gallium nitride (InGaN), indium aluminum gallium nitride (InAlGaN), diamond, silicide materials (β- _FeSi2 , _MgSi2 , _NiSi2 , _BaSi2 , _CrSi2 , _CoSi2 , TaSi, etc.), metal oxides, or metal oxynitrides.

Here, examples of the metal oxide or metal oxynitride include In-Sn-Ga-Zn-O-based oxides, In-Hf-Ga-Zn-O-based oxides, In-Al-Ga-Zn-O-based oxides, In-Sn-Al-Zn-O-based oxides, In-Sn-Hf-Zn-O-based oxides, In-Hf-Al-Zn-O-based 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-based oxides, In-Sn-Zn-O-based oxides, In-Hf-Zn-O-based oxides, In-La-Zn-O-based oxides, In-Ce-Zn-O-based oxides, In-Pr-Zn-O-based oxides, In-Nd-Zn-O-based oxides, In-Sm In-Zn-O-based oxides, In-Eu-Zn-O-based oxides, In-Gd-Zn-O-based oxides, In-Tb-Zn-O-based oxides, In-Dy-Zn-O-based oxides, In-Ho-Zn-O-based oxides, In-Er-Zn-O-based oxides, In-Tm-Zn-O-based oxides, In-Yb-Zn-O-based oxides, In-Lu-Zn-O-based oxides, In-Zn-O-based oxides, 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, Zn-ON-based oxynitrides, In-O-based oxides (indium oxide), Sn-O-based oxides (tin oxide), Zn-O-based oxides (zinc oxide), and the like can be mentioned, but are not particularly limited thereto.
Here, for example, an In-Sn-Ga-Zn-O-based oxide refers to an oxide semiconductor having indium (In), tin (Sn), gallium (Ga), zinc (Zn) and oxygen (O), and the composition ratio of each atom is not particularly important, and in some cases, atoms such as silicon (Si) may be included.

The resin may be any known or commercially available resin, and examples thereof include, but are not limited to, at least one selected from the group consisting of polyolefin resins (polyethylene, polypropylene, polynorbornene, etc.), polyvinyl chloride resins, vinylidene chloride resins, fluorine-based resins, polyester resins (polyethylene terephthalate, polyethylene naphthalate, etc.), polystyrene resins, polyimide resins, polyamide resins, polyamideimide resins, polysulfone resins, polysulfide resins, polyether ketone resins, polyether resins, polyurethane resins, polycarbonate resins, acrylic resins, ABS resins, and the like.
Preferably, at least one selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polyethylene-based resins, polypropylene-based resins, polynorbornene-based resins, polyamide-based resins, polyamideimide-based resins, polyimide-based resins, polycarbonate-based resins, acrylic-based resins, and the like is used.

For example, when the laminate is used as an indicator for a semiconductor manufacturing device, the substrate 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 substrate 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 substrate is preferably made of 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 substrate 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 solar cells, the substrate is preferably silicon, glass, germanium, or the like.
For example, when the laminate is used as an indicator for an apparatus for manufacturing liquid crystal displays, 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 substrate is preferably glass or the like.
For example, when the laminate is intended to be an inexpensive or simple indicator, the substrate is preferably made of 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 ppm by mass, for example, less than 1.0 ppm by mass, preferably less than 0.5 ppm by mass, further preferably less than 0.1 ppm by mass, even more preferably less than 1 ppt by mass, and most preferably less than 0.5 ppt by mass.
Here, "metal atom" means an atom other than hydrogen, carbon, nitrogen, oxygen, silicon, fluorine, chlorine, bromine, iodine and rare gases.
In order to make the content of each metal atom in the laminate less than 5.0 ppm by mass, for example less than 1.0 ppm by mass, the detection layer and the base layer are made of materials that do not contain metal atoms. In addition, all components related to the laminate (including solvents, etc.) are made to be free of metal atoms, and furthermore, metal atom-containing substances contained as impurities are removed by purification. Furthermore, it is preferable not to use tools, etc. that may cause contamination of metal atoms in the manufacturing process.
In the present invention, the content of each metal atom in each material constituting the detection layer and the base material layer is measured by ICP-MS (Inductively Coupled Plasma Mass Spectrometry) or the like, and if each is less than 5.0 ppm by mass, the content of each metal atom in the laminate is deemed to be less than 5.0 ppm by mass.
Also, an indicator including the laminate of the present invention is introduced into a treatment device together with a material to be treated, and treatment such as plasma treatment is carried out. Thereafter, each metal atom on the surface of the material to be treated introduced into the treatment device is recovered with hydrofluoric acid or the like, and the content of each metal atom is measured by ICP-MS or the like. If each is less than 5.0 ppm by mass, it can be determined that each metal atom in the laminate is less than 5.0 ppm by mass.
By making the content of each metal atom in the laminate less than 5.0 ppm by mass, for example less than 1.0 ppm by mass, when the laminate is used as an indicator in an electronic device manufacturing equipment, it is possible to prevent contamination of the treated material or the inside of the manufacturing equipment by metal atoms.
This makes it possible to obtain an indicator that can be used in the manufacturing process of semiconductor electronic devices (particularly the etching process in the first half of the process) where the presence of metal atoms is particularly undesirable.

<Content of each halogen atom>
In the present invention, the content of each halogen atom in the laminate can be less than 30 ppm by mass, for example less than 5 ppm by mass, preferably less than 1 ppm by mass, more preferably less than 0.5 ppm by mass, and most preferably less than 1 ppt by mass .
In order to make the content of each halogen atom in the laminate less than 30 ppm by mass, for example less than 5 ppm by mass, it is preferable that the detection layer and the base layer are made of materials that do not contain halogen atoms. It is also preferable to use all components (including solvents, etc.) related to the laminate that do not contain halogen atoms and to remove halogen atom-containing substances contained as impurities by purification. Furthermore, it is preferable to use a method, etc. that does not use tools, etc. that cause contamination of halogen atoms in the manufacturing process.
In the present invention, the content of each halogen atom in each material constituting the detection layer and the base material layer is measured by combustion ion chromatography, ICP-MS (Inductively Coupled Plasma Mass Spectrometry), or the like, and if each is less than 30 ppm by mass, the content of each halogen atom in the laminate is deemed to be less than 30 ppm by mass.
Also, an indicator including the laminate of the present invention is introduced into a treatment device together with a material to be treated, and treatment such as plasma treatment is carried out. Thereafter, halogen atoms present on the surface of the material to be treated introduced into the treatment device are recovered and the content of each halogen atom is measured by combustion ion chromatography, ICP-MS, or the like, and if each is less than 30 ppm by mass, it can be determined that the content of each halogen atom in the laminate is less than 30 ppm by mass.
By making the content of each halogen atom in the laminate less than 30 ppm by mass, for example less than 5 ppm by mass, when the laminate is used as an indicator in an electronic device manufacturing equipment, it is possible to prevent contamination of the treated material and the manufacturing equipment with halogen atoms.
This makes it possible to obtain an indicator that can be used in the manufacturing process of semiconductor electronic devices (particularly the etching process in the first half of the process) where the presence of halogen atoms is particularly undesirable.

<Layer structure>
The laminate of the present invention may have a non-detection layer whose color tone does not change even when plasma or the like is detected, in addition to the detection layer and the base layer whose color tone changes upon detection of plasma or the like.
The detection layer, the base material layer and the non-detection layer may be laminated in any order.
The detection layer and the non-detection layer may each be formed as a single layer, or as a plurality of layers. Also, color-changing layers or non-color-changing layers may be laminated together. In this case, the detection layers may have the same composition or different compositions, and the non-color-changing 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 substrate layer or each layer, or may be formed partially. In these cases, the detection layer and the non-detection layer can be formed so that a part or the whole of at least one detection layer is exposed to plasma or the like, particularly in order to ensure a change in color tone of the detection layer.

The laminate of the present invention may have any combination of color-changing layers and non-color-changing layers, so long as the completion of each of the above-mentioned treatments and the in-plane uniformity can be confirmed.
For example, the detection layer and non-detection layer can be formed so that the color tone of the detection layer before the color tone changes is the same as the color tone of the non-detection layer, and the detection layer and non-detection layer can be formed so that the color difference between the detection layer and non-detection layer can be distinguished by changing the color tone of the detection layer due to plasma or the like.
In addition, the detection layer and the non-detection layer can be formed so that the color tone of the detection layer before the color tone change is different from the color tone of the non-detection layer, and the color difference between the detection layer and the non-detection layer can be eliminated by changing the color tone of the detection layer due to plasma or the like.

In the laminate of the present invention, it is particularly preferable to form a detection layer and a non-detection layer so that the color difference between the detection layer and the non-detection layer can be distinguished by changing the color tone of the detection layer due to plasma or the like.
For example, when the color difference of the color-changing layer can be identified by a change in the color tone of the detection layer due to plasma or the like, the color-changing layer and the non-color-changing layer can be formed so that at least one of letters, patterns, and symbols appears due to the change in color of the color-changing layer.
The letters, designs and symbols include all information to inform users of the discoloration, and these letters, designs and symbols can be appropriately designed depending on the purpose of use, etc.

In the laminate of the present invention, the detection layer and the non-detection layer may not overlap each other, or the detection layer and the non-detection layer may overlap each other.
Furthermore, in the laminate of the present invention, a further detection layer or non-detection layer can be formed on at least one of the detection layer and non-detection layer.
For example, if a detection layer having a different design is formed on top of a layer (referred to as a "detection-non-detection layer") in which a detection layer and a non-detection layer are formed so that the detection layer and the non-detection layer do not overlap, the boundary between the detection layer and the non-detection layer in the detection-non-detection layer can be made substantially indistinguishable, thereby achieving better design.
In the laminate of the present invention, preferred embodiments of the layer structure are as follows:
(1) A laminate in which a detection layer is formed adjacent to at least one main surface of a base layer;
(2) A laminate in which a non-detection layer and a detection layer are formed in this order on a base layer, the non-detection layer is formed adjacent to a main surface of the base layer, and the detection layer is formed adjacent to the main surface of the non-detection layer.
The laminate of (1) above may be a laminate in which the non-detection layer is formed adjacent to the main surface of the detection layer.

<Shape>
The laminate of the present invention may have any shape depending on the application.
For example, the shape can be the same as that of a substrate used in an electronic device manufacturing device.
This allows the laminate to be used as a so-called dummy substrate, making it possible to easily detect whether the above-mentioned processing has been performed uniformly over the entire substrate.
Here, "the same shape as the substrate used in the electronic device manufacturing equipment" refers to not only the case where the shape is completely the same as the shape of the substrate used in the electronic device manufacturing equipment, but also the case where the shape is substantially the same as the shape of the substrate used in the electronic device manufacturing equipment to the extent that the substrate can be placed (fitted) in the installation location of the substrate in each electronic device equipment where the above-mentioned processing is performed. "Substantially the same" may be, for example, if the difference in the length of the substrate's main surface relative to the length of the substrate's main surface (the diameter when the main surface shape is circular, or the length and width when the main surface shape is square or rectangular, etc.) is within ±5.0 mm, and the difference in the thickness of the substrate relative to the substrate is within ±1000 μm.

<Method of manufacturing laminate>
Examples of methods for producing the laminate include, but are not limited to, the following methods (1) to (4).
(1) A method in which a structure having an internal space communicating with the openings on the surface is provided on a base layer by any known suitable means, and then a detecting agent or a detecting agent solution is applied, impregnated or sprayed, etc., to retain the detecting agent in the internal space.
(2) A method in which a structure having an internal space communicating with the openings on the surface is formed by any suitable known means, and a detecting agent or a detecting agent solution is applied, impregnated or sprayed onto the structure to retain the detecting agent within the internal space, and then the detecting agent is fixed onto a base layer by any suitable known means.
(3) A method in which a composition containing a component for forming a structure, a component for forming an internal space in the structure that communicates with the openings on the surface, and the detecting agent is provided on a base layer, and then a treatment is performed to form an internal space in the structure that communicates with the openings on the surface.
(4) A method of preparing a composition containing a component that forms a structure, a component that forms an internal space in the structure that communicates with the openings on the surface, and the detecting agent, forming an internal space in the structure that communicates with the openings on the surface and retaining the detecting agent in the internal space, and then fixing the composition on a base layer by any suitable known means.
In the present invention, from the viewpoints of ease of production of the laminate and prevention of impurities from being mixed into the laminate, the above method (1) or (2) is preferred, and method (1) is more preferred.

When mixing, dissolving or dispersing, a known stirrer may be used as necessary. In this case, it is preferable to prevent contaminants originating from the stirrer from being mixed.
For mixing, dissolving or dispersing, a known method can be used, for example, a method of adding the sensing component to the solvent, a method of adding the solvent to the sensing component, a method of adding each component constituting the sensing agent to the solvent in order, etc.
When the sensing component is retained in the internal space, the solvent can be removed by known means such as drying, if necessary.

When providing a structure on a base layer, the base layer may be subjected to a surface treatment as necessary to improve adhesion. The surface treatment may be at least one selected from the group consisting of well-known methods such as primer treatment, chemical conversion treatment, plasma treatment, corona treatment, flame treatment, sandblasting treatment, etc.
As a means for providing the structures on the base layer, for example, the following method (1) or (2) can be used, but is not particularly limited.
(1) A solution for preparing a structure is applied onto the substrate layer that has been subjected to the above-mentioned surface treatment.
(2) After preparing the structure in advance, it is adhered onto the base layer using an adhesive or the like.
In the present invention, the above method (1) can be preferably used from the viewpoints of ease of production of the laminate and prevention of impurities from being mixed into the laminate due to the adhesive.

<Applications of the laminate>
The laminate of the present invention can be used not only to detect plasma or the like, but also as an indicator for detecting the uniformity of treatment with plasma or the like, by measuring the color difference based on the color of the detection layer before treatment.
For example, the laminate can be used as an indicator for use in equipment 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, a commercially available colorimeter is used to measure the color tone of the detection layer before and after detecting plasma or the like, thereby obtaining the values of L*, which represents lightness, and the chromaticities a ^{* and b*, which represent hue and saturation, in the L* a* b* color space (} note that the L ^* a*b* color space is a color system commonly used to represent the color of an object, which was standardized in 1976 by ^the International Commission on Illumination (CIE), and is also adopted in JIS Z 8781-4 and JIS Z 8781-5). Using these L ^* , a ^{* ,} and b ^* values, the following equation ΔE ^* =[(ΔL ^* ) ²⁺ (Δa ^* ) ²⁺ (Δb ^* ) ² ] ^1/2
The color difference ΔE is calculated by:
Based on the color difference ΔE, it is possible to measure the detection of plasma or the like by the detection layer, and in addition, to quantitatively obtain the in-plane uniformity of plasma or the like on the plane of the detection layer.
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, etc. Therefore, understanding the in-plane distribution of color difference can be used as an indicator for understanding the flow of plasma, etc., which is important in the manufacture of electronic devices, and for quickly evaluating the uniformity of the processing surface.
The laminate of the present invention is preferably one in which ΔE is 0.9 or more, preferably 3.0 or more, when treated with plasma or the like for a predetermined time, since this can be accurately judged by visual observation. It is also preferable that the color change after the maximum value of ΔE is less than 3.0 within the predetermined treatment time. By making the laminate have such a ΔE, the treatment with plasma or the like can be accurately grasped, and it is also easy to grasp the in-plane uniformity, etc.

When using the indicator, the indicator of the present invention may be placed at a substrate placement location in each electronic device manufacturing apparatus where the above-mentioned processes are carried out during the manufacture of electronic devices.
For example, the wafer may be placed horizontally (horizontally) relative to a wafer stage, heater, vacuum chuck table, etc., or may be placed vertically (vertically) using a wafer boat, etc.
When the indicator of the present invention has the same shape as a substrate used in manufacturing an electronic device, it can be handled and installed in the same manner as a substrate.
In such a case, an indicator placed within the apparatus changes color when exposed to the treatment, and the in-plane uniformity of the treatment can be easily detected.

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

Example 1
A silicon substrate used in the manufacture of semiconductors was used as the base layer.
After the surface of the silicon substrate was treated, a polyamideimide resin solution for forming a porous body was applied to the treated surface and dried to form a polyamideimide resin porous body (polyamideimide resin porous coating) having a thickness of about 20 μm on the treated surface of the silicon substrate. It was confirmed by observation with an electron microscope that the polyamideimide resin porous body had pores with open pores on the surface.
A solution (concentration 2% by mass (Example 1)) of CISolvent Violet 14, which is a dye containing no atoms other than carbon, hydrogen, oxygen, and nitrogen, was prepared.
The prepared sensing agent solution was applied to and impregnated into the polyamide-imide resin porous body, and then dried to prepare a laminate.
For the produced laminate, the content of each metal atom and the content of each halogen atom were measured, and the performance as a plasma indicator was evaluated as described below.
The results are shown in Table 1.

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

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

(Performance evaluation)
The laminate was used as a dummy substrate, and plasma treatment was performed using a commercially available plasma irradiation device with _CF4 gas under the conditions of gas flow rate: 10 cc/min, output: 50 W, initial pressure: 5 Pa, and treatment pressure: 20 Pa.
The L ^* , a ^* and b ^* of the laminate not subjected to the plasma treatment and the laminate subjected to the plasma treatment for a predetermined time were measured by a colorimeter, and the color difference ΔE before and after the plasma treatment was calculated. The results are shown in Table 1.

(Examples 2 to 16)
A laminate was prepared in the same manner as in Example 1, except that a solution of CI Solvent Red 52, CI Solvent Blue 35, CI Solvent Violet 13, CI Solvent Violet 14, CI Solvent Green 3, or Lumogen F Red 305 (the concentrations are shown in Table 1), which are dyes that do not contain atoms other than carbon, hydrogen, oxygen, and nitrogen, was used as the detector solution.
For the produced laminate, the contents of each metal atom and each halogen atom were measured, and the performance as a plasma indicator was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
A laminate was prepared in the same manner as in Example 1, except that the sensing agent solution was not applied to or impregnated into the polyamideimide resin porous body.
For the produced laminate, the contents of each metal atom and each halogen atom were measured, and the performance as a plasma indicator was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Example 17)
A laminate was prepared in the same manner as in Example 1, except that a polyimide-based resin solution for forming a porous body was used instead of the polyamideimide-based resin solution for forming a porous body. Thereafter, a performance evaluation as a plasma indicator was performed in the same manner as in Example 1, except that the treatment time was changed, and the color difference ΔE was obtained. In addition, the contents of metal atoms and halogen atoms 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 CI Solvent Violet 14. Thereafter, 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 the surface of a silicon substrate used in semiconductor manufacturing was treated, a polyimide resin solution for forming a porous body was applied to the treated surface and dried, thereby forming a polyimide resin porous body (polyimide resin porous coating) having a thickness of about 20 μm and having pores with open pores on the surface on the treated surface of the silicon substrate.
Lumogen F Red 305 is a dye that does not contain any atoms other than carbon, hydrogen, oxygen, and nitrogen. A 1.0% by mass solution (Example 19) and a 0.25% by mass solution (Example 20) of Lumogen F Red 305 were prepared as detector solutions.
The prepared sensing agent solution was applied to and impregnated into the polyimide-based resin porous body, and then dried to prepare a laminate.
For the produced laminate, the content of each metal atom, the content of each halogen atom, and the performance as a plasma indicator were each measured in the same manner as in Example 1.
The results are shown in Table 3.

From Tables 1 to 3, it can be seen that, although it depends on the type of dye and the structure having an internal space communicating with the openings on the surface, when the concentration of dye in the detector solution is high, it takes a long time for the color change to begin (the amount of plasma irradiation required to cause the color change is large), and when the concentration is low, the color change is small.
The indicator including the laminate of the present invention can determine whether the treatment has been properly performed based on the visual change in color tone. In this case, the sensitivity can be adjusted by adjusting the type and concentration of the dye in the detector solution, and it is possible to easily visually detect whether the treatment has been performed uniformly over the entire object to be treated.
Furthermore, the indicator containing the laminate of the present invention has a low content of metal atoms and halogen atoms, which makes it possible to avoid contamination of the treated object and the inside of the chamber due to contaminants generated during treatment with at least one selected from the group consisting of plasma, ozone, ultraviolet light, and radical-containing gas.

1 Structure 2 Detecting agent 3 Base layer 4 Detecting layer

Claims (4)

The sensor includes a detection layer that changes color when it detects at least one selected from the group consisting of plasma, ozone, ultraviolet light, and a radical-containing gas, and a substrate layer;
the detection layer has a structure having an internal space communicating with the openings on the surface;
the structure is a resin porous body obtained by a chemical means, which 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 internal space contains a detecting agent including at least one detecting component that changes color upon detecting at least one selected from the group consisting of plasma, ozone, ultraviolet light, and a radical-containing gas;
the sensing agent comprises a dye compound that does not contain any atoms other than carbon, hydrogen, oxygen, and nitrogen;
the dye compound is at least one selected from the group consisting of anthraquinone dyes, perylene dyes, methine dyes, indanthrene dyes, and azo dyes;
A laminate, in which the content of each metal atom in the laminate is less than 5.0 ppm by mass. 2. The laminate according to claim 1 , wherein the sensing agent comprises a resin and/or a resin precursor, and the resin and/or resin precursor does not contain atoms other than carbon, hydrogen, oxygen and nitrogen atoms. The laminate according to claim 1 or 2 , wherein the content of each halogen atom in the laminate is less than 30 ppm by mass. An indicator comprising the laminate according to any one of claims 1 to 3 .