Laminate and indicator

Abstract

To provide a laminate for measuring the ion intensity distribution of a surface in contact with the plasma, having a detection layer whose color tone changes upon contact with plasma containing at least ions, and further provide an ion intensity distribution indicator that can detect the ion intensity distribution on the surface of an object to be treated by a simple method.SOLUTION: A laminate includes a detection layer whose color tone changes when the detection layer comes into contact with plasma containing at least ions, and measures the ion intensity distribution of the surface in contact with the plasma.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a laminate and an indicator. [Background technology]

[0002] In the manufacture of electronic devices, including semiconductor devices, it is necessary to uniformly perform treatment using at least one selected from the group consisting of plasma, ozone, ions, ultraviolet light, and radical-containing gases (hereinafter sometimes referred to as "plasma, etc."). Furthermore, in order to improve processing performance and reduce variations during the manufacture of electronic devices, it is necessary to separately evaluate the effects of various active species contained in plasma, etc.

[0003] Among these, reactive ion etching is known as a process using plasma containing ions in the semiconductor device manufacturing process. During reactive ion etching, it is necessary to process the surface to be processed so that the ion intensity distribution is uniform. For example, in the pre-processing of semiconductor chip manufacturing, it is important that plasma processing is performed uniformly across the wafer surface, ensuring in-plane uniformity. Loss of in-plane uniformity leads to variations in the performance of each semiconductor chip formed on the semiconductor wafer, affecting yield. Furthermore, surface treatment of materials such as metals, ceramics, and resins by ion implantation is widely used in the medical and industrial fields as a means of controlling properties such as friction, wear resistance, corrosion resistance, wettability, and biocompatibility. Therefore, confirmation of the uniformity of ion treatment is essential when designing each electronic device manufacturing equipment, designing surface treatment equipment using ion implantation, and managing the manufacturing process using these equipment.

[0004] Various methods have been known so far for measuring ion intensity distribution and as indicators for detecting plasma containing ions. Patent Document 1 describes an ion intensity distribution measuring device that uses a Faraday cup assembly device to measure the ion intensity distribution of an ion beam with high accuracy. Patent Document 2 describes a plasma treatment detection indicator having a color-changing layer that changes color due to plasma treatment, in which the color-changing layer contains at least one metal element selected from the group consisting of Mo, W, Sn, V, Ce, Te, and Bi, and / or an inorganic compound containing the metal element. Patent Document 3 describes an indicator including a laminate, which has a detection layer that changes color upon detecting at least one selected from the group consisting of plasma, ozone, ultraviolet light, and radical-containing gases, and a base layer, wherein the detection layer has a structure with an internal space that communicates with an opening on the surface, and the internal space contains a detection agent that contains at least one detection component that changes color upon detecting at least one selected from the group consisting of plasma, ozone, ultraviolet light, and radical-containing gases, and the content of each metal atom in the laminate is less than 5.0 ppm by mass. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2019-121465 [Patent Document 2] Patent No. 6474390 [Patent Document 3] Japanese Patent Publication No. 2020-180963 Summary of the Invention [Problem to be solved by the invention]

[0006] The ion intensity distribution device of Patent Document 1 requires large-scale equipment and cannot be placed in a reaction chamber or the like where plasma or other treatment is performed in the pre-process of semiconductor chip manufacturing. The indicators described in Patent Documents 2 and 3 allow the progress of plasma processing or the like to be visually confirmed within a reaction chamber, but it is difficult to isolate and monitor only the ion intensity distribution. Until now, there has been no known method or ion intensity distribution indicator that can easily detect the ion intensity distribution on the surface of a workpiece in order to confirm the processing accuracy of ion processing.

[0007] The problem to be solved by the present invention is to provide a laminate having a detection layer that changes color upon contact with plasma containing at least ions, for measuring the ion intensity distribution on a surface that comes into contact with the plasma. Another problem to be solved by the present invention is to provide an ion intensity distribution indicator that can detect the ion intensity distribution on the surface of a workpiece by a simple method. [Means for solving the problem]

[0008] As a result of investigations to solve the above problems, the present inventors have found that the above problems can be solved by constructing a laminate having a specific structure and using it as an indicator. Specifically, the following applies: Section 1: A laminate having a detection layer whose color tone changes upon contact with plasma containing at least ions, for measuring the ion intensity distribution on a surface in contact with the plasma. Section 2: Item 2. The laminate according to item 1, wherein the detection layer is a layer containing a resin and / or a resin precursor that does not contain atoms other than carbon, hydrogen, oxygen, and nitrogen atoms. Section 3: Item 3. The laminate according to item 1 or 2, wherein the detection layer is a porous layer. Section 4: Item 3. The laminate according to item 1 or 2, which is for measuring only the ion intensity distribution on the surface in contact with plasma. Section 5: A laminate having a substrate layer and a detection layer partially provided on the substrate layer, the detection layer changing color upon contact with plasma containing at least ions, for measuring the ion intensity distribution on the surface that comes into contact with the plasma. Item 6: Item 6. An ion intensity distribution indicator for detecting an ion intensity distribution occurring during plasma irradiation, comprising the laminate according to item 1 or 5. [Effects of the Invention]

[0009] The present invention provides a laminate having a detection layer that changes color upon contact with plasma containing at least ions, for measuring the ion intensity distribution on a surface that comes into contact with plasma. The present invention also provides an ion intensity distribution indicator that can detect the ion intensity distribution on the surface of a workpiece in a simple manner. [Brief explanation of the drawings]

[0010] [Figure 1] 10 is a photograph showing the use of an indicator in which a detection layer is partially provided on a base layer. [Figure 2] FIG. 1 is a schematic diagram of an ion intensity distribution indicator according to an embodiment of the present invention. [Figure 3] FIG. 1 is a schematic diagram of an ion intensity distribution indicator according to another embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0011] [Laminate] The laminate of the present invention has a detection layer whose color changes upon contact with plasma containing at least ions, and is used to measure the ion intensity distribution on a surface that comes into contact with the plasma. The detection layer is provided on a substrate layer. If necessary, an intermediate layer can be provided between the detection layer and the substrate layer to eliminate the influence of the color tone of the substrate layer or to improve the adhesion of the substrate layer. The laminate of the present invention is preferably used for measuring only the ion intensity distribution on the surface in contact with plasma. The sensing layer of the laminate of the present invention preferably does not change color even when it comes into contact with active species other than ions (e.g., radicals, etc.). For example, it is preferable that the color of the sensing layer changes when it comes into contact with plasma containing ions whose source gas is argon, and that the color of the sensing layer does not change when it comes into contact with plasma that mainly contains radicals whose source gas is oxygen and contains almost no ions. In this specification, plasma and ions are defined as follows.

[0012] <Plasma> The plasma refers to plasma generated by applying AC voltage, DC voltage, pulse voltage, high frequency, microwaves, etc. to a plasma generating gas, and includes both low-pressure plasma and atmospheric pressure plasma. The plasma generating gas may be at least one 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. Examples of plasma include plasma generated in plasma processing apparatuses (apparatuses that perform plasma processing by applying AC voltage, DC voltage, pulse voltage, high frequency, microwaves, etc. in an atmosphere containing a plasma-generating gas) used in film-forming processes, etching processes, ashing processes, impurity-adding processes, cleaning processes, etc. during the manufacture of electronic devices.

[0013] <AEON> Examples of ions include those generated by applying high-frequency power to gases such as argon, methane, acetylene, etc. For example, ions may be used in sputtering, which involves accelerating ionized argon in an electric field in a vacuum and irradiating and colliding it with a metal surface or the like, thereby scraping off surface atoms by taking advantage of the property of hardly undergoing chemical reactions, or in ion beam etching, doping, etc. The ions may be ions contained in plasma. For example, plasma containing ions can be generated by applying AC voltage, DC voltage, pulse voltage, high frequency, microwaves, or the like to argon, nitrogen, air, or the like as a plasma generating gas.

[0014] <Detection layer> The sensing layer of the present invention is not particularly limited as long as it is a layer whose color tone changes upon contact with plasma containing at least ions. Upon contact with plasma containing at least ions, the sensing layer undergoes one or more color tone changes, including discoloration, decolorization, and color development. The sensing layer of the present invention preferably changes color when it comes into contact with plasma containing at least ions, causing ion bombardment to sever the molecular bonds of the components that make up the sensing layer, increasing the carbon atom concentration on the surface of the sensing layer (carbonization). It is believed that there is a correlation between the collision energy of ions and the severance of the molecular bonds of the components that make up the sensing layer, and the intensity distribution of ion energy can be evaluated from the degree of color change. In addition, the binding energy of the molecular bonds can be changed by adjusting the molecular structure of the components that make up the sensing layer, the structure of the sensing layer, etc. By adjusting the components that make up the sensing layer, it is possible to adjust the severance of molecular bonds (color change) in response to ion energy. As a result, the detection layer not only detects plasma containing at least ions, but also allows the ion intensity distribution of ions contained in the plasma to be easily detected visually.

[0015] (color tone) The color tone of the detection layer may be any color tone that allows the change in color tone of the detection layer surface upon contact with plasma containing at least ions to be recognized. For example, transparent, colored transparent, white, and light-colored are preferred. Light-colored ones include, for example, L * a * b * L in color space * Examples of colors include those with a value of 75 or higher. The color tone of the detection layer may be such that it can conceal the color tone of the substrate layer on which the detection layer is provided. When the detection layer comes into contact with plasma containing at least ions and the carbon atom concentration on the surface of the detection layer increases (carbonization), the color of the detection layer is preferably white or light-colored. When the substrate layer is white or light-colored, the color of the detection layer may be transparent or colored transparent.

[0016] (Detection layer forming material) The material constituting the detection layer is at least one selected from the group consisting of organic materials and organic-inorganic composite materials. Examples of organic materials include, but are not limited to, one or more selected from the group consisting of resins, resin precursors, paper, and composites thereof. Resins and / or resin precursors are particularly preferred, and resins and / or resin precursors containing no atoms other than carbon, hydrogen, oxygen, and nitrogen are more preferred. The resin or resin precursor is not particularly limited and may be a synthesized or commercially available material. Examples include at least one selected from the group consisting of polyimide resins, polyamideimide resins, polybenzimidazole resins, polyamide resins, polyolefin resins, polyurethane resins, melamine resins, polyester resins, and polycarbonate resins. In particular, using a heat-resistant polymer such as a polyamideimide resin (precursor), polyimide resin (precursor), polybenzimidazole resin (precursor), or polyamide resin as the structure results in a laminate with excellent heat resistance, making it possible to construct an indicator that can be used under high-temperature conditions and has strong resistance to plasma treatment. The organic-inorganic composite material includes a composite of the organic material and an inorganic material (metal, glass, ceramics, etc.). Examples of the composite include a laminate and a composition.

[0017] In the present invention, when the content of each metal atom in the laminate is less than 5.0 mass ppm and / or the content of each halogen atom is less than 30 mass ppm, it is preferable that the detection layer is made of an organic material, in particular, a resin or a resin precursor. In order to prevent contamination of the interior of the electronic device manufacturing equipment by metal atoms and / or halogen atoms, it is preferable to use an organic material, particularly a resin, as the detection layer. In the present invention, the detection layer is preferably a layer made of a compound that does not contain metal atoms, particularly a resin and / or resin precursor that does not contain atoms other than carbon, hydrogen, oxygen, and nitrogen. Furthermore, it is preferable to prevent impurities such as metal atoms and halogen atoms from being mixed into the detection layer by thoroughly purifying its components and not using metal tools during preparation. This allows the content of each metal atom in the laminate to be less than 5.0 ppm by mass, and when the laminate is used as an indicator for detecting plasma or the like, contamination within electronic device manufacturing equipment, particularly contamination by metal atoms and halogen atoms, can be effectively prevented. The detection layer may contain various components within a range that does not impair the effect of the color change, for the purpose of adjusting sensitivity, improving the visibility of the color difference before and after detection, etc. Examples of such components include at least one selected from the group consisting of additives such as dyes, resins and / or resin precursors, surfactants, fillers, color change retarders, color change accelerators, solvents, leveling agents, and antifoaming agents.

[0018] (detection layer thickness) The thickness of the detection layer is not particularly limited as long as it exhibits detection function, and can be appropriately optimized depending on the application, desired properties, etc. From the viewpoint of cleanliness and visibility, it is, for example, less than 100 μm, preferably 50 μm, more preferably 30 μm or less, and for example, 0.5 μm or more, preferably 5 μm, more preferably 15 μm or more. If the detection layer thickness is 100 μm or more, the amount of gas released from the detection layer may increase, resulting in a decrease in cleanliness. Furthermore, if it is less than 0.5 μm, the color change range may be narrowed due to the influence of the color tone of the layer below the detection layer.

[0019] (Film density of the sensing layer) The film density of the detection layer is not particularly limited as long as it does not impair the detection function, and can be optimized appropriately depending on the application, desired properties, etc. For example, when the detection layer is a non-porous layer, it is the film density of the base material. Furthermore, when the detection layer is a porous layer, the film density of the base material when it is a non-porous layer is taken as 100%, and the relative film density is, for example, 75.0% or less, preferably 35.0% or less, more preferably 30.0% or less, more preferably 25.0% or less, and preferably 15.0% or more. If it is less than 15.0%, it is difficult to form a color-change layer, and the film strength of the color-change layer will be insufficient. If it exceeds 75.0%, penetration of plasma into the color-change layer will be hindered, the decomposition of the detection agent will be insufficient, and the color-change sensitivity of the color-change layer will be reduced. In the present invention, the detection layer is preferably a porous layer.

[0020] When the detection layer is a porous layer, the film density is not particularly limited as long as it is within a range that allows the detection function to be exhibited, and can be appropriately optimized depending on the application, desired properties, etc. From the viewpoint of sensitivity, for example, a film density of 0.20 g / cm 3 or more, preferably 0.25 g / cm 3 More preferably, 0.30 g / cm 3 The upper limit is not particularly limited, but for example, it is 1.00 g / cm 3 It can be said that: When the sensing layer is a porous layer, the film density is 0.20 g / cm 3If the thickness is less than this, it will be difficult to form the detection layer, and the film strength of the detection layer will be insufficient. In the present invention, by forming the detection layer as a porous layer, it is possible to satisfy the color change speed of the detection layer, the accuracy of the color change evaluation, and the color change sensitivity.

[0021] When the sensing layer is a porous layer, the film density can be adjusted by adjusting the porosity. For example, (1) Porosity is created by chemical means such as using a pore-forming agent (for example, porosity is created using a foaming agent, porosity is created using gas generated during molding, porosity is created by removing the porosity-forming agent after molding by dissolving, vaporizing, sublimating, etc., porosity is created by phase separation using mixed solvents with different solubilities or boiling points, etc.) (2) Porosity due to stretching (3) Porosity due to fusion of powder particles (4) When making the material porous by mechanical means such as perforation, there is a means for adjusting the porosity.

[0022] In the present invention, in the means (1) above, it is preferable to use a means for adjusting the type and amount of a good solvent in which the resin constituting the detection layer, the resin or its precursor, has a high solubility, and the type and amount of a poor solvent in which the resin has a low solubility. When one or more types of resin selected from the group consisting of polyimide resins, polyamideimide resins, polybenzimidazole resins, etc. are used as the resin constituting the structure, one or more types of nitrogen-containing polar solvents selected from the group consisting of amide solvents, urea solvents, etc. are preferably used as the good solvent, and one or more types of organic solvents selected from the group consisting of ether solvents, hydrocarbon solvents, ester solvents, etc. are preferably used as the poor solvent. Examples of amide solvents include N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide (DMAc), etc. Examples of urea solvents include tetramethylurea and dimethylethyleneurea. Examples of ether solvents include diglyme, triglyme, tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, dipropylene glycol dimethyl ether, tetrahydrofuran, and dioxane. Examples of hydrocarbon solvents include n-hexane, cyclohexane, benzene, toluene, xylene, and petroleum ether. Examples of ester solvents include ethyl carbitol acetate, butyl carbitol acetate, dimethyl succinate, diethyl succinate, dimethyl glutarate, diethyl glutarate, dimethyl adipate, and diethyl adipate. In the present invention, a good solvent for a resin or resin precursor is a solvent that dissolves 0.1 g or more of the resin or resin precursor in 100 g of the solvent at 25° C. A poor solvent for a resin or resin precursor is a solvent that dissolves less than 0.1 g of the resin or resin precursor in 100 g of the solvent at 25° C.

[0023] In the present invention, when the total amount of the resin or resin precursor, good solvent, and poor solvent is taken as 100 mass %, the amounts of the resin or resin precursor, good solvent, and poor solvent used are preferably as follows: Resin or resin precursor: For example, 7.0% by mass or more, preferably 8.0% by mass or more, and for example, 15.0% by mass or less, preferably 11.0% by mass or less. Good solvent: for example, 10.0% by mass or more, preferably 15.0% by mass or more, and for example, 50.0% by mass or less, preferably 40.0% by mass or less. Poor solvent: For example, 35.0% by mass or more, preferably 40.0% by mass or more, and for example, 80.0% by mass or less, preferably 70.0% by mass or less. If the amount of resin or resin precursor exceeds 15.0% by mass, it may be difficult to adjust the porosity and the discoloration range may be narrowed, while if the amount of resin is less than 7.0% by mass, the porous layer may not be formed and the discoloration sensitivity may be poor. If the amount of the good solvent exceeds 50.0% by mass, it may be impossible to form a porous layer, and if the amount of the good solvent is less than 10.0% by mass, unevenness may occur and phase separation may occur. If the amount of the poor solvent exceeds 80.0% by mass, unevenness may occur and phase separation may occur, whereas if the amount of the poor solvent is less than 35.0% by mass, it may be impossible to form a porous layer.

[0024] In the present invention, a varnish containing a resin or a resin precursor and an organic solvent may be used, and a good solvent and a poor solvent may be mixed with the varnish. The varnish may contain 10 to 20 mass %, preferably 10 to 15 mass %, of the resin or resin precursor. In this case, when the total amount of the varnish, good solvent, and poor solvent is taken as 100 mass %, the amounts of the varnish, good solvent, and poor solvent used are preferably as follows: Varnish: For example, 60% by mass or more, preferably 70% by mass or more, and for example, 90% by mass or less, preferably 80% by mass or less. Good solvent: For example, 1% by mass or more, preferably 10% by mass or more, and for example, 20% by mass or less, preferably 15% by mass or less. Poor solvent: For example, 1% by mass or more, preferably 10% by mass or more, and for example, 20% by mass or less, preferably 15% by mass or less. If the amount of varnish exceeds 90% by mass, it may be difficult to adjust the porosity and the discoloration range may be narrowed, whereas if the amount of varnish is less than 60% by mass, the porous layer may not be formed and the discoloration sensitivity may be reduced. If the amount of the good solvent exceeds 20% by mass, it may be impossible to form a porous layer, and if the amount of the good solvent is less than 1% by mass, unevenness may occur and phase separation may occur. If the amount of the poor solvent exceeds 20% by mass, unevenness may occur and phase separation may occur, whereas if the amount of the poor solvent is less than 1% by mass, it may be impossible to form a porous layer.

[0025] The sensing layer has a film density of 0.20 g / cm 3 or more, preferably 0.20 g / cm 3 More than 1.00g / cm 3 The following porous layers are preferred: In particular, the detection layer is preferably "a porous layer of polyimide resin obtained from a resin solution containing a polyimide resin precursor, an amide solvent (a good solvent for the polyimide resin precursor), and an ether solvent (a poor solvent)" or "a porous layer of polyamideimide resin obtained from a resin solution containing a polyamideimide resin precursor, an amide solvent (a good solvent for the polyamideimide resin precursor), and an ether solvent (a poor solvent)."

[0026] <Base material layer> The substrate layer is not particularly limited as long as it can support 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. The thickness of the substrate layer is not particularly limited as long as it can reliably support the detection layer, and is, for example, 0.01 mm or more, preferably 0.1 mm or more, and for example, 10 mm or less, preferably 1 mm or less. The shape of the base material layer is not particularly limited. For example, it can be any shape such as a circle, a square, a rectangle, a triangle, or a hexagon depending on the application. In the present invention, by making the shape of the laminate described below the same or substantially the same as the shape of a substrate used in an electronic device manufacturing apparatus, for example, the laminate can be used as a so-called dummy substrate, and it becomes possible to easily detect whether the above-mentioned treatment is being performed uniformly on the entire substrate.

[0027] Examples of inorganic materials constituting the substrate layer include at least one selected from the group consisting of metals or alloys, semiconductor materials, ceramics, glass, quartz, sapphire, and concrete. Examples of organic materials constituting the substrate layer include 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, etc. 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, resins, and paper as the substrate layer.

[0028] Examples of the semiconductor material include silicon (Si), germanium (Ge), tellurium (Te), zinc oxide (ZnO), gallium arsenide (GaAs), gallium nitride (GaN), gallium oxide (Ga2O3), and nitride semiconductors. and at least one selected from the group consisting of aluminum (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, metal oxynitrides, etc. However, there is no particular limitation.

[0029] Here, the metal oxide or metal oxynitride may be, for example, an In—Sn—Ga—Zn—O-based oxide. , In-Hf-Ga-Zn-O system oxides, In-Al-Ga-Zn-O system oxides, In-Sn-Al-Zn-O system oxides, In-Sn-Hf-Zn-O system oxides, In-Hf-Al-Zn-O system oxides, In-Ga-Zn-O system oxides, In-Sn-Zn-O system oxides, In-Al-Zn-O system oxides, Sn-Ga-Zn-O system oxides, Al-Ga-Zn-O system oxides, Sn-Al-Zn-O system oxides, In-Sn-Zn-O system oxides, In-Hf-Zn-O system oxides, In-La-Zn-O system oxides, In-Ce-Zn-O system oxides, In-Pr-Zn-O system oxides, In-Nd-Zn- O oxide, In-Sm-Zn-O oxide, In-Eu-Zn-O oxide, In-Gd-Zn-O oxide, In-Tb-Zn-O oxide, In-Dy-Zn-O oxide, In-Ho-Zn-O oxide, In-Er-Zn-O oxide, In-Tm-Zn-O oxide, In-Yb-Z n-O oxide, In-Lu-Zn-O oxide, In-Zn-O oxide, Sn-Zn-O oxide, Al-Zn-O oxide, Zn-Mg-O oxide, Sn-Mg-O oxide, In-Mg-O oxide, In-Ga-O oxide, Zn-ON oxynitride, In-O oxide (indium oxide). At least one selected from the group consisting of Sn-O-based oxides (tin oxide), Zn-O-based (zinc oxide), etc. Species include, but are not limited to: Here, for example, an In-Sn-Ga-Zn-O-based oxide refers to an oxide semiconductor containing 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.

[0030] The resin may be a 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 resins, polyethylene naphthalate resins, polybutylene terephthalate resins, 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, etc. is used.

[0031] When the laminate is used as an indicator in the manufacturing equipment of each product, examples of materials constituting the base layer include the following. Indicators for semiconductor manufacturing equipment: silicon, gallium arsenide, silicon carbide, etc. Indicators for LED manufacturing equipment: sapphire, gallium nitride, gallium arsenide, etc. Indicators for semiconductor laser manufacturing equipment: gallium arsenide, gallium nitride, sapphire, etc. Indicators for power device manufacturing equipment: silicon carbide, gallium nitride, silicon, etc. Indicators for solar cell manufacturing equipment: silicon, glass, germanium, etc. Indicators for LCD manufacturing equipment: silicon, glass, germanium, etc. Indicators for organic EL display manufacturing equipment: glass, etc. General-purpose and simple indicators: resin, paper, glass, etc.

[0032] <Hidden Layer> The laminate of the present invention may have a masking layer between the detection layer and the substrate layer. The concealing layer is a layer for preventing the color tone of the base layer from affecting the color tone of the detection layer, observation of discoloration of the detection layer, etc. Furthermore, the color tone of the concealing layer is preferably a color tone that does not affect the color tone of the detection layer, observation of discoloration of the detection layer, etc. The components constituting the masking layer are not particularly limited. For example, the masking layer may be composed of the same components as those constituting the detection layer. In this case, the color tone of the masking layer and the color tone of the detection layer after discoloration will be similar, making it possible to more clearly observe the discoloration of the detection layer. Furthermore, even if the components of the masking layer are different from those of the detection layer, it is advantageous to consider the color tone and make it similar to the color tone of the detection layer after discoloration. Furthermore, by using a masking layer that has a primer function, the adhesion between the substrate layer and the detection layer can be improved. The thickness of the concealing layer is not particularly limited, but is, for example, 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and is, for example, 35 μm or less, more preferably 30 μm or less.

[0033] <Other layers> The laminate of the present invention may have other layers in addition to the detection layer, the substrate layer, and the optional masking layer. Examples of the other layers include a spacer layer, a primer layer, a release layer, and a buffer layer. The order of lamination of the detection layer, substrate layer, masking layer, and other layers is not particularly limited, as long as the masking layer, which is provided as needed, is provided between the detection layer and the substrate layer. The detection layer, the hiding layer, and the other layers may each be formed as a single layer or as multiple layers. Furthermore, the same layers may be adjacent to each other. In this case, the same layers may have the same or different compositions. The detection layer, the masking layer, and other layers 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 other layers can be formed so that part or all of at least one detection layer is exposed to plasma or the like, particularly to ensure a change in color tone of the detection layer. The materials constituting the other layers are not particularly limited, and may be any of organic materials, inorganic materials, and organic-inorganic composite materials.

[0034] <Detection layer placement> In the present invention, the detection layer can be formed entirely or partially on the substrate layer. For example, when the detection layer is partially formed on the substrate layer, (a) The area of ​​the detection layer exposed to the plasma can be reduced, thereby reducing the total amount of impurities entering the chamber of the plasma processing device; (b) When manufacturing an indicator for use in a manufacturing process using a large substrate such as a liquid crystal display or an organic EL display, the detection layer can be produced at a lower cost. (c) When evaluating the color tone that changes upon contact with plasma, regardless of the size of the substrate, there is no need to use an expensive large-area colorimeter, and an inexpensive commercially available colorimeter can be used. It is advantageous in the following respects.

[0035] When a detection layer is provided on a portion of the plasma-exposed surface of the laminate, it can be provided in one or more locations on the base layer, as shown in Figures 1 to 3, for example. When provided in two or more locations, the location of the detection layer is not particularly limited. It can be provided at any desired location for measurement, and can be arranged so that the distribution of plasma irradiation over the entire base layer (substrate) can be grasped. For example, the detection layer can be arranged so that it is evenly spaced on the base layer, or so that it is evenly spaced from the center of the base layer to its periphery. Furthermore, when the base layer (substrate) is circular (e.g., for use as an indicator for semiconductor manufacturing equipment), the detection layer can be arranged circumferentially, and when the base layer (substrate) is square or rectangular (e.g., for use as an indicator for liquid crystal display manufacturing equipment), the detection layer can be arranged in a quadrangular shape.

[0036] <Layer structure of laminate> The laminate of the present invention may have any layer structure using a detection layer, a substrate layer, a masking layer and other layers, as long as the completion of each of the above treatments and in-plane uniformity can be confirmed. For example, the color tone of the detection layer before the color tone change is made similar to the color tone of layers other than the detection layer (hereinafter sometimes referred to as "non-detection layers"), and each layer can be formed so that the color difference between the detection layer and the non-detection layer can be distinguished due to the color tone change of the detection layer caused by ions. For example, the color tone of the detection layer before the color tone changes can be formed to be different from the color tone of the non-detection layer, and the layers can be formed so that the color difference between the detection layer and the non-detection layer disappears as the color tone of the detection layer changes due to ions. For example, by forming a detection layer with a different design on a layer in which a detection layer and a non-detection layer are formed so that they do not overlap (hereinafter, sometimes referred to as a "detection-non-detection layer"), 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.

[0037] In the laminate of the present invention, a preferred embodiment of the layer structure is as follows: (1) A laminate in which a detection layer is formed adjacent to at least one main surface of a base material layer; (2) A laminate in which a non-detection layer and a detection layer are formed in this order on a base material layer, the non-detection layer is formed adjacent to the main surface of the base material layer, and the detection layer is formed adjacent to the main surface of the non-detection layer. The laminate (1) may be a laminate in which the non-detection layer is formed adjacent to the main surface of the detection layer. The laminate of the present invention may be configured so that at least one of letters, designs, and symbols appears due to the change in color of the sensing layer, in order to notify the user that the sensing layer has changed in color due to ions. The letters, designs, and symbols include all information that notifies the user of the color change, and these letters, designs, and symbols can be designed appropriately depending on the intended use, etc.

[0038] <shape> The laminate of the present invention can be formed into any shape depending on the application. For example, the laminate can be made to have the same or nearly the same shape as a substrate used in an electronic device manufacturing apparatus and used as a so-called dummy substrate, making it possible to easily detect whether the above-mentioned processing is being performed uniformly over the entire substrate. Here, "the same shape as the substrate used in the electronic device manufacturing equipment" means not only completely the same as the shape of the substrate used in the electronic device manufacturing equipment, but also substantially the same as the shape of the substrate used in the electronic device manufacturing equipment to the extent that it 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" means, for example, that the difference in the length of the main surface of the laminate relative to the length of the main surface of the substrate (diameter if the main surface shape is circular, or length and width if the main surface shape is square, rectangular, etc.) is within ±5.0 mm, and the difference in thickness of the laminate relative to the substrate is within ±1000 μm.

[0039] <Content of each metal atom in the laminate> The content of each metal atom in the laminate is preferably less than 5.0 ppm by mass, more preferably less than 1.0 ppm by mass, even more preferably less than 0.5 ppm by mass, still more preferably less than 0.1 ppm by mass, most preferably less than 1.0 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. To make the content of each metal atom in the laminate less than 5.0 ppm by mass, all materials contained in the laminate should be free of metal atoms. Furthermore, all components (including solvents) related to the laminate should be free of metal atoms, and metal-atom-containing substances present as impurities should be removed by purification. Furthermore, it is preferable not to use tools or the like that may cause contamination of metal atoms in the manufacturing process.

[0040] In the present invention, the content of each metal atom in all layers, including the detection layer, base layer, and concealing 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. Furthermore, an indicator including the laminate of the present invention is introduced into a processing device together with a material to be processed, and a process such as plasma processing is carried out. Thereafter, each metal atom on the surface of the material to be processed introduced into the processing device is recovered using 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 is 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, when the laminate is used as an indicator in an electronic device manufacturing apparatus, it is possible to prevent contamination of the treated object or the inside of the manufacturing apparatus with metal atoms. This makes it possible to obtain an indicator that can be used in the manufacturing process of semiconductor electronic devices (particularly in the etching process in the first half of the process) where the presence of metal atoms is particularly undesirable.

[0041] <Content of each halogen atom> The content of each halogen atom in the laminate is preferably less than 30 ppm by mass, more preferably less than 5 ppm by mass, even more preferably less than 1 ppm by mass, still more preferably less than 0.5 ppm by mass, and most preferably less than 1.0 ppt by mass. To keep the content of each halogen atom in the laminate to less than 30 ppm by mass (preferably 5 ppm by mass), it is preferable that all materials contained in the laminate are halogen-free. It is also preferable that all components (including solvents) related to the laminate are halogen-free and that halogen-containing substances contained as impurities are removed by purification. Furthermore, it is preferable to use a method in the manufacturing process that does not use tools that may cause contamination with halogen atoms.

[0042] In the present invention, the content of each halogen atom in each material used in all layers, including the detection layer, substrate layer, and concealing 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. Furthermore, an indicator including the laminate of the present invention is introduced into a processing device together with a material to be processed, and a process such as plasma processing is carried out. Thereafter, halogen atoms present on the surface of the material to be processed introduced into the processing device are recovered, and the content of each halogen atom is measured by combustion ion chromatography, ICP-MS, or the like. If each is less than 30 ppm by mass, the content of each halogen atom in the laminate is determined to be 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 apparatus, it is possible to prevent contamination of the treated object and the inside of the manufacturing apparatus with halogen atoms. This makes it possible to obtain an indicator that can be used in the manufacturing process of semiconductor electronic devices (particularly in the etching process in the first half of the process) where the presence of halogen atoms is particularly undesirable.

[0043] <Method of manufacturing laminate> The method for producing the laminate is not particularly limited, and examples thereof include: (1) a method in which a masking layer or the like is provided on a base layer as needed, and then a detection layer-forming material is applied or printed, and then dried and heated to form a detection layer, thereby producing a laminate; and (2) a method in which a detection layer is formed from a detection layer-forming material, and then fixed onto a base layer on which a masking layer or the like is provided as needed. In the present invention, either of the methods (1) and (2) may be used as long as it is possible to ensure ease of production of the laminate and prevention of impurities from being mixed into the laminate.

[0044] In the present invention, when emphasis is placed on preventing impurities from being mixed in, it is preferable to provide a detection layer on only a portion of the plasma-exposed surface of the laminate, rather than providing a detection layer on the entire plasma-exposed surface of the laminate. The method for providing a detection layer of any shape on a portion of the plasma-exposed surface of the laminate is not particularly limited. For example, a detection layer can be provided at any position on the substrate layer by a coating or printing method, a separately prepared detection layer of any shape can be fixed at any position on the substrate layer, or a detection layer can be provided by providing a mold, depression (recess), through-hole, etc. at any position on the substrate layer and pouring (filling) a detection layer-forming material into it.

[0045] There are no particular limitations on the method for providing a detection layer of any shape at any position by coating or printing. Coating methods include, for example, spray coating, coating with a brush, roller, or blade, and dip coating. Printing methods include, for example, screen printing, gravure printing, offset printing, letterpress printing, flexographic printing, and inkjet printing. When using coating / printing methods to provide a detection layer of any shape at any position, a method can be used in which, for example, a pattern is formed on the plasma-exposed surface of the laminate using a masking agent, and then the substrate is immersed in a paint or ink to form the detection layer. In this case, the masking agent is removed with a chemical solution after the detection layer is formed. Alternatively, for example, a detection layer can be formed on the entire plasma-exposed surface of the laminate by coating / printing, and then a pattern is formed on the detection layer using a masking agent. The detection layer in the areas where the masking agent is not formed is removed with a chemical or solvent, and then the masking agent is removed with a chemical.

[0046] The method for fixing a separately prepared detection layer at a desired position on the base layer is not particularly limited. For example, it can be attached to the base layer by transfer, attachment with an adhesive or pressure-sensitive adhesive, attachment with double-sided tape, or other known joining methods. Alternatively, at least one depression (recess) or through-hole (e.g., stepped hole, tapered hole, female thread hole) can be formed in the base layer, and a pre-formed detection layer can be fitted and fixed.

[0047] There is no particular limitation on the method for providing a detection layer by providing a mold, depression (recess), through-hole, or the like at any position on the base layer and then pouring (packing) the detection layer-forming material into it. For example, the detection layer can be fixed by forming one or more molds of any shape, one or more depressions (recesses) or through-holes (stepped holes, tapered holes, female screw holes, etc.), and then pouring (packing) the detection layer-forming material into them.

[0048] When fitting and fixing the detection layer or when pouring (filling) the detection layer forming material into the recess or through-hole, the base layer and the fitted detection layer may be flush with each other, the detection layer may be recessed (concave, recessed, etc.) more than the base layer, or the detection layer may protrude from the base layer. Furthermore, a spacer layer or a buffer layer may be provided in the recess or through-hole as needed. When the through-hole has a step or a tapered shape, the detection layer can be easily attached to and detached from the substrate layer.

[0049] When a detection layer is provided on a portion of the plasma-exposed surface of the laminate, the detection layer can be provided at any desired location for measurement, and may be provided in one or more locations. In the case of multiple locations, the detection layers can be arranged so that they are evenly spaced apart, or evenly spaced around the center. Furthermore, in the case of an indicator for semiconductor manufacturing equipment with a circular base layer (substrate), the detection layer can be arranged circumferentially, for example. In the case of an indicator for liquid crystal display manufacturing equipment with a square or rectangular base layer (substrate), the detection layer can be arranged in a rectangular shape.

[0050] When a detection layer is provided on a portion of the plasma-exposed surface of the laminate, it can be provided in one or more locations on the substrate layer. When provided in two or more locations, the location of the detection layer is not particularly limited. It can be provided at any desired location for measurement, and can be arranged so that the distribution of plasma irradiation over the entire substrate layer (substrate) can be grasped. For example, the detection layers can be arranged so that they are evenly spaced on the substrate layer, or so that they are evenly spaced at the center and its periphery. Furthermore, when the substrate layer (substrate) is circular (e.g., for use as an indicator for semiconductor manufacturing equipment), the detection layers can be arranged circumferentially. When the substrate layer (substrate) is square or rectangular (e.g., for use as an indicator for liquid crystal display manufacturing equipment), the detection layers can be arranged in a quadrangular shape. When the base layer (substrate) is circular (used as an indicator for semiconductor manufacturing equipment, etc.), examples of the arrangement of the detection layer include, but are not limited to, the arrangements shown in Figures 1 to 3.

[0051] When providing a detection layer or the like on a substrate layer, the adhesion may be improved by subjecting the substrate layer to a surface treatment as needed. Examples of the surface treatment include 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, and sandblasting treatment.

[0052] <Applications of laminates> The laminate of the present invention can not only detect ions but also measure the ion intensity distribution by measuring the color difference based on the color of the detection layer before treatment, and therefore can be used as an indicator for detecting the uniformity of ion treatment. For example, the laminate can be used as an indicator for use in apparatus for manufacturing electronic devices such as semiconductors, LEDs, semiconductor lasers, power devices, solar cells, liquid crystal displays, organic EL displays, and MEMS. It can also be used as a general-purpose, simple indicator for detecting ions in ion-containing plasma. Furthermore, as described below, it can also be used as an ion intensity distribution indicator.

[0053] When using the indicator, the indicator of the present invention may be placed at a location where a substrate is placed in each electronic device manufacturing apparatus where the above-mentioned processes are carried out when manufacturing electronic devices. For example, the wafer may be placed horizontally (horizontally) on a wafer stage, heater, vacuum chuck table, etc., or may be placed vertically (vertically) using a wafer boat, etc. If the indicator of the present invention has the same shape as the substrate used in manufacturing the electronic device, it can be handled and installed in the same way as the substrate. In such a case, an indicator placed in the device changes color when exposed to the treatment, and the in-plane uniformity of the treatment can be easily detected.

[0054] In the present invention, a commercially available colorimeter is used to measure the color tone of the detection layer before and after detecting plasma, etc., to determine the L * a * b * Color space (Note: L * a * b * The color space is a color system commonly used to represent the color of an object. It was standardized by the International Commission on Illumination (CIE) in 1976 and is also used in JIS Z 8781-4 and JIS Z 8781-5. * , chromaticity a, which represents hue and saturation * and b * These L * , a * and b * Using the value of ΔE * ab =[(ΔL * ) 2 +(Δa * ) 2 +(Δb * ) 2 ] 1 / 2 Color difference ΔE * ab is calculated. The color difference ΔE *ab Based on this, in addition to measuring the detection of plasma etc. by the detection layer, it is possible to quantitatively obtain the in-plane uniformity of plasma etc. 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) correlates with the flow of plasma, etc. Therefore, understanding the in-plane distribution of color difference can serve as an indicator for quickly assessing the flow of plasma, etc., which is important in the manufacture of electronic devices, and the uniformity of the processed surface. The laminate of the present invention has a ΔE * ab It is preferable that ΔE is 0.9 or more, and preferably 3.0 or more, because it can be accurately judged visually. * ab It is preferable that the change in color tone after reaching the maximum value of ΔE is less than 3.0 within a predetermined processing time. * ab By forming a laminate showing this characteristic, it is possible to accurately grasp the treatment by plasma or the like, and it is also easy to grasp the in-plane uniformity and the like.

[0055] [Ion Intensity Distribution Indicator] The inventors have found that the laminate of the present invention has a correlation between the ionic strength distribution and the discoloration of the sensing layer (has ionic strength-dependent characteristics). Furthermore, the sensing layer of the laminate of the present invention hardly undergoes discoloration due to active species other than ions, such as radicals, contained in plasma. As a result, when variations (non-uniformities) in the ionic strength of the workpiece (such as a wafer) occur during processing with ion-containing plasma, particularly during plasma processing, a discoloration distribution occurs in the sensing layer of the laminate. It has been found that by reading this discoloration distribution, it is possible to easily and relatively detect the ionic strength distribution on the surface of the workpiece. Specifically, by utilizing the ionic strength-dependent characteristics of the detection layer of the laminate, whose color change sensitivity increases with ionic strength, it is possible to measure the color difference between different color change regions, thereby indirectly measuring the temperature difference within the surface. For example, the present inventors have calculated the ion intensity difference within the plane of the laminate X1 of the example as a function of plasma treatment time and ΔE *ab For example, we found that the ΔE * ab From this, it is possible to measure (estimate) the ion intensity distribution generated during plasma processing.

[0056] The ion intensity distribution indicator of the present invention is useful for detecting ion intensity distribution in a process using a plasma containing ions or in an ion implantation process in a semiconductor device manufacturing process. In particular, the ion implantation process is an essential technique for adding impurities to semiconductor devices, and the ion intensity distribution during this process can be determined by a simple and easy means, which is extremely useful in semiconductor device manufacturing. Furthermore, ion surface treatment and ion implantation are being increasingly applied in the medical and industrial fields to control the friction, wear resistance, corrosion resistance, wettability, etc. of metals, ceramics, polymeric materials, and other industrial materials, as well as to control biocompatibility, etc. In these fields as well, it is now possible to know the ion intensity distribution by a simple and easy means, which is extremely meaningful. Furthermore, the ionic strength distribution indicator of the present invention can reduce the metal content in the laminate, and can be used in semiconductor manufacturing equipment that is sensitive to contamination by metals, etc., and can easily measure ionic strength distribution.

[0057] The specific configuration of the indicator will be described in detail with reference to FIGS. Figure 1 is a photograph showing the use of an indicator having a detection layer partially provided on a base layer. Figure 1 shows the use of an indicator placed in a chamber for plasma treatment, where indicator 1 having detection layers 3 provided at multiple locations on base layer 2 is placed in the chamber of the plasma treatment device, and plasma treatment is carried out. The indicator of the present invention can also be used in the same manner. Fig. 2 is a schematic diagram of an ion intensity distribution indicator according to one embodiment of the present invention, showing an example in which the indicator 1 is constructed by providing detection layers 3 at multiple locations on a base layer 2 (substrate). Fig. 2A shows an example in which detection layers are provided at five locations on the base layer, and Fig. 2B shows an example in which detection layers are provided at 13 locations on the base layer. FIG. 3 is a schematic diagram of an ion intensity distribution indicator according to one embodiment of the present invention, showing an example in which a detection layer 3 is provided at one location on a substrate layer 2 (substrate). FIG. 3A shows an example in which a recess 4 (concave) for fixing the detection layer 3 is formed on the substrate layer 2, and FIG. 3B shows an example in which the indicator 1 is constructed by fixing the detection layer 3 to the recess 4 and providing the detection layer 3 on the substrate layer 2. Note that while FIG. 3 shows only one recess 4 (concave), two or more recesses may be provided. The shape of the recess 4 (concave) is not limited to a circle and can be any shape, such as a triangle, quadrangle (square, rectangle), or hexagon. The recess 4 (concave) can have a gap or the like to facilitate removal of the detection layer. Instead of the recess 4 (concave), a through-hole (e.g., a stepped hole, a tapered hole, or a female-threaded hole) may be used. [Example]

[0058] 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. Unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass."

[0059] [Preparation of laminate] <Laminated body X1> A detection layer forming material containing a polyimide precursor solution, an amide-based solvent (a good solvent for polyimide), and an ether-based solvent (a poor solvent for polyimide) was spin-coated onto a silicon substrate, and the substrate was dried and heat-treated in a uniform heater to form a porous detection layer on the silicon substrate, thereby preparing laminate X1.

[0060] <Laminate Y1> Bismuth oxide (coloring material), titanium oxide (opacifying agent), resin, and a cellosolve-based solvent were mixed and dispersed to form a slurry, which was then spin-coated onto a silicon substrate and dried in a dryer to form a detection layer containing bismuth oxide on the silicon substrate, thereby preparing laminate Y1.

[0061] <Laminate Y2> A porous layer-forming material containing a polyimide precursor solution, an amide-based solvent (a good solvent for polyimide), and an ether-based solvent (a poor solvent for polyimide) was spin-coated onto a silicon substrate, and the substrate was dried and heat-treated in a uniform heater to form a porous layer on the silicon substrate. A detection layer-forming material containing a polyimide precursor solution, a perylene-based dye, an amide-based solvent (a good solvent for polyimide), and an ether-based solvent (a poor solvent for polyimide) was spin-coated onto the porous layer, followed by drying and heat treatment in a uniform heating heater to form a detection layer containing the dye in the pores of the porous body on the porous layer formed on the silicon substrate, thereby preparing laminate Y2.

[0062] [No discoloration in plasmas containing almost no ions] <Examples 1 and 2, Comparative Examples 1 to 4> The detection layers of the laminates X1, Y1, and Y2 were treated with plasma containing almost no ions under the following plasma condition 1. L of the sensing layer after treatment with a plasma containing almost no ions * , a * and b * was measured with a colorimeter, and the color difference ΔE before and after plasma treatment for each plasma treatment time was * ab Furthermore, the color difference ΔE * ab The results are shown in Table 1.

[0063] (Plasma treatment condition 1) Source gas: O2 Plasma equipment: Inductively Coupled Plasma (ICP) Plasma type plasma device Gas flow rate: 40sccm Initial pressure: 5 x 10 -4 Pa or less Processing pressure: 10Pa Distance between electrodes: 40mm Power: 150W Power supply: 13.56MHz Plasma treatment time: See Table 1

[0064] (Non-discoloration evaluation criteria) S:ΔE * ab <0.4 A: 0.4≦ΔE * ab ≦3.2 B: 3.2<ΔE * ab ≦6.5 C:6.5<ΔE * ab ≦13.0 D:13.0<ΔE * ab

[0065] [Table 1]

[0066] [Discoloration due to plasma containing ions] <Examples 3 to 6> The detection layer of the laminate X1 was treated with plasma containing ions under the following plasma condition 2. L of the sensing layer after treatment with ion-containing plasma * , a * and b * was measured with a colorimeter, and the color difference ΔE before and after plasma treatment for each plasma treatment time was * ab The results are shown in Table 2.

[0067] (Plasma treatment condition 2) Source gas: See Table 2 Plasma equipment: Inductively Coupled Plasma (ICP) Plasma type plasma device Gas flow rate: 40sccm Initial pressure: 5 x 10 -4 Pa or less Processing pressure: 10Pa Distance between electrodes: 40mm Power: 150W Power supply: 13.56MHz Plasma treatment time: See Table 2

[0068] (Discoloration evaluation criteria) S:ΔE * ab ≧20.0 A: 20.0 ≥ ΔE * ab >10.0 B: 10.0 ≥ ΔE * ab >3.2 C: 3.2 ≥ ΔE * ab

[0069] [Table 2]

[0070] Example 7 The cellulose resin was dissolved in a cellosolve-based solvent to a resin concentration of 5% by mass. The resulting resin solution was applied to a glass plate and dried on a hot plate to obtain a resin film. The resulting resin film was treated with ion-containing plasma under the same conditions as in Example 3, and the color difference ΔE before and after the ion-containing plasma treatment was measured in the same manner as in Example 3. * ab The results are shown in Table 3.

[0071] <Examples 8 to 31> The resin was as shown in Table 3, and the color difference ΔE before and after the plasma treatment containing ions was measured in the same manner as in Example 7, except that the resin concentration was 15 mass %. * ab The results are shown in Table 3.

[0072] Example 32 The color difference ΔE before and after the plasma treatment containing ions was measured in the same manner as in Example 7, except that a Teflon (registered trademark) film was used. * ab The results are shown in Table 3.

[0073] [Table 3]

[0074] As shown in Tables 1 and 2, the laminate X1 exhibits excellent resistance to discoloration by plasma containing almost no ions and excellent resistance to discoloration by plasma containing ions. Since plasma containing almost no ions uses radicals as the main active species, it is clear that the laminate X1 does not undergo color change due to radicals. On the other hand, as can be seen from Table 1, laminates Y1 and Y2 are poor in resistance to discoloration by plasma containing almost no ions, and therefore undergo color changes due to radicals, making it difficult to measure only the ion distribution intensity. It is also clear that when the various resins shown in Table 3 are used as the detection layer forming material, the detection layer exhibits excellent resistance to discoloration by plasma containing ions. From these findings, the laminate according to the present invention can detect whether or not an ion intensity distribution occurs during plasma treatment and the extent of the distribution, using ΔE * ab Furthermore, the ion intensity distribution and ΔE * ab By previously determining the correlation between the ion intensity distribution and the surface to be treated with plasma, it becomes possible to easily and indirectly measure the ion intensity distribution within the surface to be treated with plasma. [Explanation of symbols]

[0075] 1: Indicator 2: Base material layer 3: Detection layer 4: Depression (recess)

Claims

1. A laminate for measuring ion intensity distribution on a surface in contact with plasma, the laminate having a detection layer whose color tone changes upon contact with plasma containing at least ions, the detection layer is a layer made of a resin and / or a resin precursor that does not contain atoms other than carbon, hydrogen, oxygen, and nitrogen atoms, When the sensing layer comes into contact with plasma containing at least ions, molecular bonds of components constituting the sensing layer are broken by ion bombardment, and the carbon atom concentration on the surface of the sensing layer increases, causing the sensing layer to change color. The laminate.

2. The laminate of claim 1 , wherein the sensing layer is a porous layer.

3. A laminate for measuring ion intensity distribution on a surface in contact with plasma, the laminate comprising: a substrate layer on which a detection layer is partially provided, the detection layer changing color upon contact with plasma containing at least ions; the detection layer is a layer made of a resin and / or a resin precursor that does not contain atoms other than carbon, hydrogen, oxygen, and nitrogen atoms, When the sensing layer comes into contact with plasma containing at least ions, molecular bonds of components constituting the sensing layer are broken by ion bombardment, and the carbon atom concentration on the surface of the sensing layer increases, causing the sensing layer to change color. The laminate.

4. The laminate described in claim 3, wherein the detection layer is a porous layer.

5. An ion intensity distribution indicator for use in detecting an ion intensity distribution occurring during plasma irradiation, comprising the laminate according to claim 1 or 2.

6. An ion intensity distribution indicator used to detect the ion intensity distribution generated during plasma irradiation, comprising the laminate described in claim 3 or 4.

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