JP2017144615A - Laminate, production method of laminate, and processing method of substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel laminate capable of preventing properly light transmitted through a separation layer from arriving at a substrate, when irradiating light to the separation layer in order to exfoliate a support medium from the substrate.SOLUTION: In a laminate 10, a shading layer 5 is formed between a substrate 1 and a separation layer 4, and the shading layer 5 contains at least one selected from a group comprising a metal, a metal oxide and a metal nitride, and the separation layer 4 does not contain the metal, the metal oxide and the metal nitride contained in the shading layer 5.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminate, a method for manufacturing a laminate, and a substrate processing method.

  In recent years, electronic devices such as IC cards and mobile phones have been required to be thinner, smaller and lighter. In order to satisfy these requirements, a thin semiconductor chip must be used as a semiconductor chip to be incorporated. For this reason, the thickness (film thickness) of the wafer substrate that is the basis of the semiconductor chip is currently 125 μm to 150 μm, but it is said that it must be 25 μm to 50 μm for next-generation chips. Therefore, in order to obtain a wafer substrate having the above film thickness, a wafer substrate thinning process is indispensable.

  Since the strength of the wafer substrate decreases due to the thinning of the wafer substrate, a circuit is formed on the wafer substrate while automatically supporting the substrate while the support is bonded to the wafer substrate to prevent damage to the thinned wafer substrate. Etc. are mounted. Then, after the manufacturing process, the wafer substrate is separated from the support. Therefore, various methods for peeling the support from the wafer substrate are used.

  As a method of peeling the substrate from the laminate, a method of irradiating the separation layer with laser light is used. For example, Patent Document 1 describes a laminate including a separation layer that changes in quality by absorbing light irradiated through a support.

  Patent Document 2 describes a laminate including an adhesive layer formed of an adhesive composition that reduces the amount of transmitted light. Patent Document 3 describes a light absorption layer and a light shielding layer. A laminate in which a separation layer comprising a layer is formed is described.

JP 2012-109538 A (released on June 7, 2012) JP 2013-126723 A (released on June 27, 2013) JP-A-10-125929 (published May 15, 1998)

  A novel laminate that can suitably prevent light transmitted through the separation layer from reaching the substrate when the separation layer is irradiated with light to peel the support from the substrate is formed on the substrate. This is useful because structures such as elements can be prevented from being damaged by light.

  As a result of intensive studies based on original knowledge, the inventors of the present application have formed a light shielding layer of at least one selected from the group consisting of metals, metal oxides, and metal nitrides in the laminate. The structure in which the separation layer does not include the metal, metal oxide, and metal nitride contained in the light shielding layer allows light transmitted through the separation layer to be suitably shielded by the light shielding layer. The headline and the present invention were completed.

  That is, the present invention has been made in view of the above-described problems, and the purpose of the present invention is that when the separation layer is irradiated with light to peel the support from the substrate, the light transmitted through the separation layer is the substrate. It is an object of the present invention to provide a novel laminate and a related technique that can suitably prevent reaching the above point.

  In order to solve the above-described problems, a laminate according to the present invention includes a substrate, a support that transmits light, an adhesive layer, a light-shielding layer, and a separation layer that is altered by absorbing light. The light shielding layer is formed between the substrate and the separation layer, and the light shielding layer comprises a metal, an oxide of the metal, and a nitridation of the metal. It comprises at least one selected from the group consisting of materials, and the separation layer is characterized by not containing the metal, metal oxide, and metal nitride contained in the light shielding layer.

  According to the present invention, when the separation layer is irradiated with light in order to peel the support from the substrate, a novel laminate that can suitably prevent the light transmitted through the separation layer from reaching the substrate and The related technique can be provided.

It is a figure explaining the outline of the layered product concerning one embodiment of the present invention. It is a figure explaining the outline of the manufacturing method of the layered product concerning one embodiment of the present invention. It is a figure explaining the outline of the support body separation method which concerns on one Embodiment of this invention.

<Laminated body 10>
The laminated body 10 which concerns on one Embodiment of this invention is demonstrated in detail using FIG. FIG. 1 is a diagram illustrating an outline of a laminate 10 according to an embodiment of the present invention.

  As shown in FIG. 1, a laminate 10 according to this embodiment is obtained by laminating a substrate 1 and a support plate (support) 2 through an adhesive layer 3, a separation layer 4, and a light shielding layer 5. It is a laminated body. That is, the laminate 10 is formed by laminating the substrate 1 and the support plate 2 that transmits light through the adhesive layer 3, the light shielding layer 5, and the separation layer 4 that is altered by absorbing light. In the laminated body, the light shielding layer 5 is formed between the substrate 1 and the separation layer 4.

  According to said structure, it can prevent suitably with the light shielding layer 5 that the light irradiated toward the separation layer 4 from the support plate 2 which permeate | transmits light reaches | attains the board | substrate 1. FIG.

  The light shielding layer 5 includes at least one selected from the group consisting of a metal, an oxide of the metal, and a nitride of the metal, and the separation layer 4 includes a metal included in the light shielding layer 5, It does not contain metal oxides and metal nitrides.

  According to the above configuration, when the separation layer 4 is irradiated with light through the support plate 2, the light transmitted through the separation layer 4 is reflected to the support plate 2 side by the light shielding layer 5, or the light shielding layer. It is possible to prevent the light from being transmitted to the substrate side while preventing the light from being deteriorated by absorbing the light. Accordingly, the light shielding layer 5 is not altered by the light applied to the separation layer 4 or is hardly altered, so that the light can be suitably prevented from reaching the substrate 1 by the light shielding layer 5.

[substrate]
The substrate 1 can be subjected to processes such as thinning and mounting while being supported by the support plate 2. Further, a structure such as an integrated circuit or a metal bump is mounted on the substrate 1.

  The substrate 1 can typically be a silicon wafer substrate, but is not limited, and a substrate made of any material such as a ceramic substrate, a thin film substrate, or a flexible substrate may be used.

[Support plate]
The support plate (support) 2 is a support that supports the substrate 1, and is attached to the substrate 1 through the adhesive layer 3. Therefore, the support plate 2 only needs to have a strength necessary for preventing damage or deformation of the substrate 1 during processes such as thinning, transporting, and mounting of the substrate 1. Moreover, the support plate 2 should just transmit the light for changing the isolation | separation layer 4. From these viewpoints, the support plate 2 may be a support made of glass, silicon, or acrylic resin. Note that the type of the support plate that supports the substrate 1 may be appropriately selected according to the wavelength of light applied to the separation layer 4.

[Adhesive layer]
The adhesive layer 3 is a layer for attaching the substrate 1 and the support plate 2, and is formed of an adhesive used for attaching the substrate 1 and the support plate 2.

  The adhesive for forming the adhesive layer 3 contains other components such as a thermoplastic resin, a diluent, and an additive. Here, the thermoplastic resin contained in the adhesive, that is, the thermoplastic resin contained in the adhesive layer 3 may be any resin having adhesiveness, such as a hydrocarbon resin or an acrylic-styrene resin. A maleimide resin, an elastomer resin, a polysulfone resin, or a combination thereof can be used more preferably. Hereinafter, the thermoplastic resin contained in the adhesive layer 3 in the present embodiment will be described.

(Hydrocarbon resin)
The hydrocarbon resin is a resin that has a hydrocarbon skeleton and is obtained by polymerizing a monomer composition. As the hydrocarbon resin, cycloolefin polymer (hereinafter sometimes referred to as “resin (A)”), and at least one resin selected from the group consisting of terpene resin, rosin resin and petroleum resin (hereinafter referred to as “resin (A)”). Resin (B) ”), and the like, but is not limited thereto.

  The resin (A) may be a resin obtained by polymerizing a monomer component containing a cycloolefin monomer. Specific examples include a ring-opening (co) polymer of a monomer component containing a cycloolefin monomer, and a resin obtained by addition (co) polymerization of a monomer component containing a cycloolefin monomer.

  Examples of the cycloolefin monomer contained in the monomer component constituting the resin (A) include bicyclic compounds such as norbornene and norbornadiene, tricyclic compounds such as dicyclopentadiene and hydroxydicyclopentadiene, and tetracyclodone. Tetracycles such as decene, pentacycles such as cyclopentadiene trimer, heptacycles such as tetracyclopentadiene, or alkyl (methyl, ethyl, propyl, butyl, etc.) substitutes of these polycycles, alkenyl (vinyl) Etc.) Substitutes, alkylidene (ethylidene, etc.) substitutes, aryl (phenyl, tolyl, naphthyl, etc.) substitutes and the like. Among these, norbornene-based monomers selected from the group consisting of norbornene, tetracyclododecene, and alkyl-substituted products thereof are particularly preferable.

  The monomer component constituting the resin (A) may contain another monomer copolymerizable with the above-described cycloolefin-based monomer, and preferably contains, for example, an alkene monomer. Examples of the alkene monomer include ethylene, propylene, 1-butene, isobutene, 1-hexene, α-olefin and the like. The alkene monomer may be linear or branched.

  Moreover, it is preferable from a viewpoint of high heat resistance (low thermal decomposition and thermal weight reduction property) to contain a cycloolefin monomer as a monomer component which comprises resin (A). The ratio of the cycloolefin monomer to the whole monomer component constituting the resin (A) is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 20 mol% or more. preferable. Further, the ratio of the cycloolefin monomer to the whole monomer component constituting the resin (A) is not particularly limited, but is preferably 80 mol% or less from the viewpoint of solubility and stability over time in a solution, More preferably, it is 70 mol% or less.

  Moreover, you may contain a linear or branched alkene monomer as a monomer component which comprises resin (A). The ratio of the alkene monomer to the whole monomer component constituting the resin (A) is preferably 10 to 90 mol%, more preferably 20 to 85 mol% from the viewpoint of solubility and flexibility. 30 to 80 mol% is more preferable.

  The resin (A) is a resin having no polar group, such as a resin obtained by polymerizing a monomer component composed of a cycloolefin monomer and an alkene monomer, at high temperatures. It is preferable for suppressing generation of gas.

  The polymerization method and polymerization conditions for polymerizing the monomer components are not particularly limited, and may be set as appropriate according to conventional methods.

  For example, a cycloolefin copolymer which is a copolymer of a repeating unit represented by the following chemical formula (1) and a repeating unit represented by the following chemical formula (2) can be used as the adhesive component resin (A).

(In chemical formula (2), n is 0 or an integer of 1 to 3)
As such cycloolefin copolymer, APL 8008T, APL 8009T, APL 6013T (all manufactured by Mitsui Chemicals, Inc.) and the like can be used.

  Examples of commercially available products that can be used as the resin (A) include “TOPAS” manufactured by Polyplastics Co., Ltd., “APEL” manufactured by Mitsui Chemicals, Inc., “ZEONOR” manufactured by Nippon Zeon Co., Ltd., and “ “ZEONEX”, “ARTON” manufactured by JSR Corporation, and the like.

  The glass transition temperature (Tg) of the resin (A) is preferably 60 ° C. or higher, and particularly preferably 70 ° C. or higher. When the glass transition temperature of the resin (A) is 60 ° C. or higher, softening of the adhesive layer 3 can be further suppressed when the laminate is exposed to a high temperature environment.

  The resin (B) is at least one resin selected from the group consisting of terpene resins, rosin resins and petroleum resins. Specifically, examples of the terpene resin include terpene resins, terpene phenol resins, modified terpene resins, hydrogenated terpene resins, hydrogenated terpene phenol resins, and the like. Examples of the rosin resin include rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, and modified rosin. Examples of petroleum resins include aliphatic or aromatic petroleum resins, hydrogenated petroleum resins, modified petroleum resins, alicyclic petroleum resins, coumarone-indene petroleum resins, and the like. Among these, hydrogenated terpene resins and hydrogenated petroleum resins are more preferable.

  Although the softening point of resin (B) is not specifically limited, It is preferable that it is 80-160 degreeC. When the softening point of the resin (B) is 80 to 160 ° C., the laminate can be prevented from being softened when exposed to a high-temperature environment, and adhesion failure does not occur.

  Although the weight average molecular weight of resin (B) is not specifically limited, It is preferable that it is 300-3,000. When the weight average molecular weight of the resin (B) is 300 or more, the heat resistance is sufficient, and the degassing amount is reduced in a high temperature environment. On the other hand, when the weight average molecular weight of the resin (B) is 3,000 or less, the dissolution rate of the adhesive layer in the hydrocarbon solvent is good. For this reason, the residue of the adhesive layer on the substrate after separating the support can be quickly dissolved and removed. In addition, the weight average molecular weight of resin (B) in this embodiment means the molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC).

  In addition, you may use what mixed resin (A) and resin (B) as resin. By mixing, heat resistance becomes good. For example, the mixing ratio of the resin (A) and the resin (B) is (A) :( B) = 80: 20 to 55:45 (mass ratio), and heat resistance in a high temperature environment, and It is preferable because of its excellent flexibility.

(Acrylic-styrene resin)
Examples of the acrylic-styrene resin include a resin obtained by polymerization using styrene or a styrene derivative and (meth) acrylic acid ester as monomers.

  Examples of the (meth) acrylic acid ester include a (meth) acrylic acid alkyl ester having a chain structure, a (meth) acrylic acid ester having an aliphatic ring, and a (meth) acrylic acid ester having an aromatic ring. . Examples of the (meth) acrylic acid alkyl ester having a chain structure include an acrylic long-chain alkyl ester having an alkyl group having 15 to 20 carbon atoms and an acrylic alkyl ester having an alkyl group having 1 to 14 carbon atoms. . As acrylic long-chain alkyl esters, acrylic or methacrylic acid whose alkyl group is n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, etc. Examples include alkyl esters. The alkyl group may be branched.

  Examples of the acrylic alkyl ester having an alkyl group having 1 to 14 carbon atoms include known acrylic alkyl esters used in existing acrylic adhesives. For example, an alkyl group of acrylic acid or methacrylic acid in which the alkyl group is a methyl group, ethyl group, propyl group, butyl group, 2-ethylhexyl group, isooctyl group, isononyl group, isodecyl group, dodecyl group, lauryl group, tridecyl group, etc. Examples include esters.

  Examples of (meth) acrylic acid ester having an aliphatic ring include cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, 1-adamantyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, and tricyclodecanyl. (Meth) acrylate, tetracyclododecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate and the like can be mentioned, and isobornyl methacrylate and dicyclopentanyl (meth) acrylate are more preferable.

  The (meth) acrylic acid ester having an aromatic ring is not particularly limited. Examples of the aromatic ring include a phenyl group, a benzyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, and an anthracenyl group. A phenoxymethyl group, a phenoxyethyl group, and the like. The aromatic ring may have a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, phenoxyethyl acrylate is preferable.

(Maleimide resin)
Examples of maleimide resins include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, N-sec as monomers. -Butylmaleimide, N-tert-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide, N-laurylmaleimide, N-stearylmaleimide, etc. Male having an aliphatic hydrocarbon group such as maleimide having an alkyl group, N-cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, N-cyclooctylmaleimide A resin obtained by polymerizing an aromatic maleimide having an aryl group such as N, N-phenylmaleimide, Nm-methylphenylmaleimide, N-o-methylphenylmaleimide, and Np-methylphenylmaleimide. It is done.

(Elastomer)
The elastomer preferably contains a styrene unit as a constituent unit of the main chain, and the “styrene unit” may have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxyalkyl group having 1 to 5 carbon atoms, an acetoxy group, and a carboxyl group. Further, the content of the styrene unit is more preferably in the range of 14 wt% or more and 50 wt% or less. Furthermore, the elastomer preferably has a weight average molecular weight in the range of 10,000 to 200,000.

  If the content of the styrene unit is in the range of 14% by weight or more and 50% by weight or less, and the weight average molecular weight of the elastomer is in the range of 10,000 or more and 200,000 or less, the hydrocarbon solvent described later Since it dissolves easily in (solvent), the adhesive layer can be removed more easily and quickly. In addition, since the content of the styrene unit and the weight average molecular weight are within the above ranges, the resist solvent (eg, PGMEA, PGME, etc.), acid (fluorinated) exposed when the wafer substrate is subjected to the resist lithography process. Hydroxic acid etc.) and alkali (TMAH etc.) exhibit excellent resistance.

  In addition, you may further mix the (meth) acrylic acid ester mentioned above with the elastomer.

  The content of styrene units is more preferably 17% by weight or more, and more preferably 40% by weight or less.

  A more preferable range of the weight average molecular weight is 20,000 or more, and a more preferable range is 150,000 or less.

  As the elastomer, various elastomers can be used as long as the content of styrene units is in the range of 14% by weight to 50% by weight and the weight average molecular weight of the elastomer is in the range of 10,000 to 200,000. Can be used. For example, polystyrene-poly (ethylene / propylene) block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene-butylene-styrene block copolymer (SBBS). And hydrogenated products thereof, styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (styrene-isoprene-styrene block copolymer) (SEPS), styrene-ethylene-ethylene- Propylene-styrene block copolymer (SEEPS), styrene-ethylene-ethylene-propylene-styrene block copolypropylene in which styrene block is reactively crosslinked -(Septon V9461 (manufactured by Kuraray Co., Ltd.), Septon V9475 (manufactured by Kuraray Co., Ltd.)), Septon V9827 (Co., Ltd., which has a reactive polystyrene-based hard block) Kuraray)), polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene block copolymer (SEEPS-OH: terminal hydroxyl group modification), etc., and the content of styrene units and weight average molecular weight of the elastomer are within the above-mentioned ranges. Can be used.

  Of the elastomers, hydrogenated products are more preferable. If it is a hydrogenated product, the stability to heat is improved, and degradation such as decomposition and polymerization hardly occurs. Moreover, it is more preferable from the viewpoint of solubility in hydrocarbon solvents and resistance to resist solvents.

  Further, among elastomers, those having both ends of a styrene block polymer are more preferable. This is because styrene having high thermal stability is blocked at both ends, thereby exhibiting higher heat resistance.

  More specifically, the elastomer is more preferably a hydrogenated product of a block copolymer of styrene and conjugated diene. Stability against heat is improved, and degradation such as decomposition and polymerization hardly occurs. Moreover, higher heat resistance is exhibited by blocking styrene having high thermal stability at both ends. Furthermore, it is more preferable from the viewpoint of solubility in hydrocarbon solvents and resistance to resist solvents.

  Examples of commercially available products that can be used as an elastomer included in the adhesive constituting the adhesive layer 3 include “Kepte (trade name)” manufactured by Kuraray Co., Ltd., “Hibler (trade name)” manufactured by Kuraray Co., Ltd. “Tuff Tech (trade name)” manufactured by JSR Corporation, “Dynalon (trade name)” manufactured by JSR Corporation, and the like can be mentioned.

  The content of the elastomer contained in the adhesive constituting the adhesive layer 3 is, for example, preferably in the range of 50 parts by weight or more and 99 parts by weight or less, with the total amount of the adhesive composition being 100 parts by weight, and 60 parts by weight or more. The range of 99 parts by weight or less is more preferable, and the range of 70 parts by weight or more and 95 parts by weight or less is most preferable. By making it within these ranges, the substrate and the support can be suitably bonded together while maintaining the heat resistance.

  A plurality of types of elastomers may be mixed. That is, the adhesive constituting the adhesive layer 3 may include a plurality of types of elastomers. And at least one should just contain the styrene unit as a structural unit of a principal chain among several types of elastomers. Further, at least one of the plurality of types of elastomers has a styrene unit content in the range of 14 wt% or more and 50 wt% or less, or a weight average molecular weight of 10,000 or more and 200,000 or less. If it is within the range, it is within the scope of the present invention. Moreover, when the adhesive agent which comprises the contact bonding layer 3 contains several types of elastomers, you may adjust so that content of a styrene unit may become in said range as a result of mixing. For example, Septon 4033 of Septon (trade name) manufactured by Kuraray Co., Ltd. having a styrene unit content of 30% by weight and Septon 2063 of Septon (trade name) having a styrene unit content of 13% by weight is 1 weight ratio. When mixed in a one-to-one relationship, the styrene content with respect to the total elastomer contained in the adhesive is 21 to 22% by weight, and therefore 14% by weight or more. For example, when a styrene unit of 10% by weight and 60% by weight are mixed at a weight ratio of 1: 1, it becomes 35% by weight and falls within the above range. The present invention may be in such a form. Moreover, it is most preferable that the plurality of types of elastomers contained in the adhesive constituting the adhesive layer 3 all contain styrene units within the above range and have a weight average molecular weight within the above range.

  Note that the adhesive layer 3 is preferably formed using a resin other than a photocurable resin (for example, a UV curable resin). By using a resin other than the photocurable resin, it is possible to prevent a residue from being generated around the minute unevenness of the substrate 1 after the adhesive layer 3 is peeled or removed. In particular, the adhesive constituting the adhesive layer 3 is preferably not soluble in any solvent but soluble in a specific solvent. This is because the adhesive layer 3 can be removed by dissolving it in a solvent without applying physical force to the substrate 1. When removing the adhesive layer 3, the adhesive layer 3 can be easily removed without damaging or deforming the substrate 1 even from the substrate 1 whose strength has been reduced.

(Polysulfone resin)
The adhesive for forming the adhesive layer 3 may contain a polysulfone resin. By forming the adhesive layer 3 with a polysulfone-based resin, even if the laminate is processed at a high temperature, the adhesive layer is dissolved in the subsequent steps, and a laminate that can peel the support from the substrate is manufactured. Can do. If the adhesive layer 3 contains a polysulfone resin, the laminate can be suitably used even in a high temperature process in which the laminate is processed at a high temperature of 300 ° C. or higher by annealing or the like.

  The polysulfone-based resin has a structure composed of at least one structural unit of a structural unit represented by the following general formula (3) and a structural unit represented by the following general formula (4).

(Wherein, ^{R 1} and ^{R 2} of ^R 1, ^{R 2} and ^{R 3,} as well as the general formula (4) of the general formula (3) are each independently a phenylene group, from the group consisting of naphthylene group and an anthrylene group And X ′ is an alkylene group having 1 to 3 carbon atoms.)
The polysulfone-based resin includes at least one of the polysulfone constituent unit represented by the formula (3) and the polyethersulfone constituent unit represented by the formula (4), whereby the substrate 1 and the support plate 2 are provided. Then, even if the substrate 1 is processed under a high temperature condition, a laminate that can prevent the adhesive layer 3 from being insolubilized due to decomposition, polymerization, or the like can be formed. The polysulfone resin is stable even when heated to a higher temperature as long as it is a polysulfone resin composed of a polysulfone structural unit represented by the above formula (3). For this reason, it can prevent that the residue resulting from an contact bonding layer arises in the board | substrate 1 after washing | cleaning.

  The weight average molecular weight (Mw) of the polysulfone-based resin is preferably in the range of 30,000 to 70,000, and more preferably in the range of 30,000 to 50,000. If the weight average molecular weight (Mw) of the polysulfone-based resin is within a range of 30,000 or more, an adhesive composition that can be used at a high temperature of 300 ° C. or more can be obtained. Moreover, if the weight average molecular weight (Mw) of polysulfone-type resin is in the range of 70,000 or less, it can melt | dissolve suitably with a solvent. That is, an adhesive composition that can be suitably removed with a solvent can be obtained.

(Diluted solvent)
The dilution solvent is used to dilute the thermoplastic resin in the adhesive for forming the adhesive layer 3. In the adhesive, the dilution solvent for diluting the thermoplastic resin can be appropriately designed depending on the type of the thermoplastic resin.

  More specifically, when a hydrocarbon resin, an elastomer, or the like is used as the thermoplastic resin, it is preferable to use a hydrocarbon or a terpene solvent as the dilution solvent. In addition, when using, for example, an acrylic-styrene resin, a maleimide resin, a polysulfone resin, or the like as the thermoplastic resin, as a diluent solvent, lactones, ketones, polyhydric alcohols, polyhydric alcohol derivatives, It is preferable to use cyclic ethers, esters, aromatic organic solvents, aprotic polar solvents, and the like.

  Hydrocarbons used as a diluent solvent include straight-chain hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, and tridecane, branched hydrocarbons having 4 to 15 carbon atoms, Examples thereof include cyclic hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene and tetrahydronaphthalene. Terpene solvents include p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpine, 1,8-terpine, bornane, norbornane, pinane, tsujang, karan, longifolene, geraniol, nerol, linalool , Citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, dihydroterpinyl acetate, 1,4-cineole, 1 , 8-cineole, borneol, carvone, yonon, thuyon, camphor, d-limonene, l-limonene, dipentene and the like.

  Examples of lactones used as a diluent solvent include γ-butyrolactone, and examples of ketones include acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone, 2- Heptanone etc. can be mentioned. Examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol. Examples of the derivatives of polyhydric alcohols include esters of the polyhydric alcohols, ethers of the polyhydric alcohols and polyhydric alcohol esters, and the like. Examples of the polyhydric alcohol esters include ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate. The polyhydric alcohol ethers and the polyhydric alcohol esters ether include monomethyl ether, monoethyl ether, monopropyl ether, monopolyether of these polyhydric alcohols or polyhydric alcohol esters. Examples thereof include monoalkyl ethers such as butyl ether, monophenyl ethers, and the like. Among these polyhydric alcohol derivatives, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferable. Examples of cyclic ethers include dioxane, and esters include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl pyruvate, and pyruvate. Examples thereof include ethyl, methyl methoxypropionate, and ethyl ethoxypropionate. Examples of the aromatic organic solvent include anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, and butyl phenyl ether. Examples of the aprotic polar solvent include N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), and dimethylacetamide (DMA).

(Other ingredients)
The adhesive constituting the adhesive layer 3 may further contain other miscible materials as long as the essential properties are not impaired. For example, various conventional additives such as additional resins, plasticizers, adhesion aids, stabilizers, colorants, thermal polymerization inhibitors and surfactants for improving the performance of the adhesive may be further used. it can.

[Separation layer]
The separation layer 4 is a layer formed from a material that is altered by absorbing light irradiated through the support plate 2.

  For example, the thickness of the separation layer 4 is more preferably in the range of 0.05 μm or more and 50 μm or less, and further preferably in the range of 0.3 μm or more and 1 μm or less. If the thickness of the separation layer 4 is in the range of 0.05 μm or more and 50 μm or less, desired alteration can be caused in the separation layer 4 by short-time light irradiation and low-energy light irradiation. . The thickness of the separation layer 4 is particularly preferably within a range of 1 μm or less from the viewpoint of productivity.

  In this specification, the “deterioration” of the separation layer means a phenomenon in which the separation layer can be broken by receiving a slight external force, or a state in which the adhesive force with the layer in contact with the separation layer is reduced. To do. As a result of the alteration of the separation layer caused by absorbing light, the separation layer loses its strength or adhesion prior to light irradiation. In other words, the separation layer becomes brittle by absorbing light. The alteration of the separation layer may mean that the separation layer causes decomposition due to absorbed light energy, a change in configuration, dissociation of a functional group, or the like. The alteration of the separating layer occurs as a result of absorbing light.

  Therefore, for example, it is possible to easily separate the support plate and the substrate by changing the quality so that the separation layer is broken only by lifting the support plate. More specifically, for example, one of the substrate and the support plate in the stacked body is fixed to the mounting table by a support separating device or the like, and the other is held and lifted by a suction pad (suction part) provided with suction means. Thus, the support plate and the substrate are separated, or a force is applied by gripping the chamfered portion of the end portion of the peripheral portion of the support plate with the separation plate provided with a clamp (claw portion) or the like. And should be separated. Further, for example, the support plate may be peeled from the substrate in the laminated body by a support separating apparatus provided with a peeling means for supplying a peeling liquid for peeling the adhesive. The peeling means supplies the peeling liquid to at least a part of the peripheral end portion of the adhesive layer in the laminate, and the adhesive layer in the laminate is swollen so that the force concentrates on the separation layer from where the adhesive layer swells. In this way, a force can be applied to the substrate and the support plate. For this reason, a board | substrate and a support plate can be isolate | separated suitably.

  The force applied to the laminated body may be appropriately adjusted depending on the size of the laminated body, and is not limited. For example, if the laminated body has a diameter of about 300 mm, a force of about 0.1 to 5 kgf is applied. By adding, a board | substrate and a support plate can be isolate | separated suitably.

  In the laminate 10, another layer may be further formed between the separation layer 4 and the support plate 2. In this case, the other layer should just be comprised from the material which permeate | transmits light. Thereby, a layer imparting preferable properties and the like to the laminate 10 can be appropriately added without hindering the incidence of light on the separation layer 4. The wavelength of light that can be used differs depending on the type of material constituting the separation layer 4. Therefore, the materials constituting the other layers do not need to transmit light of all wavelengths, and can be appropriately selected from materials capable of transmitting light of wavelengths that can alter the material constituting the separation layer 4.

  The separation layer 4 is preferably formed only from a material having a structure that absorbs light, but the material does not have a structure that absorbs light as long as the essential characteristics of the present invention are not impaired. May be added to form the separation layer 4.

  In addition, it is preferable that the surface of the separation layer 4 facing the adhesive layer 3 is flat (no irregularities are formed), so that the separation layer 4 can be easily formed and even when pasted. It becomes possible to paste on.

  The material of the separation layer 4 may be appropriately selected according to the types of the substrate and the support, and the performance required for the laminate.

(Fluorocarbon)
The separation layer 4 may be made of a fluorocarbon. Since the separation layer 4 is composed of fluorocarbon, the separation layer 4 is altered by absorbing light. As a result, the separation layer 4 loses strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, lifting the support plate 2 or the like), the separation layer 4 is broken, and the support plate 2 and the substrate 1 can be easily separated. The fluorocarbon constituting the separation layer 4 can be suitably formed by a plasma CVD (chemical vapor deposition) method.

  The fluorocarbon absorbs light having a wavelength in a specific range depending on the type. By irradiating the separation layer with light having a wavelength in a range that is absorbed by the fluorocarbon used in the separation layer 4, the fluorocarbon can be suitably altered. The light absorption rate in the separation layer 4 is preferably 80% or more.

The light applied to the separation layer 4 is a liquid such as a solid-state laser such as a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, or a fiber laser, or a dye laser, depending on the wavelength that can be absorbed by the fluorocarbon. A gas laser such as a laser, a CO ₂ laser, an excimer laser, an Ar laser, or a He—Ne laser, a laser beam such as a semiconductor laser or a free electron laser, or a non-laser beam may be used as appropriate. The wavelength at which the fluorocarbon can be altered is not limited to this, but for example, a wavelength in the range of 600 nm or less can be used.

(Polymer containing light-absorbing structure in its repeating unit)
The separation layer 4 may contain a polymer containing a light-absorbing structure in its repeating unit. The polymer is altered by irradiation with light. The alteration of the polymer occurs when the structure absorbs the irradiated light. The separation layer 4 has lost its strength or adhesiveness before being irradiated with light as a result of the alteration of the polymer. Therefore, by applying a slight external force (for example, lifting the support plate 2 or the like), the separation layer 4 is broken, and the support plate 2 and the substrate 1 can be easily separated.

  The above-mentioned structure having light absorptivity is a chemical structure that absorbs light and alters a polymer containing the structure as a repeating unit. The structure is, for example, an atomic group including a conjugated π electron system composed of a substituted or unsubstituted benzene ring, condensed ring, or heterocyclic ring. More specifically, the structure may be a cardo structure or a benzophenone structure, a diphenyl sulfoxide structure, a diphenyl sulfone structure (bisphenyl sulfone structure), a diphenyl structure or a diphenylamine structure present in the side chain of the polymer.

  When the structure is present in the side chain of the polymer, the structure can be represented by the following formula:

(In the formula, each R is independently an alkyl group, an aryl group, a halogen, a hydroxyl group, a ketone group, a sulfoxide group, a sulfone group, or N (R ⁴ ) (R ⁵ ), where R ⁴ and R ⁵ Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), Z is absent, or is —CO—, —SO ₂ —, —SO— or —NH—, and n is 0 or an integer from 1 to 5.)
In addition, the polymer includes, for example, a repeating unit represented by any one of (a) to (d) among the following formulas, is represented by (e), or (f) Contains structure in its main chain.

(In the formula, l is an integer of 1 or more, m is 0 or an integer of 1 to 2, and X is any one of the formulas shown in the above “Chemical Formula 3” in (a) to (e)). Yes, in (f), any of the formulas shown in “Chemical Formula 3” above or not present, and Y ₁ and Y ₂ are each independently —CO— or SO ₂ —. Is preferably an integer of 10 or less.)
Examples of the benzene ring, condensed ring and heterocyclic ring shown in the above “chemical formula 3” include phenyl, substituted phenyl, benzyl, substituted benzyl, naphthalene, substituted naphthalene, anthracene, substituted anthracene, anthraquinone, substituted anthraquinone, acridine, substituted Examples include acridine, azobenzene, substituted azobenzene, fluoride, substituted fluoride, fluoride, substituted fluoride, carbazole, substituted carbazole, N-alkylcarbazole, dibenzofuran, substituted dibenzofuran, phenanthrene, substituted phenanthrene, pyrene, and substituted pyrene. When the exemplified substituent further has a substituent, the substituent is, for example, alkyl, aryl, halogen atom, alkoxy, nitro, aldehyde, cyano, amide, dialkylamino, sulfonamide, imide, carboxylic acid, Selected from carboxylic acid esters, sulfonic acids, sulfonic acid esters, alkylamino and arylamino.

Of the substituents represented by “Chemical Formula 3” above, as an example of the fifth substituent having two phenyl groups and Z being —SO ₂ —, bis (2, 4-dihydroxyphenyl) sulfone, bis (3,4-dihydroxyphenyl) sulfone, bis (3,5-dihydroxyphenyl) sulfone, bis (3,6-dihydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfone, bis (3-hydroxyphenyl) sulfone, bis (2-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, and the like can be given.

  Of the substituents represented by “Chemical Formula 3” above, as an example of the fifth substituent having two phenyl groups and Z being —SO—, bis (2,3 -Dihydroxyphenyl) sulfoxide, bis (5-chloro-2,3-dihydroxyphenyl) sulfoxide, bis (2,4-dihydroxyphenyl) sulfoxide, bis (2,4-dihydroxy-6-methylphenyl) sulfoxide, bis (5 -Chloro-2,4-dihydroxyphenyl) sulfoxide, bis (2,5-dihydroxyphenyl) sulfoxide, bis (3,4-dihydroxyphenyl) sulfoxide, bis (3,5-dihydroxyphenyl) sulfoxide, bis (2,3 , 4-Trihydroxyphenyl) sulfoxide, bis (2,3,4-trihydroxy-6-methylpheny ) -Sulfoxide, bis (5-chloro-2,3,4-trihydroxyphenyl) sulfoxide, bis (2,4,6-trihydroxyphenyl) sulfoxide, bis (5-chloro-2,4,6-trihydroxy) Phenyl) sulfoxide and the like.

  Of the substituents represented by the above “Chemical Formula 3”, the fifth substituent having two phenyl groups and Z is —C (═O) — , 4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2 ′, 5,6′-tetrahydroxybenzophenone, 2-hydroxy-4- Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,6-dihydroxy-4-methoxybenzophenone, 2,2 ' -Dihydroxy-4,4'-dimethoxybenzophenone, 4-amino-2'-hydroxybenzophenone, 4-dimethyl Ruamino-2′-hydroxybenzophenone, 4-diethylamino-2′-hydroxybenzophenone, 4-dimethylamino-4′-methoxy-2′-hydroxybenzophenone, 4-dimethylamino-2 ′, 4′-dihydroxybenzophenone, and 4 -Dimethylamino-3 ', 4'-dihydroxybenzophenone and the like.

  When the structure is present in the side chain of the polymer, the proportion of the repeating unit containing the structure in the polymer is such that the light transmittance of the separation layer 4 is 0.001% or more, 10 % Or less. If the polymer is prepared so that the ratio falls within such a range, the separation layer 4 can sufficiently absorb light and can be reliably and rapidly altered. That is, it is easy to remove the support plate 2 from the laminate 10, and the light irradiation time necessary for the removal can be shortened.

  The said structure can absorb the light which has a wavelength of a desired range by selection of the kind. For example, the wavelength of light that can be absorbed by the above structure is more preferably in the range of 100 nm to 2,000 nm. Within this range, the wavelength of light that can be absorbed by the structure is on the shorter wavelength side, for example, in the range of 100 nm to 500 nm. For example, the structure can alter the polymer containing the structure by absorbing ultraviolet light, preferably having a wavelength in the range of about 300 nm to 370 nm.

  The light that can be absorbed by the above structure is, for example, a high-pressure mercury lamp (wavelength: 254 nm or more and 436 nm or less), KrF excimer laser (wavelength: 248 nm), ArF excimer laser (wavelength: 193 nm), F2 excimer laser (wavelength: 157 nm). , Light emitted from a XeCl laser (wavelength: 308 nm), XeF laser (wavelength: 351 nm) or solid-state UV laser (wavelength: 355 nm), or g-line (wavelength: 436 nm), h-line (wavelength: 405 nm) or i-line ( Wavelength: 365 nm).

  Although the separation layer 4 described above contains a polymer containing the above structure as a repeating unit, the separation layer 4 may further contain components other than the polymer. Examples of the component include a filler, a plasticizer, and a component that can improve the peelability of the support plate 2. These components are appropriately selected from conventionally known substances or materials that do not hinder or promote the absorption of light by the above structure and the alteration of the polymer.

(Compound having infrared absorbing structure)
The separation layer 4 may be formed of a compound having an infrared absorbing structure. The compound is altered by absorbing infrared rays. The separation layer 4 has lost its strength or adhesiveness before being irradiated with infrared rays as a result of the alteration of the compound. Therefore, by applying a slight external force (for example, lifting the support plate 2 or the like), the separation layer 4 is broken, and the support plate 2 and the substrate 1 can be easily separated.

Examples of the compound having an infrared absorptive structure or a compound having an infrared absorptive structure include alkanes, alkenes (vinyl, trans, cis, vinylidene, trisubstituted, tetrasubstituted, conjugated, cumulene, Cyclic), alkyne (monosubstituted, disubstituted), monocyclic aromatic (benzene, monosubstituted, disubstituted, trisubstituted), alcohol and phenol (free OH, intramolecular hydrogen bond, intermolecular hydrogen bond, saturation) Secondary, saturated tertiary, unsaturated secondary, unsaturated tertiary), acetal, ketal, aliphatic ether, aromatic ether, vinyl ether, oxirane ring ether, peroxide ether, ketone, dialkylcarbonyl, Aromatic carbonyl, 1,3-diketone enol, o-hydroxy aryl ketone, dialkyl aldehyde, aromatic aldehyde, carboxylic acid (dimer, Rubonic acid anion), formate ester, acetate ester, conjugated ester, non-conjugated ester, aromatic ester, lactone (β-, γ-, δ-), aliphatic acid chloride, aromatic acid chloride, acid anhydride ( Conjugated, non-conjugated, cyclic, acyclic), primary amide, secondary amide, lactam, primary amine (aliphatic, aromatic), secondary amine (aliphatic, aromatic), secondary Tertiary amine (aliphatic, aromatic), primary amine salt, secondary amine salt, tertiary amine salt, ammonium ion, aliphatic nitrile, aromatic nitrile, carbodiimide, aliphatic isonitrile, aromatic isonitrile, Isocyanate ester, thiocyanate ester, aliphatic isothiocyanate ester, aromatic isothiocyanate ester, aliphatic nitro compound, aromatic nitro compound, nitroamine, nitrosamine, glass Esters, nitrites, nitroso bonds (aliphatic, aromatic, monomer, dimer), sulfur compounds such as mercaptans and thiophenol and thiolic acid, thiocarbonyl groups, sulfoxides, sulfones, sulfonyl chlorides, primary It may be a sulfonamide, a secondary sulfonamide, a sulfate ester, a carbon-halogen bond, or a P—A ² bond (A ² is H, C or O).

As a structure containing halogen bond, for _{example, -CH 2 Cl, -CH 2 Br} , -CH 2 I, -CF 2 - - the _{carbon, - CF 3, -CH = CF} 2, -CF = CF 2, fluoride Aryl chloride and aryl chloride.

Examples of the structure containing the P—A ² bond include PH, PH ₂ , P—CH ₃ , P—CH ₂ —, P—C ₆ H ₅ , A ³ ₃ —PO— (A ³ is aliphatic or aromatic. _{^{family), (A 4 O) 3}} -P-O (A 4 _{alkyl), P-OCH 3, P} -OCH 2 CH 3, P-OC 6 H 5, P-O-P, P-OH, and O = P-OH and the like can be mentioned.

  The said structure can absorb the infrared rays which have the wavelength of a desired range by selection of the kind. Specifically, the wavelength of infrared rays that can be absorbed by the above structure is, for example, in the range of 1 μm or more and 20 μm or less, and more preferably in the range of 2 μm or more and 15 μm or less. In addition, those skilled in the art can easily understand the infrared wavelength that can be absorbed by each structure. For example, as an absorption band in each structure, Non-Patent Document: SILVERSTEIN / BASSLER / MORRILL, “Identification method by spectrum of organic compound (5th edition) —Combination of MS, IR, NMR and UV” (published in 1992) The description on page 146 to page 151 can be referred to.

  The compound having an infrared absorbing structure used for forming the separation layer 4 can be dissolved in a solvent (solvent) for coating among the compounds having the structure as described above, and solidified. If it can be formed and a solid layer can be formed, it will not specifically limit. However, in order to effectively alter the compound in the separation layer 4 and facilitate separation of the support plate 2 and the substrate 1, the infrared absorption in the separation layer 4 is large, that is, the separation layer 4 is irradiated with infrared rays. It is preferable that the infrared transmittance is low. Specifically, the infrared transmittance in the separation layer 4 is preferably lower than 90%, and the infrared transmittance is more preferably lower than 80%.

  Although the separation layer 4 described above contains a compound having an infrared absorbing structure, the separation layer 4 may further contain a component other than the above compound. Examples of the component include a filler, a plasticizer, and a component that can improve the peelability of the support plate 2. These components are appropriately selected from conventionally known substances or materials that do not interfere with or promote infrared absorption by the above structure and alteration of the compound.

(Infrared absorbing material)
The separation layer 4 may contain an infrared absorbing material. The separation layer 4 is configured to contain an infrared ray absorbing substance, so that it is altered by absorbing light. As a result, the strength or adhesiveness before receiving the light irradiation is lost. Therefore, by applying a slight external force (for example, lifting the support plate 2 or the like), the separation layer 4 is broken, and the support plate 2 and the substrate 1 can be easily separated.

  The infrared absorbing material only needs to have a structure that is altered by absorbing infrared rays. For example, carbon black can be suitably used. The infrared absorbing material absorbs light having a wavelength in a specific range depending on the type. By irradiating the separation layer 4 with light having a wavelength within a range that is absorbed by the infrared absorbing material used for the separation layer 4, the infrared absorbing material can be suitably altered.

(carbon)
The separation layer 4 may be made of carbon. Since the separation layer 4 is composed of carbon, the separation layer 4 is altered by absorbing light. As a result, the separation layer 4 loses its strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, lifting the support plate 2 or the like), the separation layer 4 can be broken and the substrate 1 and the support plate 2 can be easily separated.

  Carbon is a concept that may include an allotrope of carbon, for example, diamond, fullerene, diamond-like carbon, carbon nanotube, and the like.

The light applied to the carbon separation layer 4 is, for example, a solid-state laser such as a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, or a fiber laser, a dye, depending on the wavelength that can be absorbed by the inorganic substance. A liquid laser such as a laser, a gas laser such as a CO ₂ laser, an excimer laser, an Ar laser, or a He—Ne laser, a laser beam such as a semiconductor laser or a free electron laser, or a non-laser beam may be used as appropriate.

  Further, the separation layer 4 made of carbon can be formed on the support plate 2 by a known technique such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, spin coating or the like. The thickness of the separation layer 4 made of carbon is not particularly limited as long as it is a film thickness that can sufficiently absorb the light to be used. Is more preferable. Alternatively, an adhesive may be applied in advance to both sides or one side of the carbon constituting the separation layer 4 and attached to the support plate 2.

In general, as a material used to form the separation layer, a metal and an inorganic material such as an oxide or nitride of the metal may be used in the same manner as an inorganic material such as carbon. Examples of such inorganic materials include Au, Ag, Cu, Fe, Ni, Al, Ti, Cr, SiO ₂ , SiN, Si ₃ N ₄ , and TiN. However, in the stacked body 10 according to the present embodiment, the separation layer 4 does not contain a metal and a metal oxide or nitride.

[Shading layer]
The light shielding layer 5 is formed between the substrate 1 and the separation layer 4, and the light transmitted through the separation layer 4 among the light irradiated to the separation layer 4 through the support plate 2 is the substrate 1. It is a layer for shielding light so as not to reach The light shielding layer 5 shields the light transmitted through the separation layer 4 by absorbing and reflecting.

  The light shielding layer 5 includes at least one selected from the group consisting of metals, metal oxides, and metal nitrides.

  Here, the metal used to form the light shielding layer 5 includes, for example, Al, Au, Ag, Cu, Cr, Pt, Ni, Ti, Ge, In, Si, Pd, and Sn, and these Two or more alloys of metals can be mentioned, and more preferably, at least one selected from the group consisting of Au, Ag, Sn and Ag, Sn alloys can be mentioned. Thus, by employing a layer containing metal as the light shielding layer 5, the light shielding layer 5 having a mirror surface formed of metal on the surface facing the separation layer 4 can be formed. Thereby, in the laminated body 10 shown in FIG. 1, when the light irradiated through the support plate 2 permeate | transmits the separation layer 4, and is irradiated to the light shielding layer 5, the said light will be the support plate 2 side by the light shielding layer 5. It can be suitably reflected. Thereby, not only can the light be blocked by the light blocking layer 5, but also the heat generated by the light blocking layer 5 absorbing the light can be reduced.

Examples of the metal oxide used to form the light shielding layer 5 include the above metal oxides, and preferably AgO, CuO, Cr ₂ O ₃ , TiO ₂ , SnO ₂ , SiO _2. Most preferred is TiO ₂ . Among these metal oxides, for example, if TiO ₂ is used as the light shielding layer 5, a light shielding layer having high light shielding properties can be formed.

Further, examples of the metal nitride used for forming the light-shielding layer 5 include the above-mentioned metal nitrides, and preferable examples include TiN, SiN, Si ₃ N _{4 and the} like.

  The light shielding layer 5 may be a layer formed of a metal, a metal oxide, and a metal nitride as a continuous thin film as one layer. It may be a single layer in which the nitride particles are aggregated but not fused together. In addition, when the light shielding layer 5 is formed of particles of metal, metal oxide, or metal nitride, the average particle diameter of the particles is determined by metal, metal oxide, and metal nitride. Although it can design suitably and it is not limited, It is preferable that it is an average particle diameter in the range of 0.01 micrometer-5 micrometers, and it is more preferable that it is 0.1 micrometer-1 micrometer. For example, when metal particles are used, if the average particle diameter of the metal particles is 0.01 μm to 5 μm, the mirror surface is preferably formed on the surface facing the separation layer 4 and the cohesive force of the metal particles The light-shielding layer 5 having a high general strength can be formed.

  The thickness of the light shielding layer 5 is preferably in the range of 0.1 μm or more and 20 μm or less, and more preferably in the range of 0.1 μm or more and 5 μm or less. If the thickness of the light shielding layer 5 is 0.1 μm or more, the light transmitted through the separation layer 4 can be suitably prevented from reaching the substrate 1. Further, if the thickness of the light shielding layer 5 is within a range of 20 μm or less, the light shielding layer 5 can be successfully removed from the substrate 1 from which the support plate 2 is separated.

  In addition, when the light shielding layer 5 is formed using particulate metal, metal oxide, and metal nitride, the light shielding layer 5 is blended in a dispersion used for forming the light shielding layer 5. Dispersing agents may be included. Further, these particles of metal or the like may be surface-treated with, for example, a coupling agent or the like.

  In another aspect, the light-shielding layer 5 most preferably has a light transmittance of a predetermined wavelength for altering the separation layer 4 of 0%, but the light transmittance of the predetermined light is 40%. % Or less. In the separation layer 4, the transmittance of light with a predetermined wavelength that can alter the separation layer 4 is approximately 40%, and the transmittance of light with a predetermined wavelength in both the separation layer 4 and the light shielding layer 5. Is approximately 0%, it is possible to prevent the light from reaching the substrate 1.

<Method for producing laminate>
The manufacturing method of the laminated body which concerns on one Embodiment of this invention is demonstrated in detail using FIG. The manufacturing method of the laminated body according to the present embodiment includes a separation layer forming step ((a) and (b) of FIG. 2) for forming the separation layer 4 on the support plate 2, and the separation layer formed on the support plate 2. The light shielding layer forming step (FIG. 2 (c)) for forming the light shielding layer 5 by applying a dispersion on the substrate 4, and the adhesive layer forming step (FIG. 2 (d) for forming the adhesive layer 3 on the substrate 1. ) And (e)) and a laminating step ((f) of FIG. 2) for attaching the support plate 2 on which the light shielding layer 5 is formed, the substrate 1, and the adhesive layer.

[Separation layer forming step]
In the separation layer forming step, the separation layer 4 is formed on the support plate 2 shown in FIG. 2A (FIG. 2B). Note that the method for forming the separation layer 4 may be appropriately designed according to the material used to form the separation layer 4.

[Adhesive layer forming step]
In the separation layer forming step, the adhesive layer 3 is formed on the substrate 1 shown in FIG. 2D (FIG. 2E).

  The adhesive layer 3 can be formed by applying an adhesive containing a thermoplastic resin by a method such as spin coating, dipping, roller blade, spray coating, slit coating, or the like. The adhesive layer 3 is formed by, for example, attaching a film (so-called dry film) in which the adhesive is applied in advance on both sides to the substrate 1 instead of directly applying the adhesive to the substrate 1. May be.

  The thickness of the adhesive layer 3 may be set as appropriate depending on the types of the substrate 1 and the support plate 2 to be attached, the treatment applied to the substrate 1 after being attached, etc., but in the range of 10 to 150 μm. Is preferably within the range of 15 to 100 μm.

  In addition, what is necessary is just to design the density | concentration of the thermoplastic resin in an adhesive agent suitably according to the thickness etc. of the contact bonding layer 3 which should be formed. In addition, the dilution solvent for dissolving the thermoplastic resin in the adhesive may be appropriately designed with reference to the description in the above (Dilution solvent) column.

[Shading layer forming step]
In the light shielding layer forming step according to the present embodiment, the light shielding layer 5 is formed by applying a metal dispersion on the separation layer 4 formed on the support plate 2 ((c) in FIG. 2).

  The light shielding layer 5 can be formed by applying the dispersion liquid by a method such as spin coating, dipping, roller blade, spray coating, slit coating, or the like. Moreover, after apply | coating a dispersion liquid to the support plate 2, the said support plate 2 is heated at the temperature of about 90 degreeC-160 degreeC, for example, or is put under a reduced pressure environment, or under a reduced pressure environment The diluted solvent contained in the dispersion may be removed depending on whether the heating is performed.

  In the method for manufacturing a laminate according to the present embodiment, the light shielding layer 5 is formed on the separation layer 4 more lightly than when the light shielding layer 5 is formed on the adhesive layer 3 formed on the substrate 1. This is because the layer 5 can be formed more smoothly.

(Dispersion)
The dispersion for forming the light-shielding layer 5 is described in the above-mentioned column (diluting solvent) and the metal, metal oxide, or metal nitride described in the above-mentioned [light-shielding layer] column. Diluting solvent. Moreover, the dispersion liquid may contain a dispersing agent such as a metal as needed.

  The dilution solvent used for the dispersion can be appropriately designed according to the type of thermoplastic resin that forms the adhesive layer 3. For example, when the above-described hydrocarbon resin or elastomer is used as the thermoplastic resin for forming the adhesive layer 3, among the solvents other than the diluting solvent that can suitably dissolve these hydrocarbon resin or lastomer, the hydrocarbon resin Alternatively, it is more preferable to use a solvent that is hardly soluble or insoluble in the elastomer, that is, a solvent that does not substantially dissolve the hydrocarbon resin or the elastomer. Examples of the solvent that does not substantially dissolve the hydrocarbon resin or elastomer include, for example, lactones, ketones, polyhydric alcohols, polyhydric alcohol derivatives, cyclic ethers in the above-mentioned column (diluent solvent), Esters, aromatic organic solvents, aprotic polar solvents, and the like can be used. More preferably, polyhydric alcohols such as PGME and derivatives of polyhydric alcohols such as PGMEA can be used.

  Further, as the thermoplastic resin for forming the adhesive layer 3, for example, when an acrylic-styrene resin, a maleimide resin, a polysulfone resin, or the like is used, a solvent other than a dilution solvent that can suitably dissolve these resins Among them, a solvent that is hardly soluble or insoluble in these resins, that is, a solvent that is substantially incompatible with an acrylic-styrene resin, a maleimide resin, a polysulfone resin, or the like is used. More preferred. Solvents that do not substantially dissolve acrylic-styrene-based resins, maleimide-based resins, polysulfone-based resins, and the like include hydrocarbons such as decahydronaphthalene and terpene-based materials such as p-menthane in the above-mentioned column (dilution solvent). Mention may be made of solvents.

  What is necessary is just to design suitably the density | concentration of the metal in a dispersion liquid, a metal oxide, or a metal nitride according to the thickness of the light shielding layer 5 which should be formed.

<Substrate processing method>
A substrate processing method according to an embodiment of the present invention will be described in detail with reference to FIG.

  The substrate processing method according to the present embodiment includes a laminate manufacturing process (FIG. 2) for manufacturing a laminate by the laminate manufacturing method according to one embodiment, and a separation layer 4 via a support plate 2 in the laminate 10. The separation process (FIGS. 3A to 3D) for separating the substrate 1 and the support plate 2 by altering the separation layer 4 by irradiating light to the substrate, the substrate from which the support plate 2 is separated The light shielding layer removing step (FIG. 3E) for removing the light shielding layer 5 remaining on the substrate 1, and the adhesive layer removing step for removing the adhesive layer 3 from the substrate 1 from which the residue of the light shielding layer 5 has been removed (FIG. 3). (F)).

[Separation process]
In the separation step, the separation layer 4 is irradiated with the laser light L by the laser irradiation device 50 through the support plate 2 in the stacked body 10 shown in FIG. 3A (FIG. 3B).

  As for the irradiation condition of the laser beam L in the laser irradiation apparatus 50, the average output value of the laser beam L is preferably 1.0 W or more and 5.0 W or less, and more preferably 3.0 W or more and 4.0 W or less. preferable. The repetition frequency of the laser light is preferably 20 kHz or more and 60 kHz or less, and more preferably 30 kHz or more and 50 kHz or less. The scanning speed of the laser beam is preferably 100 mm / s or more and 10,000 mm / s or less. In addition, what is necessary is just to design suitably the wavelength of the laser beam L which should be irradiated as laser irradiation conditions according to the kind of separation layer 4. FIG. Under these laser irradiation conditions, the separation layer 4 can be suitably altered, and the light L transmitted through the separation layer 4 can be suitably prevented from reaching the substrate 1 by the light shielding layer 5.

  Subsequently, in the separation step, by using a separation plate (not shown) provided with suction holding means such as a bellows pad or gripping means such as a clamp, the support plate 2 in the laminate 10 is held and lifted, The support plate 2 can be separated from the substrate 1 (FIGS. 3C and 3D). In addition, it is preferable to use what provided joints, such as a floating joint and a universal joint, for a separation plate.

(Shading layer removal process)
In the light shielding layer removing step, the light shielding layer 5 is removed using a diluting solvent (solvent) contained in the dispersion used to form the light shielding layer 5 in the light shielding layer forming step ((e) in FIG. 3). . Here, using the nozzle 51, the light shielding layer 5 can be removed using a solvent that is substantially incompatible with the thermoplastic resin used to form the adhesive layer 3 as the solvent S1. For this reason, only the light shielding layer 5 can be removed, and then the metal used to form the light shielding layer 5, such as a metal, a metal oxide, or a metal nitride can be successfully recovered. . Therefore, these metals and the like can be suitably reused to form the light shielding layer 5.

  In addition, prior to performing the light shielding layer 5 removal step, it is more preferable to remove the residue of the separation layer 4 on the light shielding layer 5 by, for example, dissolving with an organic alkali compound or the like.

(Adhesive layer removal process)
In the adhesive layer removing step, the adhesive layer 3 can be suitably removed from the substrate 1 by applying a solvent S2 that can suitably dissolve the thermoplastic resin of the adhesive layer 3 with the nozzle 52 (FIG. 3). (F)).

[Laminated body according to one modification]
The laminated body which concerns on this invention is not limited to the said embodiment. For example, in one modification, the light shielding layer 5 in the laminate 10 is a thermoplastic resin used to form the adhesive layer 3 other than metal, metal oxide, or metal nitride. It is the structure containing another thermoplastic resin.

  Here, the thermoplastic resin used for forming the light shielding layer 5 is hardly soluble or insoluble in a solvent capable of suitably dissolving the thermoplastic resin in the adhesive layer 3. That is, the thermoplastic resin contained in the light shielding layer 5 is not substantially compatible with the solvent that dissolves the adhesive layer 3.

  The laminated body having the above configuration can also preferably remove only the light shielding layer 5 in the substrate 1 from which the support plate 2 is separated. Moreover, the heat resistance of the light shielding layer 5 can be improved by blending a thermoplastic resin into the light shielding layer 5.

  In the light-shielding layer of the laminate according to the present modification, 1 to 50 parts by weight of metal, metal oxide, or metal nitride is blended with respect to 100 parts by weight of the thermoplastic resin. preferable. Thereby, the laminated body which can prevent suitably the light which permeate | transmitted the separation layer reaches | attains a board | substrate can be formed.

[Method for Producing Laminate According to One Modification]
The manufacturing method of the laminated body which concerns on this invention is not limited to the said embodiment. For example, in the manufacturing method of the laminated body which concerns on one modification, in the light shielding layer formation process, the light shielding layer of a metal, a metal oxide, or a metal nitride is formed by sputtering, for example. Here, as a sputtering method, a bipolar sputtering method, a magnetron sputtering method, a sputtering of a DC (direct current) RF (high frequency) power source, a dual magnetron method, a reactive sputtering, or the like can be employed.

  According to said structure, the light shielding layer currently formed in the continuous thin film form (film form) as one layer can be manufactured suitably. Further, a mirror surface made of metal or the like can be suitably formed on the surface of the light shielding layer 5 facing the separation layer 4.

  Moreover, in the manufacturing method of the laminated body which concerns on another modification, a light shielding layer is formed by plating, chemical vapor deposition (CVD), or plasma CVD in a light shielding layer formation process.

[Substrate processing method according to one modification]
The manufacturing method of the laminated body which concerns on this invention is not limited to the said embodiment. For example, in the substrate processing method according to the modified example, the light shielding layer of the stacked body 10 according to the modified example is removed in the light shielding layer removing step. Here, the light shielding layer 5 in the laminate 10 according to the modified example includes a thermoplastic resin different from the thermoplastic resin forming the adhesive layer 3, and the other thermoplastic resin includes the adhesive layer 3. It can be dissolved by a solvent that is substantially incompatible with the thermoplastic resin to be formed. Therefore, the adhesive layer 3 can be left and only the residue of the light shielding layer 5 can be removed from the substrate 1.

  The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention.

[Example 1]
As Example 1, a separation layer and a light shielding layer were formed on a glass support, and the light shielding properties and heat resistance of the separation layer and the light shielding layer were evaluated.

(Evaluation of light shielding properties)
First, as an evaluation of light shielding properties, a glass support (sample 1), a glass support (sample 2) on which only a separation layer was formed, and a glass support (sample 3) on which only a light shielding layer was formed were prepared. The transmittance of light having a predetermined wavelength in the glass support was evaluated. For sample 1, a bare glass support having a thickness of 700 μm was used.

(Formation of separation layer)
As sample 2, the separation layer 4 was formed on the support plate 2 by the plasma CVD method using fluorocarbon on the same glass support as the glass support of sample 1. As the conditions of the separation layer forming step, the CVD method using C ₄ F ₈ as a reaction gas is performed under the conditions of a flow rate of 400 sccm, a pressure of 700 mTorr, a high frequency power of 2500 W, and a film formation temperature of 240 ° C. A certain fluorocarbon film (thickness 1 μm) was formed on the support plate 2.

(Formation of light shielding layer)
Next, as Sample 3, a light shielding layer was formed on the same glass support as that of Sample 1 using a metal dispersion. The light shielding layer was formed by applying an Ag—Sn dispersion (manufactured by Sumitomo Osaka Cement Co., Ltd.) by spin coating and baking at 90 ° C. and 160 ° C. for 3 minutes each (film thickness 300 nm). The Ag-Sn dispersion contains 20 to 30% by weight of Ag and Ag-Sn, 65 to 75% by weight of PGMEA as a solvent, and 1 to 5% by weight of a dispersant.

  About each of the samples 1-3, the light of wavelength 350-600 nm was irradiated, and the transmittance | permeability of the light of wavelength 532 nm was measured using the spectroscopic analysis measuring device UV-3600 (made by Shimadzu Corp.). Table 1 below shows the evaluation results of each evaluation sample.

  As shown in Table 1, the transmittance of the light shielding layer 5 according to the present embodiment was 0% with respect to laser light having a wavelength of 532 nm. The evaluation sample 3 always had a transmittance of 0% regardless of the change in the wavelength of the laser beam. For this reason, it has been confirmed that by forming a light shielding layer made of metal, it is possible to prevent the substrate from being irradiated with light.

[Evaluation of heat resistance]
Next, as a heat resistance evaluation, a glass support (sample 4) on which only an adhesive layer is formed, a glass support on which only a separation layer of sample 2 is formed, and a glass support on which only a light-shielding layer of sample 3 is formed. About TG-DTA apparatus TG-DTA6200 (manufactured by Seiko Instruments Inc.), the temperature was changed at 50 to 500 ° C., and the weight change rate at 220 ° C., 240 ° C., and 260 ° C. was measured to evaluate the heat resistance. Was done.

(Formation of adhesive layer)
In sample 4, a hydrocarbon-based adhesive TZNR (registered trademark) -A4017 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was spin-coated on the glass support of sample 1, and each of them was performed at temperatures of 90 ° C., 160 ° C., and 220 ° C. By baking for 4 minutes, an adhesive layer having a thickness of 50 μm was formed.

  Table 2 below shows the evaluation results of heat resistance.

  In the above heat resistance evaluation results, the weight reduction rate of the glass support (sample 3) on which the light-shielding layer was formed was larger than that of the other samples, but less than -4.5%. It is judged that the sexual requirements are satisfied.

[Evaluation of solvent resistance]
Subsequently, the solvent resistance of the separation layer in Sample 2 was evaluated using propylene glycol monomethyl ether acetate (PGMEA) that can be used as a solvent used in the dispersion. The solvent resistance was evaluated by the change in the optical density (OD value) of the separation layer of Sample 2 before and after applying PGMEA. The optical density was measured using a 310 transmission / reflection densitometer device (manufactured by X-RITE Co., Ltd.) at the center point and end portion of the flat portion of sample 2 and at the midpoint between the center point and end portion. Table 3 below shows the evaluation results of the solvent resistance of the separation layer.

  As shown in Table 3, almost no change was observed in the optical density of the separation layer before and after applying PGMEA on the separation layer made of fluorocarbon. Therefore, it is judged effective to use PGMEA as a solvent in the dispersion for forming the light shielding layer.

[Example 2]
Subsequently, as Example 2, a laminate including the light-shielding layer used in Sample 3 of Example 1 was formed, and various evaluations were performed.

(Production of laminate)
For the production of the laminate, a separation layer was formed on the 12-inch glass support used in Example 1 under the same conditions as in Example 1, and the same dispersion as in Example 1 was applied on the separation layer. As a result, a light shielding layer was formed (light shielding layer forming step). Next, an adhesive layer was formed on the semiconductor wafer substrate under the same conditions as Sample 4 except that a 12-inch semiconductor wafer substrate having a thickness of 700 μm was used. Thereafter, the wafer substrate and the glass support on which the light shielding layer was formed were heated to 215 ° C., and a pressing force of 4 t was applied for 2 to 3 minutes, thereby forming the laminate of Example 2 (laminate). Forming step).

[TTV evaluation]
Next, TTV (Total Thickness Variation) measurement was performed on the laminate of Example 2. TTV measurement is performed by (1) after laminating the laminate, and (2) using a back grind apparatus (manufactured by DISCO) to backgrind the wafer substrate to a thickness of 50 μm, 3) About the laminated body which performed the back grinding process, it measured after heating in 200 degreeC and the conditions of 1 hour in nitrogen environment. Here, the TTV measurement was evaluated by the thickness of the laminated body excluding the thickness of the thinned wafer substrate, that is, the total thickness of the glass support, the separation layer, the light shielding layer, and the adhesive layer. Table 4 shows the results of TTV evaluation.

  As shown in Table 4, it was confirmed that the TTV value of the laminated body after each step was within a change within a range where there was no problem in processing the wafer substrate.

[Evaluation of separability]
Then, about the laminated body 10 of Example 2, the separation layer was irradiated with laser light through a glass support. Irradiation conditions of the laser beam were as follows: the wavelength was 532 nm, the laser beam diameter was 180 μm, the center-to-center distance between irradiated regions in the laser pulse was 180 μm, the scanning speed was 6500 mm / s, and the repetition frequency was 40 kHz.

  Thereafter, the glass support was separated from the laminate, and the separation layer remaining on the wafer substrate side was removed by dissolution using TZNR (registered trademark) -SL Remover, and the state of the light shielding layer remaining on the wafer substrate was evaluated. . As a result, in the wafer substrate from which the glass support was separated, it was confirmed that the light shielding layer was not damaged and that only the separation layer could be altered by irradiating light. Further, it was confirmed that only the light-shielding layer made of the Ag—Sn alloy can be removed by using PGMEA.

Example 3
As Example 3, a laminated body in which a light shielding layer was formed by sputtering was prepared, and evaluation was made on stickability, heat resistance, separability, and removability of the light shielding layer.

  Except for the formation of the light shielding layer, the laminate of Example 3 was formed according to the conditions of Example 2. The light shielding layer was formed by sputtering Au on the separation layer 4 using an MPS-12In apparatus (manufactured by Vacuum Device Inc.). In addition, the thickness of the light shielding layer was 640 nm.

  Separately from the production of the laminate, a light shielding layer was formed by sputtering Au on a glass support, and the transmittance of light having a wavelength of 532 nm was measured. When the thickness of the light shielding layer was 640 nm, the transmittance of light having a wavelength of 532 nm was 12.5%. Further, when the thickness of the light shielding layer was 320 nm, the light transmittance at 532 nm was 37.5%.

(Evaluation of adhesiveness)
About the laminated body of Example 3, the thinning process of the wafer substrate was performed using the back grinding apparatus (made by DISCO). Then, it confirmed visually that there was no peeling of the glass support body from a wafer substrate in the edge part of a laminated body.

(Evaluation of heat resistance)
About the laminated body which evaluated sticking property, the heat processing for 1 hour were performed at 200 degreeC, and heat resistance was evaluated. Then, about the laminated body of Example 3, it was able to confirm visually that there were no malfunctions, such as generation | occurrence | production of a void and peeling of an edge part, in a laminated body.

(Evaluation of separability)
With respect to the laminate of Example 3 that was subjected to heat resistance evaluation under the same laser irradiation conditions as the laminate of Example 2, the separation layer was irradiated with light through a glass support to evaluate the separability. As a result, even in the laminated body of Example 2, it was confirmed that the wafer substrate and the glass support could be separated without any problems.

(Evaluation of shading layer removal)
In Example 3, the residue of both the adhesive layer and the light shielding layer remaining on the wafer substrate was removed using p-menthane. In addition, it confirmed that the light shielding layer formed by sputtering could be removed with p-menthane, maintaining the state of a thin film.

Example 4
As Example 4, a laminate including a light-shielding layer containing a metal and a thermoplastic resin was formed, and evaluation was made on stickability, heat resistance, separability, and light-shielding layer removability. In addition, the laminated body of Example 4 was manufactured on the laminated body of Example 2, and conditions other than formation of a light shielding layer.

(Production of laminate)
An acrylic adhesive TZNR (registered trademark) -A0136 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was mixed with a dispersion obtained by mixing TiO ₂ filler (manufactured by Nippon Aerosil Co., Ltd.) so as to be 10% by weight of the total amount. 4 was spin-coated at a rotation speed of 600 rpm, and baked at a temperature of 100 ° C., 150 ° C., and 200 ° C. for 3 minutes to form a light shielding layer 5 (film thickness 20 μm). Except for the formation method of the light shielding layer 5, it was the same as Example 1.

  Separately from the production of the laminate, a light shielding layer was formed by applying a dispersion containing TZNR (registered trademark) -A0136 to a glass support, and the light transmittance at a wavelength of 532 nm was measured. When the thickness of the light shielding layer was 20 μm, the transmittance of light having a wavelength of 532 nm was 16.6%.

(Evaluation of adhesiveness)
About the laminated body of Example 4, the thinning process of the wafer substrate was performed using the back grind apparatus (made by DISCO). Then, it confirmed visually that there was no peeling of the glass support body from a wafer substrate in the edge part of a laminated body.

(Evaluation of heat resistance)
About the laminated body of Example 4 which evaluated sticking property, heat processing is performed at 200 degreeC for 1 hour, heat resistance is evaluated, and there are no malfunctions, such as generation | occurrence | production of a void and peeling of an edge part, in a laminated body. Was confirmed visually. In the evaluation of heat resistance, the flow of heat from the light shielding layer is reduced at the end of the laminate, and the rheological properties of TZNR (registered trademark) -A0136 used in the light shielding layer are improved. I was able to confirm.

(Evaluation of separability)
It was confirmed that the glass support could be separated from the wafer substrate without any problems by irradiating the separation layer of the laminate with light under the same conditions as in Examples 2 and 3.

(Evaluation of shading layer removal)
In the laminate of Example 4, it was confirmed that by using PGMEA, it was possible to remove only the residue of the light shielding layer by washing the wafer substrate from which the glass support was separated. Thereafter, it was confirmed that the residue of the adhesive layer remaining on the wafer substrate could be suitably removed with p-menthane.

  The laminate according to the present invention can be suitably used in the manufacturing process of a miniaturized semiconductor device.

1 Substrate 2 Support plate (support)
3 Adhesive layer 4 Separating layer 5 Light-shielding layer 10 Laminate

Claims (14)

A laminate comprising a substrate and a light-transmitting support, which are laminated via an adhesive layer, a light-shielding layer, and a separation layer that is altered by absorbing light,
The light shielding layer is formed between the substrate and the separation layer,
The light shielding layer comprises at least one selected from the group consisting of a metal, an oxide of the metal, and a nitride of the metal,
The laminate according to claim 1, wherein the separation layer does not include a metal, a metal oxide, and a metal nitride contained in the light shielding layer.   The light shielding layer is a layer containing at least one particle selected from the group consisting of the metal particles, the metal oxide particles, and the metal nitride particles. The laminate according to claim 1.   The metal is at least one selected from the group consisting of Al, Au, Ag, Cu, Cr, Pt, Ni, Ti, Ge, In, Si, Pd, Sn, and alloys of these two or more metals. The laminate according to claim 1, wherein the laminate is one. The metal is Au, Ag, Sn and is at least one selected from the group consisting of AgSn alloy, oxides of the above metals, any one of the preceding claims, characterized in that it is TiO ₂ The laminate according to Item 1.   The layered product according to any one of claims 1 to 4, wherein the light shielding layer has a thickness of 0.05 µm or more and 50 µm or less.   The laminate according to any one of claims 1 to 5, wherein the light shielding layer further comprises a thermoplastic resin.   The adhesive layer comprises a thermoplastic resin different from the thermoplastic resin, and the separate thermoplastic resin is hardly soluble or insoluble in a solvent capable of dissolving the thermoplastic resin. The laminate according to claim 6, which is characterized. A method for producing a laminate comprising: laminating a substrate and a support that transmits light through an adhesive layer, a light shielding layer, and a separation layer that is altered by absorbing light,
On the support, a separation layer forming step of forming a separation layer that does not include the metal, metal oxide, and metal nitride contained in the light shielding layer;
At least one of the metal, the metal oxide, and the metal nitride on the substrate, the adhesive layer formed on the substrate, and the separation layer formed on the support. And a light shielding layer forming step of forming the light shielding layer comprising at least one selected from the group consisting of: A method for producing a laminate, comprising:   In the light shielding layer forming step, at least one of the metal, the oxide of the metal, and the separation layer formed on the support, the adhesive layer formed on the substrate, and the support layer. 9. The laminate according to claim 8, wherein the light shielding layer is formed by applying a dispersion containing at least one selected from the group consisting of the metal nitrides and a solvent. Body manufacturing method.   In the light shielding layer forming step, the metal, the metal, or the metal is formed on at least one of the substrate, the adhesive layer formed on the substrate, and the separation layer formed on the support by a sputtering method. The method for producing a laminated body according to claim 8, wherein the light-shielding layer including at least one selected from the group consisting of an oxide of the above and a metal nitride is formed. The dispersion further comprises a thermoplastic resin,
The adhesive layer comprises a thermoplastic resin different from the thermoplastic resin, and the separate thermoplastic resin is hardly soluble or insoluble in the solvent. A manufacturing method of a layered product.   The method for producing a laminate according to any one of claims 8 to 11, wherein, in the light shielding layer forming step, the light shielding layer is formed on a separation layer formed on the support. The laminated body manufacturing process which manufactures the said laminated body with the manufacturing method of the laminated body of any one of Claims 8-11,
A separation step of separating the substrate and the support by altering the separation layer by irradiating with light through the support in the laminate. Substrate processing method. A laminate manufacturing process for manufacturing the laminate by the laminate manufacturing method according to claim 9 or 11,
A separation step of separating the substrate and the support by altering the separation layer by irradiating light through the support in the laminate,
And a light-shielding layer removing step of removing the light-shielding layer remaining on the substrate from which the support has been separated by supplying the solvent.

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