JP2015099895A - Processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To laminate a first support body, a first adhesive layer, a substrate, a second adhesive layer, and a second support body in this order, and then suitably separate the first support body.SOLUTION: The processing method includes: forming a second adhesive layer 22 on a surface facing back-to-back to a surface to which a first support body 13 of a substrate 11 is pasted; discharging a solvent to a periphery of the second adhesive layer 22 of the substrate 11; pasting a second support body 23 to the substrate through the second adhesive layer 22; and separating the first support body 13 and the substrate 11.

Description

  The present invention relates to a substrate processing method.

  In recent years, electronic device products are required to be further reduced in size, weight, and performance. Flip chip mounting technology, which is one of chip connection technologies, has been increasingly used as a key technology for realizing miniaturization, high performance, and low cost.

  Patent Document 1 discloses an adhesive composition used for forming a film-like adhesive used when affixing to a semiconductor wafer, grinding a wafer back surface, and flip chip bonding.

  Further, Patent Document 2 discloses a method for manufacturing a semiconductor device applied when manufacturing a semiconductor device having a chip-on-chip structure using a through electrode. More specifically, a step of flip-chip mounting a semiconductor chip on the first surface of the semiconductor substrate, and a step of forming an insulating support by resin molding in a state of covering the semiconductor chip on the first surface of the semiconductor substrate. And a method of manufacturing a semiconductor device, including a step of performing a predetermined process on the second surface side of the semiconductor substrate, and a step of cutting a chip from the semiconductor substrate together with the insulating support member into pieces. Yes.

JP 2011-146731 A (published July 28, 2011) JP 2008-130704 A (published on June 5, 2008)

  In order to perform flip chip mounting, the present inventors once formed a laminate in which a first support, a first adhesive layer, a substrate, a second adhesive layer, and a second support are laminated in this order. We are independently studying the technology to form. That is, first, a substrate is bonded to the first support through an adhesive layer, and the substrate is ground and thinned. Thereafter, the second support is bonded to the ground surface of the substrate via the second adhesive layer to form the laminate. Then, it is considered to separate the first support from the laminate and perform flip chip mounting using the remaining portion.

  Here, in order to bond the second support to the wafer substrate via the second adhesive layer, an adhesive exists between the first support and the second support when a pressing force is applied between the first support and the second support. May be pushed out and the adhesive may be exposed (extruded) from the laminate. When the adhesive is exposed from the laminated body, the adhesive adheres to the side surface of the laminated body, and as a result, there is a problem that the support and the wafer substrate may not be suitably separated.

  The present invention has been made in view of the above problems, and after laminating the first support, the first adhesive layer, the substrate, the second adhesive layer and the second support in this order, the first support The main object is to provide a technique for suitably separating the two.

  In order to solve the above problems, a processing method according to the present invention includes a first pasting step of pasting a substrate to a first support via a first adhesive layer, and the substrate after the first pasting step. A second adhesive layer forming step of forming a second adhesive layer on the surface facing the surface on which the first support is attached, and after the second adhesive layer forming step, on the substrate After the first solvent discharging step of discharging the solvent to the outer peripheral portion of the second adhesive layer and removing the outer peripheral portion, and after the first solvent discharging step, the substrate is secondly supported via the second adhesive layer. It includes a second pasting step for pasting the body and a separation step for separating the first support and the substrate after the second pasting step.

  According to the present invention, by removing the outer peripheral portion of the adhesive layer before the second sticking step, the adhesive existing therebetween is pushed out when a pressing force is applied in the second sticking step. Thus, exposure of the adhesive from the laminate can be suppressed. Therefore, the first support can be suitably separated from the laminate.

It is a figure explaining the outline of the processing method concerning one embodiment of the present invention. It is a figure explaining the outline of the 1st solvent discharge process and the 2nd solvent discharge process which the processing method concerning one embodiment of the present invention includes. It is a figure explaining the outline of the laminated body formed by the 2nd sticking process which the processing method concerning one embodiment of the present invention includes, and the conventional laminated body. It is a figure explaining the outline of the separation process which the processing method concerning one embodiment of the present invention includes. It is a figure explaining the outline of the separation process which the processing method concerning other embodiments of the present invention includes.

  In the treatment method according to the present invention, the first support in the substrate is pasted to the first support after the first pasting step of pasting the substrate through the first adhesive layer and the first pasting step. A second adhesive layer forming step of forming a second adhesive layer on the surface facing away from the surface, and after the second adhesive layer forming step, on the outer periphery of the second adhesive layer on the substrate A first solvent discharging step of discharging a solvent and removing the outer peripheral portion; and a second pasting step of bonding a second support to the substrate via a second adhesive layer after the first solvent discharging step; And a separation step of separating the first support and the substrate after the second sticking step.

  An embodiment of the present invention will be described in detail with reference to FIG. FIG. 1 is a diagram for explaining the outline of a processing method according to an embodiment of the present invention.

  In the processing method according to an embodiment of the present invention, first, a first adhesive layer forming step of forming the first adhesive layer 12 on at least one of the substrate 11 and the first support 13 is performed. And a solvent is discharged to the outer peripheral part of the 1st adhesive bond layer 12 on the board | substrate 11, and the said outer peripheral part is removed. Then, the 1st sticking process which affixes the board | substrate 11 on the 1st support body 13 via the 1st adhesive bond layer 12 is implemented. Thereafter, the substrate 11 is ground to a predetermined thickness by grinding with a grinder or the like, and the circuit 15 and the bump 16 are formed on the ground side surface of the substrate 11 (see FIG. 1A). This is merely an example, and various processing can be performed on the substrate 11 according to the purpose.

  Then, the 2nd adhesive bond layer formation process which forms the 2nd adhesive bond layer 22 is implemented in the surface opposite to the surface where the 1st support body was affixed in the board | substrate 11 (refer FIG.1, (b)). ). And a solvent is discharged to the outer peripheral part of the 2nd adhesive bond layer 22 on the board | substrate 11, the 1st solvent discharge process of removing the said outer peripheral part, and the outer periphery of the 1st adhesive bond layer 12 on the 1st support body 13 A second solvent discharge step for supplying the solvent to the section is performed (see (c) and (d) of FIG. 1).

  Then, the 2nd sticking process which affixes the 2nd support body 23 on the board | substrate 11 via the 2nd adhesive bond layer 22 is performed (refer (e) of FIG. 1). Finally, a separation process for separating the first support 13 and the substrate 11 is performed.

[First adhesive layer forming step]
Then, the detail of each process is demonstrated. First, in the processing method according to the embodiment, before the first sticking step, the first adhesive layer 12 is formed by applying an adhesive to at least one of the first support 13 and the substrate 11 to form the first adhesive layer 12. An agent coating step.

  Thereby, the substrate 11 can be fixed to the first support 13. Therefore, it is possible to prevent the substrate 11 from being damaged in the subsequent process.

  First, the first adhesive layer 12 is formed by applying a first adhesive to the substrate 11. In the present embodiment, the first adhesive layer 12 is formed on the substrate 11, but the present invention is not limited to this, and the first adhesive is formed on the separation layer 14 formed on the first support 13. May be applied to form the first adhesive layer 12.

[Substrate 11]
As the substrate 11, for example, an arbitrary substrate such as a wafer substrate, a ceramic substrate, a thin film substrate, or a flexible substrate can be used.

[First adhesive layer 12]
As a formation method of the 1st adhesive bond layer 12, you may apply | coat an adhesive agent to the board | substrate 11, and may affix the adhesive tape by which the adhesive agent was apply | coated to the board | substrate 11 on both surfaces. The method for applying the adhesive is not particularly limited, and examples thereof include spin coating, dipping, roller blade, doctor blade, spray, and slit nozzle methods. Moreover, after apply | coating an adhesive agent, you may dry by heating. Further, instead of directly applying the adhesive to the substrate 11, a film (so-called double-sided tape) in which the adhesive is previously applied to both sides may be attached to the substrate 11.

  The thickness of the first adhesive layer 12 may be appropriately set according to the type of the substrate 11 and the first support 13 to be attached, the treatment applied to the substrate 11 after being attached, It is preferably within the range of 10 to 150 μm, and more preferably within the range of 15 to 100 μm.

  As the adhesive, for example, various adhesives known in the art such as acrylic, novolak, naphthoquinone, hydrocarbon, polyimide, and elastomer are adhesives constituting the first adhesive layer 12 according to the present invention. It can be used as an agent. Hereinafter, the composition of the resin contained in the first adhesive layer 12 in the present embodiment will be described.

  The resin contained in the first adhesive layer 12 may be any resin having adhesiveness, for example, a hydrocarbon resin, an acrylic-styrene resin, a maleimide resin, an elastomer resin, or a combination thereof. Etc.

  The glass transition temperature (Tg) of the adhesive varies depending on the type and molecular weight of the resin, and a compound such as a plasticizer for the adhesive. The type and molecular weight of the resin contained in the adhesive can be appropriately selected according to the type of the substrate and the support, but the Tg of the resin used for the adhesive is in the range of −60 ° C. or higher and 200 ° C. or lower. The inside is preferable, and the inside of the range of −25 ° C. or higher and 150 ° C. or lower is more preferable. When the Tg of the resin used for the adhesive is in the range of −60 ° C. or higher and 200 ° C. or lower, the adhesive force of the first adhesive layer 12 is preferably reduced without requiring excessive energy for cooling. Can do. Moreover, you may adjust Tg of the 1st adhesive bond layer 12 by mix | blending a plasticizer, resin of a low polymerization degree, etc. suitably.

  The glass transition temperature (Tg) can be measured using, for example, a known differential scanning calorimeter (DSC).

(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 dihydroxypentadiene, tetracyclododecene, and the like. Tetracyclics, pentacyclics such as cyclopentadiene trimers, heptacyclics such as tetracyclopentadiene, or alkyl (methyl, ethyl, propyl, butyl, etc.) substitutions of these polycyclics, alkenyls (vinyl, etc.) Substitution, alkylidene (ethylidene, etc.) substitution, aryl (phenyl, tolyl, naphthyl, etc.) substitution, etc. are mentioned. 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 to contain a cycloolefin monomer as a monomer component which comprises resin (A) from a viewpoint of high heat resistance (low thermal decomposition and thermal weight reduction property). 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.

  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” and “ZEONEX” manufactured by Zeon Corporation. And “ARTON” manufactured by JSR Corporation.

  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 first adhesive layer 12 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 ° C. or higher, the laminate can be suppressed from being softened when exposed to a high temperature environment, and adhesion failure does not occur. On the other hand, when the softening point of the resin (B) is 160 ° C. or less, the peeling rate when peeling the laminate is good.

  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 under a high temperature environment. On the other hand, when the weight average molecular weight of the resin (B) is 3,000 or less, the peeling rate when peeling the laminate is good. 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 and peeling speed are improved. For example, the mixing ratio of the resin (A) and the resin (B) is (A) :( B) = 80: 20 to 55:45 (mass ratio). Since it is excellent in tolerance and flexibility, it is preferable.

(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 chain 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.

  For example, a cycloolefin copolymer that 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 resin of the adhesive component.

(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.

(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 Therefore, the first adhesive layer can be removed more easily and quickly. Further, 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 (hydrogen fluoride) exposed when the wafer is subjected to the resist lithography process. Acid, etc.) and alkali (TMAH etc.).

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

  Further, 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.)), a styrene block having a reactive crosslinking type styrene-ethylene-butylene-styrene block copolymer (Septon V9827 (manufactured by Kuraray Co., Ltd.) having a reactive polystyrene hard block), etc. The styrene unit content and the weight average molecular weight are within the above-mentioned ranges.

  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.

  Among elastomers, those having both ends of a styrene block polymer are more preferred. 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 contained in the adhesive constituting the first adhesive layer 12 include “Septon (trade name)” manufactured by Kuraray Co., Ltd., “Hibler (trade name)” manufactured by Kuraray Co., Ltd., Asahi Kasei Co., Ltd. “Tuftec (trade name)”, JSR Corporation “Dynaron (trade name)” and the like.

  The content of the elastomer contained in the adhesive constituting the first adhesive layer 12 is preferably within 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, for example, 60 More preferably within the range of not less than 99 parts by weight and most preferably not less than 70 parts by weight and not more than 95 parts by weight. By setting it within these ranges, the wafer 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 first adhesive layer 12 may contain a plurality of types of elastomers. It is sufficient that at least one of the plurality of types of elastomers includes a styrene unit as a constituent unit of the main chain. 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 which comprises the 1st adhesive bond layer 12 contains several types of elastomer, 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. The plurality of types of elastomers contained in the adhesive constituting the first adhesive layer 12 all contain styrene units within the above range, and most preferably have a weight average molecular weight within the above range. .

  In addition, it is preferable to form the 1st adhesive bond layer 12 using resin other than photocurable resin (for example, UV curable resin). By using a resin other than the photocurable resin, it is possible to prevent a residue from remaining around the minute unevenness of the supported substrate after the first adhesive layer 12 is peeled or removed. In particular, the adhesive constituting the first adhesive layer 12 is preferably not soluble in any solvent but soluble in a specific solvent. This is because it can be removed by dissolving the first adhesive layer 12 in a solvent without applying physical force to the substrate 11. When the first adhesive layer 12 is removed, the first adhesive layer 12 can be easily removed without damaging or deforming the substrate 11 even from the substrate 11 whose strength has decreased.

(Diluted solvent)
Examples of the dilution solvent used when forming the first adhesive layer 12 (and the later-described separation layer 14) include linear chains such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, and tridecane. Hydrocarbons, branched hydrocarbons having 4 to 15 carbon atoms, for example, cyclic hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, tetrahydronaphthalene, p-menthane, o-menthane, m Menthane, Diphenylmenthane, 1,4-Terpin, 1,8-Terpin, Bornan, Norbornane, Pinan, Tujan, 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, ionone, thuyon, camphor, d-limonene Terpene solvents such as l-limonene and dipentene; lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone and 2-heptanone; ethylene Polyhydric alcohols such as glycol, diethylene glycol, propylene glycol, dipropylene glycol; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene A compound having an ester bond such as glycol monoacetate, a monoalkyl ether such as monomethyl ether, monoethyl ether, monopropyl ether or monobutyl ether of the polyhydric alcohol or the compound having ester bond, or an ether bond such as monophenyl ether Derivatives of polyhydric alcohols such as compounds having a propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monomethyl ether (PGME) among these; cyclic ethers such as dioxane, methyl lactate, Ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, etc. Esters; anisole, ethylbenzyl ether, cresyl methyl ether, diphenyl ether, can be mentioned dibenzyl ether, phenetole, the aromatic organic solvent such as butyl phenyl ether.

(Other ingredients)
The adhesive constituting the first adhesive layer 12 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.

[Removal of the outer peripheral portion of the first adhesive layer 12]
In the processing method according to the present embodiment, after the first adhesive layer 12 is formed, the outer peripheral portion of the first adhesive layer 12 formed on the substrate 11 may be removed. Thereby, the excessively applied first adhesive can be removed. For this reason, it can prevent that the 1st adhesive bond layer 12 protrudes from the outer peripheral part of the board | substrate 11 and the 1st support body 13, and adheres to the 1st support body 13 excessively in a 1st sticking process.

  A method for removing the first adhesive layer 12 formed on the outer peripheral portion on the substrate 11 may be a known method, and is not particularly limited. For example, for the outer peripheral portion of the first adhesive layer 12 The solvent may be sprayed, or the solvent may be supplied using a dispensing nozzle. Further, spraying and supplying the solvent may be performed while rotating the substrate 11.

  The solvent for dissolving the first adhesive layer 12 may be appropriately selected according to the type of the adhesive and is not particularly limited. For example, the solvent used as the dilution solvent described above can be used. In particular, linear hydrocarbons, branched hydrocarbons having 4 to 15 carbon atoms, cyclic hydrocarbons (terpenes) such as monoterpenes and diterpenes can be preferably used.

[First support 13]
The first support 13 is a support plate that supports the substrate 11 and is also referred to as a support plate. The first support 13 is attached to the substrate 11 via the first adhesive layer 12.

  The first support 13 has a strength necessary for preventing the substrate 11 from being damaged or deformed during processes such as thinning, transporting, and mounting of the substrate 11, and is used for altering the separation layer 14. Any material that transmits light may be used. From the above viewpoint, examples of the first support 13 include those made of glass, silicon, and acrylic resin.

[Separation layer 14]
The separation layer 14 is a layer that is altered by light irradiation, and is provided on the surface of the first support 13 on the side where the substrate 11 is bonded via the first adhesive layer 12. Thereby, the substrate 11 and the first support 13 can be easily separated by irradiating the separation layer with light via the first support 13.

  For example, the thickness of the separation layer 14 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 14 is in the range of 0.05 μm or more and 50 μm or less, desired alteration can be caused in the separation layer 14 by short-time light irradiation and low-energy light irradiation. . Further, the thickness of the separation layer 14 is particularly preferably within a range of 1 μm or less from the viewpoint of productivity.

  Note that another layer may be further formed between the separation layer 14 and the first support 13. 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 can be appropriately added without hindering the incidence of light on the separation layer 14. The wavelength of light that can be used varies depending on the type of material constituting the separation layer 14. Therefore, the material constituting the other layer does not need to transmit all light, and can be appropriately selected from materials capable of transmitting light having a wavelength that can alter the material constituting the separation layer 14.

  The separation layer 14 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 14. Further, it is preferable that the surface of the separation layer 14 on the side facing the first adhesive layer 12 is flat (no irregularities are formed), whereby the separation layer 14 can be easily formed and attached. Can be applied evenly.

The separation layer 14 may be altered by absorbing light irradiated from the laser. That is, the light applied to the separation layer 14 to alter the separation layer 14 may be light emitted from a laser. Examples of lasers that emit light to irradiate the separation layer 14 include YAG lasers, ruby lasers, glass lasers, YVO ₄ lasers, solid state lasers such as LD lasers, fiber lasers, liquid lasers such as dye lasers, CO ₂ lasers, Examples thereof include a gas laser such as an excimer laser, an Ar laser, and a He—Ne laser, a laser beam such as a semiconductor laser and a free electron laser, or a non-laser beam. The laser that emits light to irradiate the separation layer 14 can be appropriately selected according to the material constituting the separation layer 14 and irradiates light having a wavelength that can alter the material constituting the separation layer 14. The laser to be selected may be selected.

(Fluorocarbon)
The separation layer 14 may be made of a fluorocarbon. Since the separation layer 14 is composed of fluorocarbon, the separation layer 14 is altered by absorbing light. As a result, the separation layer 14 loses strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, lifting the first support 13 or the like), the separation layer 14 is broken, and the first support 13 and the substrate 11 can be easily separated. The fluorocarbon constituting the separation layer 14 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 within a range that is absorbed by the fluorocarbon used in the separation layer 14, the fluorocarbon can be suitably altered. The light absorption rate in the separation layer 14 is preferably 80% or more.

As light to irradiate the separation layer 14, for example, a liquid such as a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, 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 14 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 14 loses 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 first support 13 or the like), the separation layer 14 is broken, and the first support 13 and the substrate 11 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 an N (R ¹ ) (R ² ) group (where R ¹ and R ² is each independently 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 of 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, represented by (e), or represented by (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 2” in (a) to (e)). Yes, in (f), any of the formulas shown in “Chemical Formula 2” above or not present, and Y ₁ and Y ₂ are each independently —CO— or —SO ₂ —. l is preferably an integer of 10 or less.)
Examples of the benzene ring, condensed ring and heterocyclic ring shown in the above “chemical formula 2” include phenyl, substituted phenyl, benzyl, substituted benzyl, naphthalene, substituted naphthalene, anthracene, substituted anthracene, anthraquinone, substituted anthraquinone, acridine, substituted Examples include acridine, azobenzene, substituted azobenzene, fluorene, substituted fluorene, fluorenone, substituted fluorenone, 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 2” 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 mentioned.

  Of the substituents represented by “Chemical Formula 2” 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 2”, 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 ratio of the repeating unit containing the structure to the polymer is such that the light transmittance of the separation layer 14 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 14 can sufficiently absorb light and can be surely and rapidly altered. That is, the first support 13 can be easily removed from the laminate 100, 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, 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 14 described above contains a polymer containing the above structure as a repeating unit, the separation layer 14 may further contain a component other than the polymer. Examples of the component include a filler, a plasticizer, and a component that can improve the peelability of the first support 13. 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.

(Inorganic)
The separation layer 14 may be made of an inorganic material. The separation layer 14 is composed of an inorganic substance, and is thereby altered by absorbing light. As a result, the separation layer 14 loses strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, lifting the first support 13 or the like), the separation layer 14 is broken, and the first support 13 and the substrate 11 can be easily separated.

The said inorganic substance should just be the structure which changes in quality by absorbing light, for example, 1 or more types of inorganic substances selected from the group which consists of a metal, a metal compound, and carbon can be used conveniently. The metal compound refers to a compound containing a metal atom, and can be, for example, a metal oxide or a metal nitride. Examples of such inorganic materials include, but are not limited to, gold, silver, copper, iron, nickel, aluminum, titanium, chromium, SiO ₂ , SiN, Si ₃ N ₄ , TiN, and carbon. One or more inorganic substances selected from the group consisting of: Carbon is a concept that may include an allotrope of carbon, for example, diamond, fullerene, diamond-like carbon, carbon nanotube, and the like.

  The inorganic material absorbs light having a wavelength in a specific range depending on the type. By irradiating the separation layer with light having a wavelength within a range that the inorganic material used for the separation layer 14 absorbs, the inorganic material can be suitably altered.

The light applied to the separation layer 14 made of an inorganic material may be, 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, or a dye depending on the wavelength that can be absorbed by the inorganic material. 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.

  The separation layer 14 made of an inorganic material can be formed on the first support 13 by a known technique such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, or spin coating. The thickness of the separation layer 14 made of an inorganic material is not particularly limited as long as it is a film thickness that can sufficiently absorb light to be used. For example, the film thickness is in a range of 0.05 μm or more and 10 μm or less. Is more preferable. Alternatively, an adhesive may be applied in advance to both surfaces or one surface of an inorganic film (for example, a metal film) made of an inorganic material constituting the separation layer 14 and attached to the first support 13 and the substrate 11.

  When a metal film is used as the separation layer 14, laser reflection or charging of the film may occur depending on conditions such as the film quality of the separation layer 14, the type of laser light source, and laser output. Therefore, it is preferable to take measures against them by providing an antireflection film or an antistatic film on the upper and lower sides of the separation layer 14 or one of them.

(Compound having infrared absorbing structure)
The separation layer 14 may be formed of a compound having an infrared absorbing structure. The compound is altered by absorbing infrared rays. The separation layer 14 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), the separation layer 14 is broken, and the first support 13 and the substrate 11 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 Sulfonamide, secondary sulfonamide, sulfate ester, carbon-halogen bond, Si-A ¹ bond (A ¹ is H, C, O or halogen), PA ² bond (A ² is H, C or O), or Ti—O bonds.

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 Si—A ¹ bond include SiH, SiH ₂ , SiH ₃ , Si—CH ₃ , Si—CH ₂ —, Si—C ₆ H ₅ , SiO-aliphatic, Si—OCH ₃ , Si— _{OCH 2 CH 3, Si-OC} 6 H 5, Si-O-Si, Si-OH, SiF, SiF 2, and SiF _3, and the like. As a structure including a Si—A ¹ bond, a siloxane skeleton and a silsesquioxane skeleton are particularly preferably formed.

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. Furthermore, in the case where the structure is a Si—O bond, a Si—C bond, or a Ti—O bond, it may be in the range of 9 μm or more and 11 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.

  As the compound having an infrared-absorbing structure used for forming the separation layer 14, among the compounds having the structure as described above, it can be dissolved in a solvent for coating, and is solidified and solidified. There is no particular limitation as long as the layer can be formed. However, in order to effectively alter the compound in the separation layer 14 and facilitate separation of the first support 13 and the substrate 11, the absorption of infrared rays in the separation layer 14 is large, that is, the separation layer 14 has infrared rays. It is preferable that the transmittance of infrared rays when irradiated with is low. Specifically, the infrared transmittance in the separation layer 14 is preferably lower than 90%, and the infrared transmittance is more preferably lower than 80%.

  For example, as the compound having a siloxane skeleton, for example, a resin that is a copolymer of a repeating unit represented by the following chemical formula (3) and a repeating unit represented by the following chemical formula (4), or A resin that is a copolymer of a repeating unit represented by the following chemical formula (3) and a repeating unit derived from an acrylic compound can be used.

(In the chemical formula (4), R ³ is hydrogen, an alkyl group having 10 or less carbon atoms, or an alkoxy group having 10 or less carbon atoms.)
Among them, as a compound having a siloxane skeleton, a t-butylstyrene (TBST) -dimethylsiloxane copolymer which is a copolymer of a repeating unit represented by the above chemical formula (3) and a repeating unit represented by the following chemical formula (5) is used. A polymer is more preferable, and a TBST-dimethylsiloxane copolymer containing a repeating unit represented by the above formula (3) and a repeating unit represented by the following chemical formula (5) in a ratio of 1: 1 is further preferable.

  As the compound having a silsesquioxane skeleton, for example, a resin that is a copolymer of a repeating unit represented by the following chemical formula (6) and a repeating unit represented by the following chemical formula (7) can be used. .

(In chemical formula (6), R ⁴ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and in chemical formula (7), R ⁵ is an alkyl group having 1 to 10 carbon atoms, or a phenyl group. .)
Other compounds having a silsesquioxane skeleton include JP 2007-258663 A (published on October 4, 2007), JP 2010-120901 A (published on June 3, 2010), Each silsesquioxane resin disclosed in JP 2009-263316 A (published on November 12, 2009) and JP 2009-263596 A (published on November 12, 2009) is preferably used. Can do.

  Among these, as the compound having a silsesquioxane skeleton, a repeating unit represented by the following chemical formula (8) and a copolymer of a repeating unit represented by the following chemical formula (9) are more preferable. A copolymer containing the repeating unit represented by the formula (9) and the repeating unit represented by the following chemical formula (9) at 7: 3 is more preferable.

  The polymer having a silsesquioxane skeleton may have a random structure, a ladder structure, and a cage structure, and any structure may be used.

Examples of the compound containing a Ti—O bond include (i) tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, and titanium-i-propoxyoctylene glycolate. (ii) di -i- propoxy bis (acetylacetonato) titanium, and propane di oxytitanium bis (ethylacetoacetate) chelate titanium such as; alkoxy titanium etc. _{(iii) i-C 3 H} 7 O - [- _{Ti (O-i-C 3} H 7) 2 -O-] n -i-C 3 H 7, and _{n-C 4 H 9 O -} [- Ti (O-n-C 4 H 9) 2 -O _-] n _-n-C 4 titanium polymers such as _{H 9;} (iv) tri -n- butoxy titanium monostearate, titanium stearate, di -i- propoxytitanium diisopropyl Examples include sostearate and acylate titanium such as (2-n-butoxycarbonylbenzoyloxy) tributoxytitanium; (v) water-soluble titanium compounds such as di-n-butoxy-bis (triethanolaminato) titanium.

Among them, as a compound containing a Ti—O bond, di-n-butoxy bis (triethanolaminato) titanium (Ti (OC ₄ H ₉ ) ₂ [OC ₂ H ₄ N (C ₂ H ₄ OH) ₂ ] ₂ ) is preferred.

  Although the separation layer 14 described above contains a compound having an infrared absorbing structure, the separation layer 14 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 first support 13. 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 14 may contain an infrared absorbing material. The separation layer 14 is configured to contain an infrared absorbing material, so that the separation layer 14 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 first support 13 or the like), the separation layer 14 is broken, and the first support 13 and the substrate 11 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, iron particles, or aluminum particles 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 14 with light having a wavelength in a range that is absorbed by the infrared absorbing material used for the separation layer 14, the infrared absorbing material can be suitably altered.

[First sticking step]
Then, the detail of a 1st sticking process is demonstrated. First, in one embodiment, in the first pasting step, the substrate 11 on which the first adhesive layer 12 is formed and the first support 13 on which the separation layer 14 is formed are pasted together. However, this invention is not limited to this, You may provide the 1st adhesive bond layer 12 in the 1st support body 13 side. Further, the separation layer 14 may not be formed.

  In the first attaching step, the attaching temperature for attaching the substrate 11 and the first support 13 is preferably 100 ° C. or more and 250 ° C. or less. By setting the sticking temperature within the above temperature range, the substrate 11 and the first support 13 can be suitably stuck by flowing the first adhesive layer 12. In addition, the sticking temperature which affixes the board | substrate 11 and the 1st support body 13 in a 1st sticking process is higher than the sticking temperature which affixes the board | substrate 11 and the 2nd support body 23 in the 2nd sticking process mentioned later. Is preferred.

  Hereinafter, the laminate in which the substrate 11, the first adhesive layer 12, the separation layer 14, and the first support 13 are attached in this order may be referred to as an intermediate laminate 50.

[Second adhesive layer forming step]
In one embodiment, in the second adhesive layer forming step, the second adhesive layer 22 is formed by applying an adhesive to the surface of the substrate 11 on which the circuit 15 or the like is provided. The method for applying the adhesive can be performed in the same manner as the method for applying the adhesive in the first adhesive layer 12.

  Here, the thickness of the second adhesive layer 22 is appropriately set according to the types of the substrate 11 and the second support 23 to be bonded, the treatment applied to the substrate 11 applied after bonding, and the like. It is possible. The thickness of the second adhesive layer 22 is preferably 10 μm or more and 200 μm or less, and more preferably 30 μm or more and 150 μm or less.

  As the adhesive constituting the second adhesive layer 22, the same adhesive as the adhesive constituting the first adhesive layer 12 may be used, or a different adhesive may be used.

[First solvent discharge process]
In the first solvent discharge step, the solvent is discharged to the outer peripheral portion of the second adhesive layer 22 on the substrate 11 and the outer peripheral portion is removed.

  Thereby, the outer peripheral part of the 2nd adhesive bond layer 22 formed on the board | substrate 11 of the intermediate | middle laminated body 50 can be removed suitably. In this way, by removing the outer peripheral portion of the second adhesive layer 22 in advance, even if the second adhesive layer 22 flows in the second sticking step, the second adhesive layer 22 is removed from the laminate. You can avoid exposure.

  In addition, it is assumed that the distance which the 2nd adhesive bond layer 22 flows in a 2nd sticking process is longer than the distance which the 1st adhesive bond layer 12 flows in a 2nd sticking process. Therefore, in the first solvent discharge step, the outer peripheral portion of the second adhesive layer 22 is removed so that the end portion of the second adhesive layer 22 is inside the end portion of the first adhesive layer 12. Is preferred.

  The position to which the solvent discharged in the first solvent discharge step is applied can be appropriately adjusted depending on the film thickness of the second adhesive layer 22 and the like. For this reason, although not particularly limited, as shown in FIG. 2A, the position to which the solvent discharged in the first solvent discharge step is applied is inward from the end of the planar portion of the first support 13. For example, the width a is more preferably 0.1 mm or more and 5.0 mm or less, and particularly preferably 0.1 mm or more and 3.0 mm or less. If width a is 0.1 mm or more and 5.0 mm or less, the outer peripheral part of the 2nd adhesive bond layer 22 can be removed suitably. As a result, when the substrate 11 and the second support 23 are pasted via the second adhesive layer 22 in the subsequent second pasting step, the second adhesive layer 22 becomes the first adhesive layer 12 and the first adhesive layer 12. Bonding to the support 13 can be more suitably suppressed.

  The solvent used in the first solvent discharge step may be appropriately selected according to the type of the adhesive and is not particularly limited. For example, the solvent used as the dilution solvent described above can be used. And cyclic hydrocarbons (terpenes) such as branched hydrocarbons having 4 to 15 carbon atoms, monoterpenes and diterpenes can be preferably used.

  In the first solvent discharge step, a method for discharging the solvent may be a known method and is not particularly limited. For example, the solvent may be sprayed on the outer peripheral portion of the second adhesive layer 22. However, it may be discharged using a dispensing nozzle. In the first solvent discharge step, the second adhesive layer 22 formed on the outer peripheral portion on the substrate 11 may be removed while rotating the substrate 11.

  Moreover, what is necessary is just to adjust the supply amount and discharge time of a solvent suitably in a 1st solvent discharge process according to the kind of 2nd adhesive bond layer to be used, and the kind of solvent.

[Second solvent discharge process]
In the second solvent discharge step, the solvent is supplied to the outer peripheral portion of the first adhesive layer 12 on the first support 13. Thereby, as shown in FIG. 2B, the outer peripheral portion of the first adhesive layer 12 on the first support 13 can be removed to a position closer to the inner peripheral side than the substrate 11.

  When the outer peripheral portion of the first adhesive layer 12 on the first support 13 is removed to the position on the inner peripheral side of the substrate 11, the fluidized first adhesive layer 12 and the substrate 11 in the second pasting step. Excessive protrusion from between the first support 13 and the first support 13 can be suppressed. Thereby, the protruding first adhesive layer 12 can be prevented from firmly bonding the first support 13 and the substrate 11, and the first support 13 can be suitably separated from the laminate 100.

  In the second solvent discharge step, it is preferable to discharge the solvent toward the position where the end of the substrate overlaps on the first support. By discharging the solvent toward such a position, a part of the substrate 11 wraps around the substrate 11 and reaches the first adhesive layer 12, and a part of the solvent directly reaches the first adhesive layer 12. Thereby, the outer periphery of the 1st adhesive bond layer 12 can be removed suitably. In particular, the end portion of the first adhesive layer 12 on the first support 13 is at a position of 0 mm or more and 0.5 mm or less, preferably 0.1 mm or more and 0.5 mm or less on the inner peripheral side of the substrate 11. Thus, it is preferable to remove the outer periphery of the first adhesive layer 12.

  For example, in the second solvent discharge step, the position at which the solvent is discharged is in the range of 0.3 mm or more and 1.5 mm or less from the end of the surface of the first support 13 on which the first adhesive layer 12 is formed. It is preferable that it is in the range of 0.3 mm or more and 1.0 mm or less. Here, as shown in FIG. 2B, the reference for the position at which the solvent is discharged in the second solvent discharge step can be expressed by a width b that extends inward from the end of the flat portion of the first support 13. . That is, the width b is preferably 0.3 mm or more and 1.5 mm or less, and more preferably 0.3 mm or more and 1.0 mm or less.

  Moreover, what is necessary is just to select suitably the angle which supplies a solvent to the outer peripheral part of the 1st adhesive bond layer 12 on the 1st support body 13 in the 2nd solvent discharge process.

  The second solvent discharging step is performed after the second adhesive layer forming step and before the second sticking step, similarly to the first solvent discharging step. The execution order of the first solvent discharge step and the second solvent discharge step is not particularly limited, the first solvent discharge step may be performed first, the second solvent discharge step may be performed first, or the first solvent The discharge step and the second solvent discharge step may be performed in parallel. Alternatively, the solvent may be discharged through the nozzle in the first solvent discharge step and the nozzle may be moved, and then the solvent may be discharged through the same nozzle in the second solvent discharge step.

  The solvent used in the second solvent discharge step may be appropriately selected according to the type of the adhesive and is not particularly limited. For example, the solvent used as the dilution solvent described above can be used. And cyclic hydrocarbons (terpenes) such as branched hydrocarbons having 4 to 15 carbon atoms, monoterpenes and diterpenes can be preferably used.

  Further, in the second solvent discharging step, a method for discharging the solvent may be a known method and is not particularly limited. For example, the solvent may be sprayed on the outer peripheral portion of the first adhesive layer 12. However, it may be discharged using a dispensing nozzle. In the first solvent discharge step, the first adhesive layer 12 formed on the outer peripheral portion on the substrate 11 may be removed while rotating the substrate 11.

  Moreover, what is necessary is just to adjust suitably the supply amount and discharge time of a solvent in a 2nd solvent discharge process according to the kind of 1st adhesive bond layer to be used, and the kind of solvent.

[Second sticking process]
In the second attaching step, the second support 23 and the substrate 11 in the intermediate laminate 50 are attached via the second adhesive layer 22.

  In the second sticking step, the second adhesive layer 22 formed on the substrate 11 of the intermediate laminate 50 and the second support 23 are overlapped by a pair of heated plate members so as to face each other, and these are sandwiched. May be pasted together. Thereby, the laminated body 100 can be formed. In the second pasting step, the pasting temperature, pasting pressure, and pasting time for pasting the substrate 11 and the second support 23 may be appropriately adjusted according to the type of the second adhesive layer 22.

[Second support 23]
The second support 23 has a strength necessary to prevent the substrate 11 from being damaged or deformed during processes such as transporting the substrate 11 and flip-chip mounting, for example, to alter the separation layer 14. Any material that transmits light may be used. From the above viewpoint, as the second support member 23, as in the first support member 13, for example, one made of glass, silicon, or acrylic resin can be used.

[Separation layer 24]
The separation layer 24 is a layer that is altered by light irradiation, and is provided on the surface of the second support 23 on the side where the substrate 11 is bonded via the second adhesive layer 22. Thereby, the substrate 11 and the second support 23 can be easily separated by irradiating the separation layer with light via the second support 23.

  The thickness, material, manufacturing method, and the like of the separation layer 24 can be the same as those described for the separation layer 14. In addition, as a material which comprises the separation layer 24, the same material as the material which comprises the separation layer 14 may be used, and a different material may be used.

[Laminate 100]
FIG. 3 is a view for explaining the laminate obtained by the above steps and the conventional laminate. Here, (a) of FIG. 3 is a figure explaining the laminated body 100 formed by the 2nd sticking process which the processing method concerning this embodiment includes, (c) of FIG. 3 is conventional. It is a figure explaining the laminated body 102 formed by the method.

  As shown to (a) of FIG. 3, since the laminated body 100 has removed the outer peripheral part of the 2nd adhesive bond layer 22 by the 1st solvent discharge process, the 2nd adhesive bond layer 22 is the 1st adhesive bond layer 12. The first support 13 is not bonded. Moreover, since the outer peripheral part of the 1st adhesive bond layer 12 was removed by the 2nd solvent discharge process, the 1st adhesive bond layer protrudes from the isolation | separation layer 14, and it does not adhere to the 1st support body 13 excessively. For this reason, the 1st support body 13 can be successfully isolate | separated from the laminated body 100 by a later separation process.

  On the other hand, as shown in FIG. 3C, in the laminate 102 formed by the conventional method, the excessive second adhesive layer 22 is bonded to the first adhesive layer 12. Further, the excessive first adhesive layer 12 protruding from the separation layer 14 is adhered to the first support 13. For this reason, it may be difficult to separate the first support 13 from the stacked body 102 in the subsequent separation step.

(Modification)
As described above, in the second solvent discharge step included in the processing method according to the present invention, the outer peripheral portion of the first adhesive layer 12 is removed, but the embodiment of the second solvent discharge step is not limited to this. For example, in the second solvent discharge step included in one modification of the processing method according to the present invention, by supplying a solvent to the outer peripheral portion of the first adhesive layer 12 on the first support 13, ( As shown in c), the inside of the first adhesive layer 12 can be dissolved by allowing a solvent to enter the inside of the first adhesive layer 12.

  Further, as shown in FIG. 3B, the outer peripheral portion of the first adhesive layer 12 is formed in the laminate 101 formed by the present modification by allowing the solvent to enter the outer peripheral portion of the first adhesive layer 12. The solvent is soaked in Thereby, the adhesive force of the outer peripheral part of the 1st adhesive bond layer 12 can be reduced. For this reason, even if the 1st adhesive bond layer 12 adheres to the outer peripheral part of the 1st support body 13, by irradiating light to the separation layer 14 via the 1st support body 13 in a separation process, it is the 1st from the board | substrate 11. One support 13 can be successfully separated.

[Separation process]
4A and 4B are diagrams for explaining the outline of the separation step included in the processing method according to the present embodiment. The separation step included in the processing method according to the present embodiment includes a separation step of separating the first support (support) 13 and the substrate 11 after the second sticking step. Here, the first support (support) 13 has translucency, and a separation layer 14 that is altered by light irradiation is provided on the surface of the first support 13 to which the substrate 11 is attached. In the separation step, the first support 13 and the substrate 11 are separated by irradiating the separation layer 14 with light.

  Here, as shown to (a) of FIG. 4, the 1st adhesive bond layer 12 in the laminated body 100 does not protrude excessively on the 1st support body 13. FIG. Further, the second adhesive layer does not flow to the first support 13. For this reason, if the separation layer 14 is altered by irradiating light through the first support 13, the substrate 11 and the first support 13 can be successfully separated (FIG. 4B). )). For this reason, when the 1st support body 13 is isolate | separated from the laminated body 100, it can prevent that the board | substrate 11 and the 2nd support body 23 isolate | separate. For this reason, the board | substrate 11 can be suitably supported by the 2nd support body 23 in processes, such as subsequent flip chip mounting. Further, when the role of the second support 23 is finished, the second support 23 can be easily separated from the substrate 11 by irradiating the separation layer 24 with light through the second support 23. .

Other Embodiment
The processing method according to the present invention is not limited to the above embodiment. For example, instead of the embodiment in which the first support 13 and the substrate 11 are separated by irradiating the separation layer 14 with light through the first support 13, a perforated support is used as the first support, It can also be set as the embodiment which isolate | separates the board | substrate 11 and a perforated support body by supplying a solvent to the 1st adhesive bond layer 12. FIG.

  (A) of FIG. 5 is a figure explaining the outline of the isolation | separation process which the processing method concerning this embodiment includes, and the outline of the laminated body 103 which used the perforated support body 33 as a 1st support body is shown. It is a figure explaining. Here, the laminated body 103 can supply the solvent to the first adhesive layer 12 from a plurality of through holes provided in the perforated support 33. By supplying the solvent from the through hole of the perforated support 33, the inner part of the laminated body 103 from the outer peripheral part of the first adhesive layer 12 can be dissolved.

  Here, the laminated body 103 has the solvent infiltrated into the outer peripheral portion of the first adhesive layer 12 of the laminated body 103 by the second solvent discharge step included in the processing method according to the present invention. For this reason, the adhesive force of the outer peripheral part of the 1st adhesive bond layer 12 in the laminated body 103 is falling. Therefore, the substrate 11 and the perforated support 33 can be preferably separated by dissolving the first adhesive layer 12 in the inner portion of the outer peripheral portion with the solvent supplied from the through hole of the perforated support 33. ((B) of FIG. 5).

  In the processing method according to still another embodiment, a perforated support is used instead of the second support 23, and the second adhesive layer 22 is dissolved with a solvent supplied from the through-hole of the perforated support. A separation step may be performed.

  In the processing method according to still another embodiment, a separation layer may be formed on the second support 23 in the same manner as the first support 13. That is, the laminate may be formed such that the substrate 11 and the second support 23 are laminated via the separation layer and the second adhesive layer 22. In the present embodiment, the separation layer can be altered by irradiating light through the second support 23 after performing a process such as flip chip mounting on the substrate 11. Therefore, the second support 23 can be separated from the substrate 11 without applying a large force to the substrate 11 after flip-chip mounting.

  In yet another embodiment, in the first adhesive layer application step, the separation layer 14 of the first support 13 on which the separation layer 14 is formed is formed instead of applying the adhesive to the substrate 11. The first adhesive layer may be formed by applying an adhesive to the side surface. In the second adhesive layer application step, the second adhesive layer is formed by applying an adhesive to the second support instead of applying the adhesive to the substrate 11 in the intermediate laminate 50. Good.

  In still another embodiment, the method further includes a step of discharging a solvent to the first adhesive layer 12 and the second adhesive layer 22 in the outer peripheral portion of the laminate 100 after the second sticking step. May be.

[Example 1]
(Formation of first and second adhesive layers)
TZNR (registered trademark) -A3007T (manufactured by Tokyo Ohka Kogyo Co., Ltd.) is spin-coated on a semiconductor wafer substrate (12 inches, silicon) at a film thickness of 50 μm and baked at 90 ° C., 160 ° C., and 220 ° C. for 4 minutes each. A first adhesive layer was formed. Then, while rotating the semiconductor wafer substrate on which the first adhesive layer was formed at 1,500 rpm, the EBR nozzle was used to feed TZNR (registered trademark) HC thinner (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at a supply rate of 10 cc / min. By supplying for 15 minutes, the outer peripheral portion of the first adhesive layer formed on the outer peripheral portion of the semiconductor wafer substrate is adjusted to 1.3 mm inward with reference to the end portion of the wafer substrate. The layer was removed.

Next, a bare glass support (12 inches, thickness 700 μm) was used as the first support, and a separation layer was formed on the first support by a plasma CVD method using fluorocarbon. As conditions for the first separation layer forming step, a separation layer is formed by performing a CVD method using C ₄ F ₈ as a reaction gas 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 fluorocarbon film (thickness 1 μm) was formed on the first support.

  Next, the first support, the separation layer, the first adhesive layer, and the wafer substrate are overlapped in this order, preheated at 215 ° C. for 180 seconds under vacuum, and then for 360 seconds at a pressure of 2000 kgf. The first support and the wafer substrate were pasted by pressing (first pasting step). This produced the intermediate laminated body.

  Next, the back surface of the wafer substrate of the obtained intermediate laminate was subjected to a thinning process (50 μm) with a back grinder manufactured by DISCO. Further, TZNR (registered trademark) -A4012 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) is spin-coated on the surface of the wafer substrate that has been thinned so as to have a film thickness of 120 μm. For 5 minutes (second adhesive layer forming step).

  A first solvent discharge step was performed on the intermediate laminate obtained by the above step, and the width of the first adhesive layer removed by the step was evaluated. In addition, the reference | standard of the discharge position of the solvent in a 1st solvent discharge process is an edge part of the plane part in the outer periphery of the 1st support body 13. As shown in FIG. (See (a) in FIG. 2).

  While rotating the intermediate laminate at 1,500 rpm, the EBR nozzle is positioned at a position of 2.5 mm from the end of the planar portion on the outer periphery of the bare glass support (first support) toward the inside of the intermediate laminate 50. TZNR (registered trademark) HC thinner (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was discharged at a supply rate of 10 cc / min for 5 minutes. Thereby, the outer peripheral part of the 2nd adhesive bond layer was removed.

  Then, the width | variety of the part from which the 1st adhesive bond layer was removed by the 1st solvent discharge process was measured. The width of the portion from which the first adhesive layer was removed was measured at four points on the upper, lower, right, and left sides of the outer peripheral portion of the laminate when the laminate was viewed in plan. The lower portion corresponds to a notch portion in the stacked body.

  The reference for measuring the width of the part from which the adhesive layer has been removed is based on the end of the outer peripheral part of the wafer substrate, and the width when going to the inside of the intermediate laminate is evaluated as a negative value. The width when going to the outside was evaluated with a positive value.

  As a result, in the first solvent discharge step, although slight solvent permeation into the first adhesive layer was observed, the measured value was 0 μm at three locations, and the first adhesive layer was the end of the substrate. It was removed neatly along the edge of the outer peripheral portion of the wafer substrate without protruding.

  A second solvent ejection step was performed on the intermediate laminate subjected to the above evaluation, and the width of the first adhesive layer removed by the step was evaluated. In addition, the reference | standard of the discharge position of the solvent in a 2nd solvent discharge process was based on the edge part of the plane part in the outer periphery of the 1st support body 13 (refer FIG.2, (b)).

  While the intermediate laminate is rotated at 1,500 rpm, a supply amount of 10 cc / min is provided by the EBR nozzle at a position of 1.0 mm from the end of the flat portion on the outer periphery of the first support toward the inside of the intermediate laminate. TZNR (registered trademark) HC thinner (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was discharged for 2 minutes. Thereby, the outer peripheral part of the 1st adhesive bond layer was removed (2nd solvent discharge process). In this state, the portion where the first adhesive layer was removed was evaluated.

  As a result, the first adhesive layer is directed inward from the end of the outer peripheral portion of the wafer substrate at the four points of the upper, lower, right, and left sides of the outer peripheral portion of the intermediate laminate by the second solvent discharge step. It was confirmed that it was removed.

  A bare glass support (12-inch size, thickness 700 μm) was used as the second support, and a separation layer was formed on the first support (second separation layer forming step). The second separation layer forming step was performed by the same method as the first separation layer forming step.

  Next, the intermediate laminate, the separation layer, and the second support are overlapped in this order, preheated at 180 ° C. for 180 seconds under vacuum, and pressed for 600 seconds at a pressure of 1500 kgf, The intermediate laminate was pasted (second pasting step).

(Evaluation of flow width of adhesive layer)
After performing the 2nd sticking process, it evaluated about the width | variety which the 1st adhesive bond layer in the laminated body flowed.

  The part where the flow width of the first and second adhesive layers is measured is the end of the outer peripheral part of the wafer substrate. Moreover, the reference | standard of the width | variety which the 1st adhesive bond layer moved was also made into the edge part of the outer peripheral part of a wafer substrate, and the distance when it flowed toward the outer side of a laminated body from that was evaluated by the positive value.

  As a result, the 1st adhesive bond layer was flowing over the width | variety of 76.3-280.4 micrometers from the edge part of a wafer board | substrate by being pressed in a 2nd sticking process. Therefore, when the first adhesive layer is added to the width of the portion where the first adhesive layer is removed by the second solvent discharge step, the width is 174, 7 to 453.9 μm by being pressed in the second application step. It was flowing for a long time. Here, no protrusion of the first and second adhesive layers was observed, and these adhesive layers remained inside from the end portions of the outer peripheral portions of the first support and the second support.

[Examples 2 to 4]
An intermediate laminate having different types of the first adhesive layer was prepared, and the first solvent ejection step and the second solvent ejection step were performed, and the state of each first adhesive layer in the outer peripheral portion of the laminate was evaluated. The first adhesive used for the evaluation is as follows.
Example 2: TZNR (registered trademark) -A3007T (manufactured by Tokyo Ohka Kogyo Co., Ltd.)
Example 3: TZNR (registered trademark) -A4005 (manufactured by Tokyo Ohka Kogyo Co., Ltd.)
Example 4: TZNR (registered trademark) -A4012 (manufactured by Tokyo Ohka Kogyo Co., Ltd.)
(Formation of first and second adhesive layers)
First, the adhesives of Examples 2 to 4 were separately spin-coated on a semiconductor wafer substrate (12 inches, silicon) so as to have a film thickness of 50 μm, and each temperature was 90 ° C., 160 ° C., and 220 ° C. for 4 minutes. Baking was performed to form a first adhesive layer (first adhesive layer forming step).

Next, a bare glass support (12 inches, thickness 700 μm) was used as the first support, and a separation layer was formed on the first support (first separation layer forming step). As conditions for the first separation layer forming step, a separation layer is formed by performing a CVD method using C ₄ F ₈ as a reaction gas 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 fluorocarbon film (thickness 1 μm) was formed on the first support.

  Next, each of the wafer substrates on which the adhesive layers of Examples 2 to 4 were formed was separately superposed so that the first support, the separation layer, the first adhesive layer, and the wafer substrate were in this order, and vacuum was applied. Below, the 1st support body and the wafer board | substrate were affixed by pressing for 180 second with the affixing pressure of 215 degreeC and 2000 kgf (1st affixing process). Thereby, the intermediate | middle laminated body of Examples 2-4 was produced.

  Next, the back surface of the wafer substrate was thinned (50 μm) using a DISCO back grinder (thinning step). In the intermediate laminates of Examples 2 to 4, spin coating of TZNR (registered trademark) -A4012 (manufactured by Tokyo Ohka Kogyo Co., Ltd., viscosity 10000 cP) on the surface of the wafer substrate subjected to the thinning treatment was performed to a thickness of 120 μm. did. Thereafter, the intermediate laminates of Examples 2 to 4 were baked under the conditions of 90 ° C./5 minutes in the pin-up state, 90 ° C./5 minutes, 160 ° C./10 minutes, and 220 ° C./5 minutes in the pin-down state. .

(First and second solvent discharge process)
While rotating the intermediate laminated body of Examples 2-4 at 1,500 rpm, it is 10 cc / min by the EBR nozzle in the position of 2.5 mm toward the inside from the edge part of the plane part in the outer periphery of a 1st support body. TZNR (registered trademark) HC thinner (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was discharged at a supply amount for 4 minutes (first solvent discharge step). Next, TZNR (registered trademark) HC thinner (Tokyo Ohka Kogyo Co., Ltd.) is placed at a position of 0.8 mm inward from the edge of the outer peripheral portion of the wafer substrate with an EBR nozzle at a supply rate of 10 cc / min for 2 minutes. Made). Thereby, the outer peripheral part of the 1st adhesive bond layer and the 2nd adhesive bond layer was removed (2nd solvent discharge process).

(Evaluation of end state in intermediate laminate)
As above-mentioned, the state of the 1st adhesive bond layer of the outer peripheral part of the intermediate | middle laminated body of Examples 2-4 which performed the 1st and 2nd solvent discharge process was evaluated. As a result, in any of the intermediate laminates of Examples 2 to 4, the outer peripheral portion of the first adhesive layer was not dissolved on the appearance and remained. Moreover, in Example 2, the bubble generation | occurrence | production was recognized by the 1st adhesive bond layer in the outer peripheral part of an intermediate | middle laminated body by preheating.

(Evaluation of end state in laminate)
About the intermediate | middle laminated body of Examples 2-4, the 2nd support body was affixed, the laminated body was produced, and the state of the 1st and 2nd adhesive bond layer in the outer peripheral part of a laminated body was evaluated.

  For Examples 2-4, the first support, the separation layer, the first adhesive layer, the wafer substrate, the second adhesive layer, the separation layer, and the second support were superposed in this order, under vacuum, Preheating was performed at 215 ° C. for 3 minutes, and the second support and the wafer substrate were attached by pressing for 6 minutes at an application pressure of 1500 kgf (second application step).

  When the 1st and 2nd adhesive bond layers of the outer peripheral part of the laminated body of Examples 2-4 were evaluated, in any of Examples 2-4, contact of the 1st adhesive bond layer and the 2nd adhesive bond layer was recognized. I couldn't. In any of the laminates of Examples 2 to 4, it was recognized that HC thinner soaked into the first adhesive layer and the inside was dissolved.

[Evaluation of separability]
About the laminated body of the said Examples 1-4, the separation process which irradiates light to a separation layer through a 1st support body was performed. As conditions for the separation process, the laser beam wavelength is set to 532 nm and the laser beam diameter is set to 180 μm from the first support side, and the distance between centers of irradiated regions in the laser pulse is set to 180 μm. The laser beam was irradiated at a repetition rate of 40 kHz at a scanning speed of 7200 mm / s (separation step). Then, about each laminated body, the separability from the laminated body of a 1st support body was evaluated.

  In any of the laminates of Examples 1 to 4, the first support could be separated by the weight of the laminate without having to apply a large force.

  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.

  The present invention can be widely used, for example, in a manufacturing process of a miniaturized semiconductor device.

DESCRIPTION OF SYMBOLS 11 Board | substrate 12 1st adhesive layer 13 1st support body 14 Separation layer 22 2nd adhesive layer 23 2nd support body 33 Perforated support body (1st support body)

Claims (7)

A first attaching step of attaching a substrate to the first support via a first adhesive layer;
After the first attaching step, a second adhesive layer forming step for forming a second adhesive layer on the surface facing away from the surface on which the first support in the substrate is attached;
After the second adhesive layer forming step, a first solvent discharging step of discharging a solvent to the outer peripheral portion of the second adhesive layer on the substrate and removing the outer peripheral portion;
After the first solvent discharge step, a second attaching step of attaching a second support to the substrate via a second adhesive layer;
The processing method characterized by including the separation process which isolate | separates a 1st support body and this board | substrate after a 2nd sticking process.   After the second adhesive layer forming step, before the second sticking step, including a second solvent discharge step of supplying a solvent to the outer peripheral portion of the first adhesive layer on the first support. The processing method according to claim 1, wherein:   The processing method according to claim 2, wherein in the second solvent discharge step, the outer peripheral portion of the first adhesive layer on the first support is removed to a position on the inner peripheral side with respect to the substrate.   The processing method according to claim 2, wherein in the second solvent discharge step, the solvent is allowed to enter the first adhesive layer.   5. The processing method according to claim 2, wherein in the second solvent discharge step, the solvent is discharged toward a position where the end of the substrate overlaps on the first support.   3. The solvent is discharged through the nozzle in the first solvent discharge step, the solvent is moved, and then the solvent is discharged through the nozzle in the second solvent discharge step. The processing method of any one of -5. Before the first sticking step, including a first adhesive layer forming step of forming an adhesive layer by applying an adhesive to at least one of the first support and the substrate,
The processing method according to any one of claims 1 to 6, wherein an outer peripheral portion of the first adhesive layer is removed after the first adhesive layer forming step and before the first sticking step.

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