JP6298393B2 - Support separation method - Google Patents

Description

  The present invention relates to a support separating method.

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

  Since the strength of the wafer substrate is reduced due to the thin plate, in order to prevent damage to the thinned wafer substrate, a circuit is placed on the wafer substrate while automatically supporting the support plate on the wafer substrate during the manufacturing process. Etc. are mounted. Then, after the manufacturing process, the wafer substrate is separated from the support plate. So far, various methods for peeling the support from the wafer have been used.

  As a method for manufacturing a semiconductor chip in which a support is bonded to a semiconductor wafer, the semiconductor wafer is processed, and then the support is separated, a method described in Patent Document 1 is known. In the method described in Patent Document 1, a light-transmitting support and a semiconductor wafer are bonded together via a photothermal conversion layer and an adhesive layer provided on the support, and after the semiconductor wafer is processed, the support side The photothermal conversion layer is decomposed by irradiating radiant energy from the substrate to separate the semiconductor wafer from the support.

JP 2004-64040 A (published February 26, 2004)

  However, in the technique described in Patent Document 1, light is irradiated to the entire surface of the separation layer of the laminate that faces the support. For this reason, after irradiation of the light to the separation layer, before the support separation device separates the support from the laminate, there is a problem that the support may be detached from the laminate and cause a positional shift.

  The present invention has been made in view of the above-described problems, and the object of the present invention is to displace the support after the light is applied to the separation layer and before the support separation device separates the support from the laminate. It is an object of the present invention to provide a method for separating a support capable of preventing the occurrence of the problem.

  In order to solve the above problems, a support separating method according to the present invention comprises a substrate and a material that transmits light, and absorbs an adhesive layer between the support that supports the substrate. A support separating method for separating a support from a laminate formed by laminating a separation layer that is altered by the method, wherein the surface of the separation layer facing the support is 0.5% or more of the surface, Including a first preliminary separation step of altering the separation layer by irradiating the separation layer with light through the support so that an unirradiated region occupying an area of 65% or less is generated. It is a feature.

  According to the present invention, it is possible to prevent the support from being displaced after the light is applied to the separation layer and before the support separation device separates the support from the laminated body.

It is a figure explaining the outline of the support body separation method which concerns on one Embodiment (1st Embodiment). It is a figure explaining the outline of the support body separation method which concerns on one Embodiment (2nd Embodiment). It is a figure explaining the outline of the irradiation pattern of the light to the separation layer in the support body separation method which concerns on one Embodiment, and the irradiation pattern of the light to the separation layer in the conventional support body separation method. It is a figure explaining the outline of the unirradiated area | region of the light in the support body separation method which concerns on one Embodiment. It is a figure explaining the outline of the support body separation apparatus used in the support body separation method which concerns on one Embodiment. It is a figure explaining the outline of the evaluation method of the adhesive force in an Example and a comparative example.

<First Embodiment>
The support separating method according to one embodiment (first embodiment) will be described in more detail with reference to FIGS.

  As shown in FIG. 1 (a), in the support separating method according to this embodiment, an adhesive layer and a light are formed between a substrate and a support that supports the substrate. The laminated body 10 formed by laminating the separation layer that changes in quality by absorbing water is separated.

  Further, in the support separating method according to the present embodiment, the light-irradiated region 14a occupying an area of 0.5% or more and 65% or less of the surface of the separation layer 14 facing the support plate 12 is provided. As shown in FIG. 1, after the preliminary separation step (FIGS. 1B and 1C) for altering the separation layer 14 by irradiating the separation layer 14 with light through the support plate 12, and after the preliminary separation step, the substrate 11 includes a separation step ((d) and (e) in FIG. 1) including a separation step of separating the support plate 12 from the stacked body 10 by fixing 11 and applying a force to the support plate 12.

  In the present specification, the phrase “deterioration” of the separation layer 14 refers to a state in which the separation layer 14 can be broken by receiving a slight external force, or a state in which the adhesive force with the layer in contact with the separation layer 14 is reduced. Means a phenomenon. The alteration of the separation layer 14 includes decomposition (exothermic or non-exothermic) due to absorbed light energy, cross-linking, configuration change or dissociation of functional groups (and curing or desorption of the separation layer 14 accompanying these). Gas, contraction or expansion) and the like. In this way, the adhesive strength of the separation layer 14 is reduced by altering the separation layer 14.

  As shown in FIG. 4A, in the first pre-separation step, the regions 14b1 and 14b2 in the separation layer 14 are irradiated by irradiating the separation layer 14 with light L so that a region 14a not irradiated with light is generated. To deteriorate the adhesive strength. That is, in the first preliminary separation step, the adhesive force of the separation layer 14 can be sufficiently reduced in the regions 14b1 and 14b2 irradiated with the light L, and the adhesive force can be maintained in the region 14a not irradiated with the light L. As described above, preliminary separation is performed on the laminate 10. Thereby, before the support body separation apparatus separates the support plate 12 from the laminated body 10, it can prevent that the support plate 12 detaches | leaves from the laminated body 10, and a position shift arises.

  For this reason, after performing a 1st pre-separation process to the laminated body 10, a support body separation apparatus does not receive to the influence by position shift of the support plate 12 of the laminated body 10, For example, it shows to (e) of FIG. The support plate 12 of the laminate 10 can be suitably captured by a holding means such as the bellows pad 31 of the separation plate 30.

  In the first preliminary separation step, the adhesive strength of the regions 14b1 and 14b2 irradiated with the light L in the separation layer 14 of the laminate 10 is sufficiently reduced. The substrate 11 and the support plate 12 can be suitably separated by fixing and applying a slight force to the support plate 12.

  Therefore, according to the support separating method according to the present embodiment, a series of steps from the irradiation of the light L to the separation layer 14 of the stacked body 10 to the separation of the support plate 12 from the stacked body 10 are automated to succeed. Can be done well.

[First preliminary separation step]
As shown in FIG. 1B, in the first preliminary separation step, the light L is irradiated through the support plate 12 in the stacked body 10 by laser irradiation means (not shown). As a result, the separation layer 14 is altered, and the adhesive force of the separation layer 14 is reduced. Here, by irradiating the separation layer 14 of the laminate 10 with light by the laser irradiation means while relatively moving the laminate 10 and the laser irradiation means, the region 14a where the light L is not irradiated to the separation layer 14 is irradiated. (FIG. 1 (c)).

  In the first preliminary separation step included in the support separation method according to the present embodiment, as shown in FIG. 3A, the laser irradiation means (not shown) is formed so as to form a locus along two solid arrows. The separation layer 14 is irradiated with light L. Thus, in the first preliminary separation step, light is scanned linearly so as to form tracks that do not overlap each other on the surface of the separation layer 14 facing the support plate 12. Therefore, it is possible to prevent the beam spots of the light L from overlapping, and it is possible to prevent the substrate 11 from being damaged by the light L.

  Also, the laser irradiation means (not shown) is scanned so as to form a locus along two solid arrows, thereby supporting the laser irradiation means in the separation layer 14 as shown in FIG. The unirradiated region 14a is generated in a strip shape having a length direction of a straight line passing through any two points on the outer periphery of the surface facing the plate 12 and the center of gravity of the surface facing the support plate 12. Here, the width W of the unirradiated region 14a shown in FIG. 4A is 2 mm or more and 150 mm or less, more preferably 2 mm or more and 80 mm or less, and most preferably 2 mm or more and 10 mm or less. is there.

  From another viewpoint, in the first preliminary separation step, the area of the unirradiated region 14a is 0.5% or more and 65% or less of the surface of the separation layer 14 facing the support plate 12, more preferably 0.5% or more and 35% or less, and most preferably, laser irradiation is performed so as to occupy an area of 0.5% or more and 3% or less. If the area of the unirradiated region 14a is 0.5% or more with respect to the surface facing the support plate 12, after the first preliminary separation step and before the separation step, the support plate is removed from the stacked body 10. It is possible to suitably prevent the 12 from being detached and causing a positional shift. Further, if the area of the unirradiated region is 65% or less with respect to the surface facing the support plate 12, the support plate 12 is removed from the laminate 10 by applying a slight force in the subsequent separation step. It can be preferably separated.

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.

  The laser beam irradiation conditions in the first preliminary separation step may be appropriately adjusted depending on the type of the separation layer, and are not limited, but the average output value of the laser beam is in the range of 1.0 W or more and 5.0 W or less. Is preferable, and the range of 3.0 W or more and 4.0 W or less is more preferable. The repetition frequency of the laser light is preferably in the range of 20 kHz to 60 kHz, and more preferably in the range of 30 kHz to 50 kHz. The wavelength of the laser light is preferably 300 nm or more and 700 nm or less, and more preferably 450 nm or more and 650 nm or less. According to such conditions, the energy of the pulsed light applied to the separation layer 14 can be set to an appropriate condition for altering the separation layer 14. For this reason, it is possible to prevent the substrate 11 from being damaged by the laser light.

  Further, the beam spot diameter of the pulsed light used in the first preliminary separation step is preferably 100 μm or more and 250 μm or less, and more preferably 120 μm or more and 230 μm or less.

  Further, the irradiation pitch of the pulsed light may be any pitch as long as adjacent beam spots do not overlap and can change the separation layer 14, but is preferably 110 μm or more and 250 μm or less, preferably 160 μm or more, More preferably, it is 220 μm or less. Thereby, it can prevent that light is irradiated with respect to the separation layer 14 in duplicate. Moreover, it can prevent that the board | substrate 11 receives a damage by irradiation of a laser beam by irradiating with light overlapping. Further, by preventing the beam spots formed on the separation layer 14 from overlapping each other, a region not irradiated with light may be formed between the beam spots, and the adhesive force of the separation layer 14 may be adjusted.

[Separation process]
In the separation step included in the support separation method according to the present embodiment, a part of the substrate 11 is fixed and a force is applied by the support plate 12 ((d) in FIG. 1). Thus, the substrate 11 and the support plate 12 are separated ((e) in FIG. 1). Moreover, since the support body separation method according to the present embodiment can suitably prevent the support plate 12 from being displaced before the separation step, the support body separation apparatus fails to hold the support plate 12, It is possible to prevent an error from occurring. Accordingly, the substrate 11 and the support plate 12 can be automatically and successfully separated.

(Support Separator 50)
In the support separating method according to this embodiment, the substrate 11 and the support plate 12 are separated using the support separating apparatus 50 shown in FIG. Further, as shown in FIG. 5, the substrate 11 side of the laminate 10 may be attached to a dicing tape 20 provided with a dicing frame 21 and placed on the stage 27 with the substrate 11 side as a bottom surface.

  As shown in FIG. 5, the support separating apparatus 50 includes a porous portion 26, a stage 27, a separating plate 30, a bellows pad (holding means) 31, a floating joint 32, a stopper 33, and an elevating / lowering portion 35.

  The porous portion 26 is provided on a stage 27 on which the stacked body 10 is placed, and the stage 27 fixes the stacked body 10 to the stage 27 by suction by a decompression unit (not shown).

  The separation plate 30 includes a bellows pad 31 that sucks and holds the support plate 12 by decompression means (not shown). Further, the separation plate 30 is provided with a floating joint 32 on the opposite side of the surface on which the bellows pad 31 is provided.

  The floating joint 32 is movable so as to have a circular orbit parallel to the plane of the stacked body 10 and an arc-shaped trajectory perpendicular to the plane of the stacked body 10, thereby allowing the separation plate 30 to freely move. Can tilt to. Note that the floating joint 32 can be prevented from excessively tilting the separation plate 30 by bringing the stopper 33 into contact with the separation plate 30. The elevating unit 35 moves the separation plate 30 up and down via the floating joint 32.

  The separation plate 30 lifts the support plate 12 upward in the direction perpendicular to the plane of the stacked body 10 via the floating joint 32. Here, the floating joint 32 tilts the separation plate 30 and utilizes the principle of wrinkles, thereby concentrating the force on a particularly weak portion of the light-irradiated region 14 a in the separation layer 14. As a result, the support plate 12 is separated from the laminate 10 by applying a smaller force to the unirradiated region 14 a of the light in the separation layer 14 than the force required to shift the position of the support plate 12 from the laminate 10. be able to. Therefore, the substrate 11 and the support plate 12 can be preferably separated without imposing an excessive burden on the substrate 11 and the support plate 12.

  As shown in FIG. 1E, if the substrate 11 and the support plate 12 are separated in the separation step, then the residue of the adhesive layer 13 and the separation layer 14 remaining on the surface of the substrate 11 is removed by washing, A desired process may be performed on the substrate 11. Here, as shown in FIG. 5, if the substrate 11 side of the laminate 10 is bonded to a dicing tape 20 provided with a dicing frame 21, the support plate 12 is separated, and then the substrate 11 is washed and diced. Thus, the process of manufacturing the semiconductor chip from the substrate 11 can be performed continuously.

  In addition, the support body dividing device used in the separation step is not limited to the separation plate 30 provided with the bellows pad 31. The support separating apparatus may be any apparatus that separates the substrate 11 and the support plate 12 by fixing one of the substrate 11 and the support plate 12 and applying a force to the other.

[Laminate 10]
The laminate 10 used in the support separating method according to this embodiment will be described in more detail. As shown to (a) of FIG. 1, in the support body separation method which concerns on this embodiment, from the material which permeate | transmits the board | substrate 11, the contact bonding layer 13, the separation layer 14 which changes in quality by absorbing light, and light is transmitted. Thus, a support plate (support) 12 that supports the substrate 11 is laminated in this order.

[Substrate 11]
The substrate 11 is attached to the support plate 12 provided with the separation layer 14 via the adhesive layer 13. The substrate 11 can be subjected to processes such as thinning and mounting while being supported by the support plate 12. The substrate 11 is not limited to a silicon wafer substrate, and an arbitrary substrate such as a ceramic substrate, a thin film substrate, a flexible substrate, or a mold substrate can be used.

[Support plate 12]
The support plate (support body) 12 is a support body that supports the substrate 11, and is attached to the substrate 11 through the adhesive layer 13. Therefore, the support plate 12 only needs to have a strength necessary for preventing damage or deformation of the substrate 11 during processes such as thinning, transporting, and mounting of the substrate 11. Moreover, what is necessary is just to be able to permeate | transmit the light for changing a separated layer. From the above viewpoint, examples of the support plate 12 include those made of glass, silicon, and acrylic resin.

[Adhesive layer 13]
The adhesive layer 13 is a layer formed by an adhesive used for attaching the substrate 11 and the support plate 12.

  As the adhesive, for example, various adhesives known in the art such as acrylic, novolak, naphthoquinone, hydrocarbon, polyimide, and elastomer are used as the adhesive constituting the adhesive layer 13 according to the present invention. Is possible. Hereinafter, the composition of the resin contained in the adhesive layer 13 in the present embodiment will be described.

  As the resin contained in the adhesive layer 13, any resin having adhesiveness may be used, and examples thereof include hydrocarbon resins, acrylic-styrene resins, maleimide resins, elastomer resins, and combinations thereof. It is done.

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

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

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

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

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

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

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

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

  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 adhesive layer 13 can be further suppressed when the laminate is exposed to a high temperature environment.

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

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

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

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

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

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

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

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

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

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

  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 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, a resist solvent (eg, PGMEA, PGME, etc.), acid (hydrogen fluoride) exposed when the wafer is subjected to a 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.), Septon V9475 (manufactured by Kuraray Co., Ltd.)), Septon V9827 (manufactured by Kuraray Co., Ltd.), styrene block having reactive cross-linked styrene-ethylene-butylene-styrene block copolymer (reactive polystyrene hard block) Kuraray)), polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene block copolymer (SEEPS-OH: terminal hydroxyl group modification), and the like. What has content and weight average molecular weight of the styrene unit of an elastomer in the above-mentioned range can be used.

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

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

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

  Examples of commercially available products that can be used as an elastomer included in the adhesive that constitutes the adhesive layer 13 include “Kepte (trade name)” manufactured by Kuraray Co., Ltd., “Hibler (trade name)” manufactured by Kuraray Co., Ltd., Asahi Kasei Corporation. “Tuff Tech (trade name)” manufactured by JSR Corporation, “Dynalon (trade name)” manufactured by JSR Corporation, and the like can be mentioned.

  The content of the elastomer contained in the adhesive constituting the adhesive layer 13 is, for example, preferably in the range of 50 parts by weight or more and 99 parts by weight or less, with the total amount of the adhesive composition being 100 parts by weight, and 60 parts by weight or more. The range of 99 parts by weight or less is more preferable, and the range of 70 parts by weight or more and 95 parts by weight or less is most preferable. By 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 adhesive layer 13 may include 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 agent which comprises the contact bonding layer 13 contains several types of elastomers, you may adjust so that content of a styrene unit may become in said range as a result of mixing. For example, Septon 4033 of Septon (trade name) manufactured by Kuraray Co., Ltd. having a styrene unit content of 30% by weight and Septon 2063 of Septon (trade name) having a styrene unit content of 13% by weight is 1 weight ratio. When mixed in a one-to-one relationship, the styrene content with respect to the total elastomer contained in the adhesive is 21 to 22% by weight, and therefore 14% by weight or more. For example, when a styrene unit of 10% by weight and 60% by weight are mixed at a weight ratio of 1: 1, it becomes 35% by weight and falls within the above range. The present invention may be in such a form. Moreover, it is most preferable that the plurality of types of elastomers included in the adhesive constituting the adhesive layer 13 all contain styrene units within the above range and have a weight average molecular weight within the above range.

  Note that the adhesive layer 13 is preferably formed using a resin other than a photocurable resin (for example, a UV curable resin). By using a resin other than the photocurable resin, it is possible to prevent a residue from remaining around the minute unevenness of the substrate to be supported after the adhesive layer 13 is peeled or removed. In particular, the adhesive constituting the adhesive layer 13 is preferably not soluble in any solvent but soluble in a specific solvent. This is because the adhesive layer 13 can be removed by dissolving it in a solvent without applying physical force to the substrate 11. Even when the adhesive layer 13 is removed, the adhesive layer 13 can be easily removed without damaging or deforming the substrate 11 even from the substrate 11 having a reduced strength.

(Diluted solvent)
Examples of the diluting solvent used when forming the adhesive layer 13 include straight-chain hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, and tridecane, and those having 4 to 15 carbon atoms. Branched hydrocarbons, for example, cyclic hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, tetrahydronaphthalene, p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4- Terpin, 1,8-terpine, bornin, norbornane, pinan, tsujang, karan, longifolene, geraniol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineo Terpinen-1-ol, terpinen-4-ol, dihydroterpinyl acetate, 1,4-cineole, 1,8-cineole, borneol, carvone, yonon, tuyon, camphor, d-limonene, l-limonene, Terpene solvents such as dipentene; lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone; ethylene glycol, diethylene glycol, propylene Polyhydric alcohols such as glycol and dipropylene glycol; S such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate or dipropylene glycol monoacetate A compound having a ter bond, a compound having an ether bond such as a monoalkyl ether such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether of the polyhydric alcohol or the compound having an ester bond, etc. Derivatives of polyhydric alcohols (in these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred); cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL) , Esters such as methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; anisole, ethyl Nji ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, and phenetole, the aromatic organic solvent such as butyl phenyl ether.

(Other ingredients)
The adhesive constituting the adhesive layer 13 may further contain other miscible materials as long as the essential properties are not impaired. For example, various conventional additives such as additional resins, plasticizers, adhesion aids, stabilizers, colorants, thermal polymerization inhibitors and surfactants for improving the performance of the adhesive may be further used. it can.

[Separation layer 14]
Next, the separation layer 14 is a layer formed of a material that is altered by absorbing light irradiated through the support plate 12.

  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.

  The separation layer 14 is provided on the surface of the support plate 12 on the side where the substrate 11 is bonded via the adhesive layer 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.

  In the laminate 10, another layer may be further formed between the separation layer 14 and the support plate 12. In this case, the other layer should just be comprised from the material which permeate | transmits light. Thereby, a layer imparting preferable properties and the like to the laminate 10 can be appropriately added without hindering the incidence of light on the separation layer 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.

  In addition, 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 in 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 adhesive layer 13 is flat (unevenness is not formed), whereby the separation layer 14 can be easily formed, and even when pasted. It becomes possible to paste on.

(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 support plate 12 or the like), the separation layer 14 is broken, and the support plate 12 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 support plate 12 or the like), the separation layer 14 is broken, and the support plate 12 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 N (R ¹ ) (R ² ) (where R ¹ and R ² Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), Z is absent or is CO—, —SO ₂ —, —SO— or —NH—, and n is 0 Or an integer 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, is represented by (e), or (f) Contains structure in its main chain.

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

Of the substituents represented by “Chemical Formula 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 given.

  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-trihydroxyphenyl) ) Sulphoxide 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, it is easy to remove the support plate 12 from the laminate 10, and the light irradiation time necessary for the removal can be shortened.

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

  The light that can be absorbed by the above structure is, for example, a high-pressure mercury lamp (wavelength: 254 nm or more, 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 support plate 12. 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 support plate 12 or the like), the separation layer 14 is broken, and the support plate 12 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 support plate 12 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 support plate 12 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 support plate 12 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 support plate 12 and the substrate 11, the absorption of infrared rays in the separation layer 14 is large, that is, the separation layer 14 is irradiated with infrared rays. It is preferable that the infrared transmittance 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.

  Moreover, 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 a ratio of 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 di- Examples include isostearate and acylate titanium such as (2-n-butoxycarbonylbenzoyloxy) tributoxytitanium; (v) water-soluble titanium compounds such as di-n-butoxy-bis (triethanolaminato) titanium and the like. It is done.

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 support plate 12. 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 support plate 12 or the like), the separation layer 14 is broken, and the support plate 12 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.

[Laminated body according to one modification]
The laminate used in the support separating method according to one embodiment of the present invention is not limited to that used in the first embodiment. For example, the laminated body used in the support separating method according to the modification includes the substrate 11, the separation layer 14 that is altered by absorbing light, the adhesive layer 13, and a material that transmits light. And a support plate (support body) 12 that supports the layers.

  Even if it is the said structure, the support body separation method which concerns on one Embodiment can be implemented suitably. Moreover, the laminated body which concerns on this modification can be used suitably in the laminated body which used the mold substrate as a board | substrate, for example.

<Support Separating Method According to Second Embodiment>
The support separating method according to the present invention is not limited to the first embodiment. For example, in the support separating method according to one embodiment (second embodiment), light is irradiated to the unirradiated region 14a in the separation layer 14 via the support plate 12 before the separation step. Thus, a configuration including a second preliminary separation step in which the region 14a in the separation layer 14 is altered may be included ((c) in FIG. 2).

  Since the first preliminary separation step ((a) to (c) in FIG. 2) and the separation step ((e) and (f) in FIG. 2) are the same as those in the first embodiment, Description is omitted.

[Second preliminary separation step]
As shown in FIG. 2D, in the support separating method according to the present embodiment, the region 14 a of the separation layer 14 is altered by irradiating light L through the support plate 12. For example, in the first embodiment, the region 14a of the separation layer 14 formed as shown in FIG. 3A is irradiated with light.

  Thereby, the adhesive force of the region 14a in the separation layer 14 can be adjusted. Therefore, after the second preliminary separation step and before the separation step, it is possible to suitably prevent the support plate 12 from being detached from the stacked body 10 and causing the positional displacement of the support plate 12. Moreover, since the adhesive force of the area | region 14a in the separation layer 14 can be adjusted suitably, the support plate 12 can be more suitably separated from the laminated body 10 in the separation step.

  The beam spot diameter of the pulsed light used in the second preliminary separation step is preferably 100 μm or more and 250 μm or less, and more preferably 120 μm or more and 230 μm or less.

  In the second preliminary separation step, the light irradiation pitch is preferably 120% or more with respect to the spot diameter of the pulsed light. When the light irradiation pitch is 120% or more with respect to the spot diameter of the pulsed light, the separation layer 14 is preferably prevented from being detached from the stacked body 10 in the second preliminary separation step. It is possible to suitably adjust the adhesive strength of the region 14a. Therefore, the support plate 12 can be suitably separated from the laminate 10 by applying a slight force in the subsequent separation step. In the second preliminary separation step, it is only necessary to adjust the adhesive force of the region 14a in the separation layer 14 by irradiating the region 14a in the separation layer 14, and it is necessary to provide an upper limit for the light irradiation pitch. Absent.

  The laser type and laser light irradiation conditions in the second pre-separation step are the same as those in the first pre-separation step, and a description thereof is omitted.

<Support Separating Method According to Another Embodiment>
The support separating method according to the present invention is not limited to the first and second embodiments. For example, in the support separation method according to the embodiment, in the first preliminary separation step, the region 14b ′ in the separation layer 14 is irradiated with laser light in accordance with the trajectories of a plurality of solid arrows shown in FIG. As a result, an unirradiated region 14a ′ is generated. Thereby, as shown in FIG. 4B, a region 14a ′ may be generated in a portion including the center of gravity of the surface of the separation layer 14 facing the support plate 12.

  According to the above configuration, the region 14a ′ in the separation layer 14 can prevent the support plate 12 from being detached in the vicinity of the center of gravity of the stacked body 10. For this reason, the support plate 12 is more preferably detached from the stacked body 10. Separation can be prevented. Further, by lifting the support plate 12 upward in the direction perpendicular to the plane of the stacked body 10, even if the separation plate 30 is inclined in any direction, the force is concentrated on the region 14 a, The support plate 12 can be separated.

  In still another embodiment, as shown in FIG. 4C, a region 14a ″ that is not irradiated with light may be provided by irradiating the region 14b ″ in the separation layer 14 with light. Also with the above configuration, the support separating method according to the present invention can be suitably implemented.

  In the support separating method according to the present invention, an unirradiated region of light that occupies an area of 0.5% or more and 65% or less of the surface of the separation layer 14 facing the support plate 12 is generated. Various shapes can be adopted for the unirradiated region. Therefore, according to the present invention, a non-irradiated region of light is generated in a band shape having a line segment connecting two arbitrary points on the outer periphery of the surface of the separation layer 14 facing the support plate 12 as a length direction. The support separation method can be suitably carried out.

  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.

[Evaluation of light irradiation pattern]
For Example 1, Example 2, and Comparative Example 1, the separation layer of the laminate was irradiated with laser light with different irradiation patterns, and the state of the laser spot in the separation layer was evaluated.

(Production of laminate)
First, the laminated body used in Example 1, Example 2, and Comparative Example 1 was produced according to the following procedures.

  TZNR (registered trademark) -A4017 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) is spin-coated on a semiconductor wafer substrate (12 inches of silicon), and baked at 90 ° C., 160 ° C., and 220 ° C. for 4 minutes each to form an adhesive layer. Formed (film thickness 50 μm). Thereafter, while rotating the semiconductor wafer substrate on which the adhesive layer is formed at 1,500 rpm, the EBR nozzle is used to supply TZNR (registered trademark) -HC thinner (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at a supply rate of 10 cc / min. By supplying for a minute, the outer peripheral portion of the adhesive layer formed on the outer peripheral portion of the semiconductor wafer substrate was removed up to 1.2 mm inward with respect to the end portion of the wafer substrate.

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

  Next, the wafer substrate, the adhesive layer, the separation layer, and the glass support are superposed in this order, preheated at 215 ° C. for 180 seconds under vacuum, and then pressed for 360 seconds with an application pressure of 2000 kgf. The support and the wafer substrate were attached. Thereby, the laminated body used for Example 1, Example 2, and Comparative Example 1 was produced.

(Laser irradiation)
Next, the laser beam irradiation pattern (Example 1) shown in FIG. 3A, the laser beam irradiation pattern (Example 2) shown in FIG. 3B, and the laser shown in FIG. 3C. With the light irradiation pattern (Comparative Example 1), the separation layer of the laminate was irradiated with laser light, and the state of the laser spot was evaluated.

  In addition, the conditions of laser irradiation in Example 1, Example 2, and Comparative Example 1 are as shown below.

  Further, the conditions for laser beam irradiation to the separation layer were a wavelength of 532 nm, a repetition frequency of 40 kHz, a laser scanning speed of 6500 mm / second, and a laser spot pitch of 180 μm.

(Evaluation of laser light irradiation pattern)
Regarding Example 1, Example 2, and Comparative Example 1 having different laser light irradiation patterns, the state of the laser spot at the measurement points (1) to (5) shown in (a) to (c) of FIG. 3 was evaluated. . The evaluation criteria for the state of the laser spot are those in which the laser spots do not overlap (A), those in which the laser spots slightly overlap but do not damage the wafer substrate (B), and damage the wafer substrate. Evaluation was made as (C).

  As shown in Table 1, in Example 1, as in Comparative Example 1, no overlap of laser spots was observed. From this, according to the irradiation pattern of Example 1, similarly to Comparative Example 1 in which the region not irradiated with the laser beam is not provided, the laser beam is not irradiated on the separation layer without causing overlapping of the laser spot. It has been confirmed that can be provided. In Example 2, the laser spot was slightly overlapped at the measurement point 4, which was the position where the irradiation of the laser beam was once stopped, on the separation layer, but it was not enough to damage the substrate (B). Therefore, according to the irradiation pattern of Example 2, it was confirmed that an unirradiated region of light could be provided inside the outer periphery of the separation layer while avoiding damage to the substrate.

[Evaluation of Separability of Support (First Embodiment)]
Next, as Example 2, Example 3, Comparative Example 3, and Comparative Example 4, the separation performance of the support was evaluated by performing the first preliminary separation step. The separation of the support was evaluated under the same conditions as the laminate used for the evaluation of the light irradiation pattern and the laminate used for the evaluation of the light irradiation pattern except that the thickness of the adhesive layer was changed from 50 μm to 70 μm. The produced laminate was used under the laser light irradiation conditions shown below.

  In the laser beam irradiation in the first preliminary separation step, the irradiation pattern of Example 1 was adopted to form the separation layer region 14a shown in FIG. Here, laminates of Example 3, Example 4, Comparative Example 2, and Comparative Example 3 in which the width W of the region 14a shown in FIG. The laser light irradiation conditions in the first preliminary separation step were a wavelength of 532 nm, a repetition frequency of 40 kHz, a laser scanning speed of 4800 mm / second, and a laser spot pitch of 120 μm.

  Thereafter, the tensile strength in the X direction and the tensile strength in the Y direction shown in FIG. 5 were evaluated. In addition, evaluation of tensile strength used the support body separation apparatus (made by Tokyo Ohka Kogyo Co., Ltd.), and employ | adopted the inside pad of the adsorption part 3mm for the separation plate. Table 2 below shows the evaluation results of the separation of the support.

  As shown in Table 2, in Example 3 where the width W of the region 14a is 2 mm and Example 4 where the width W is 3 mm, the tensile strength in the X direction shown in FIG. 5 is 5 kgf or more, and Y shown in FIG. The tensile strength in the direction was 0.7 kgf or less. On the other hand, in the laminates of Comparative Example 2 and Comparative Example 3, not only the tensile strength in the Y direction was low, but also the tensile strength in the X direction was low. From this, the laminates of Example 3 and Example 4 showing higher tensile strength in the X direction are less likely to be detached from the support in the X direction than the laminates of Comparative Example 2 and Comparative Example 3, and misalignment occurs. It was confirmed that it was difficult to occur.

  Moreover, the laminated body of Example 3 and Example 4 has confirmed that a support body and a wafer substrate could be suitably isolate | separated by applying a low force in the Y direction.

[Evaluation of Separability of Support (Evaluation of Second Preliminary Separation Process)]
Next, as Examples 5 to 8, the laminated body subjected to the first preliminary separation step was subjected to the second preliminary separation step by changing the laser irradiation pitch, and the separation property of the support was evaluated.

  First, the first preliminary separation step was performed on the laminated body having the adhesive layer thickness of 50 μm and the laminated body having the adhesive layer thickness of 70 μm so that the width W of the region 14a was 4 mm. The same conditions as in Example 3 were adopted as the laser beam irradiation conditions in the first preliminary separation step.

  Next, a second preliminary separation step was performed on the region 14a of the stacked body on which the first preliminary separation step was performed. Laser light irradiation conditions in the second preliminary separation step are a wavelength of 532 nm, a repetition frequency of 40 kHz, and a laser scanning speed of 4800 mm / second. The irradiation pitch of the laser spot is as shown in Table 3 below. The evaluation of the separation of the support was performed under the same conditions as in Example 3. The evaluation results are shown in Table 3 below.

  As shown in Table 3, the tensile strength in the X direction was high in the laminates of Examples 5 to 8 in which the second preliminary separation step was performed, and the laminates of Examples 5 to 8 were misaligned with the support in the X direction. We were able to confirm that it was hard to produce. Moreover, in the laminated body of Example 5 and Example 6, it has confirmed that a wafer substrate and a support body were suitably separable by applying force to a Y direction.

  The support separating method according to the present invention can be suitably used, for example, in a manufacturing process of a miniaturized semiconductor device.

10 Laminated body 11 Substrate 12 Support plate (support)
13 Adhesive layer 14 Separation layer 14a Region (separation layer)
14a 'region (separation layer)
14a "region (separation layer)
L light

Claims (10)

The support is separated from the laminate formed by laminating an adhesive layer and a separation layer that changes in quality by absorbing light between the substrate and a support that supports the substrate. A support separating method that comprises:
In the surface of the separation layer facing the support, an unirradiated region of light occupying an area of 0.5% or more and 65% or less of the surface is formed on the separation layer via the support. A support separation method comprising a first preliminary separation step of altering the separation layer by irradiating light.   2. The support separating method according to claim 1, wherein, in the first preliminary separation step, the region is formed inside an outer periphery of a surface of the separation layer facing the support.   3. The support separation method according to claim 1, wherein, in the first preliminary separation step, the region is generated in a portion including a center of gravity of a surface of the separation layer facing the support.   In the first preliminary separation step, the region is formed in a strip shape having a length direction of a line connecting two arbitrary points on the outer periphery of the surface of the separation layer facing the support. Item 2. The support separating method according to Item 1.   The said 1st preliminary separation process WHEREIN: The said area | region is produced in the strip | belt shape which makes the length direction the straight line which passes through the gravity center of the surface which faces the said support body in the said separation layer. Support separation method.   In the first preliminary separation step, the region is formed between the beam spots by adjusting the light irradiation pitch so that the beam spots formed on the separation layer do not overlap each other. Item 6. The support separating method according to any one of Items 1 to 5.   In the first preliminary separation step, the separation layer is altered by scanning light linearly so as to form a locus that does not overlap each other on a surface of the separation layer facing the support. The support separating method according to any one of claims 1 to 6.   After the first preliminary separation step, the method includes a separation step of fixing one of the substrate and the support and separating the substrate and the support by applying a force to the other. The support separating method according to any one of claims 1 to 7. Before the separation step, including a second preliminary separation step of altering the separation layer by irradiating light to the unirradiated region of the light in the separation layer through the support,
9. The support separation method according to claim 8, wherein, in the second preliminary separation step, a light irradiation pitch is 120% or more with respect to the spot diameter of the light. The support separating method according to any one of claims 1 to 9, wherein a width W of the unirradiated region of the light is 2 mm or more and 150 mm or less.

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