JP2014187327A - Method of processing substrate and laminate for temporarily supporting substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To temporarily fix a substrate to a substrate in a more suitable manner.SOLUTION: The method of processing substrate includes: a laminate formation step for forming a laminate 1 formed by laminating a substrate 11, an adhesive layer 13, a separation layer 14, and a support plate 12 in this order; and, after the laminate formation step, a separation step for separating the substrate 11 from the support plate 12. In the laminate formation step, the separation layer 14 on the support plate 12 is covered by the adhesive layer 13.

Description

  The present invention relates to a technique for temporarily fixing a substrate to a support, and relates to a substrate processing method and a substrate for temporary support of a substrate.

  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 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 step is indispensable.

  Since the strength of the wafer substrate is reduced by thinning, a known lithography process or the like is performed while automatically transporting the wafer substrate with the support plate attached to prevent the damage of the thinned wafer substrate during the manufacturing process. Then, a structure such as a circuit is mounted on the wafer substrate. Then, after the manufacturing process, the wafer substrate is separated from the support plate. Therefore, it is preferable that the wafer substrate and the support plate are firmly bonded during the manufacturing process, but it is preferable that the wafer substrate can be smoothly separated from the support plate after the manufacturing process.

  When the wafer substrate and the support plate are firmly bonded, depending on the adhesive material, it is difficult to separate the support plate from the wafer substrate without damaging the structure mounted on the wafer substrate. Therefore, it is a very difficult temporary fixing technology that realizes strong adhesion between the wafer substrate and the support plate during the manufacturing process and separates the elements mounted on the wafer substrate without damaging them after the manufacturing process. Development is required.

  For example, Patent Document 1 describes a technique for bonding a wafer and a holding plate using an adhesive.

  Patent Document 2 describes a technique in which a first substrate and a second substrate are joined with an edge bond lacking a central region, and a filling material is filled in the central region.

  Patent Document 3 describes a technique in which a substrate to be processed is bonded to a support substrate via a photothermal conversion layer and an adhesive layer.

JP 2001-189292 A (released July 10, 2001) Special Table 2011-510518 (published on March 31, 2011) International Publication WO2009 / 142078 Pamphlet (released November 26, 2009)

  In the technique described in Patent Document 1, in order to separate the wafer and the holding plate, it is necessary to remove all the adhesive between the wafer and the holding plate.

  On the other hand, in the technique described in Patent Document 2, in order to separate the first substrate and the second substrate, the edge bond may be removed. However, a complex process is required to form an edge bond that lacks a central area.

  On the other hand, in the technique described in Patent Document 3, in order to separate the support substrate and the substrate to be processed, the photothermal conversion layer may be irradiated with light, and a complicated process is not required for forming the adhesive layer. However, according to the knowledge of the present inventors, when a desired process is performed on the substrate to be processed bonded to the support substrate via the photothermal conversion layer and the adhesive layer, the chemicals used in the process (for example, In some cases, the photothermal conversion layer may be partially denatured and peeled off from the support substrate by a stripping solution such as N-methyl-2-pyrrolidone used in the resist stripping step.

  This invention is made | formed in view of such a problem, and makes it the main objective to provide the technique for temporarily fixing a board | substrate more suitably on a support body.

  In order to solve the above problems, a substrate processing method according to the present invention includes a laminate forming step of forming a laminate in which a substrate, an adhesive layer, a separation layer, and a support are laminated in this order, and the laminate A separation step of separating the substrate from the support after the formation step, wherein the laminate formation step covers the surface of the separation layer on the support with the adhesive layer.

  The temporary support laminate of the substrate according to the present invention is a temporary support laminate of a substrate in which a substrate, an adhesive layer, a separation layer, and a support are laminated in this order, and the support layer is supported by the adhesive layer. The surface of the separation layer is covered.

  According to the present invention, the substrate can be temporarily fixed onto the support more suitably.

It is a figure explaining a part of process of the processing method of the substrate concerning one embodiment of the present invention. It is a figure explaining a part of process of the processing method of the substrate concerning one embodiment of the present invention. It is a figure explaining a part of process of the processing method of the substrate concerning one embodiment of the present invention. It is a figure explaining the laminated body for temporary support of the board | substrate which concerns on one Embodiment of this invention.

<Embodiment 1>
The substrate processing method according to the present invention includes a laminate forming step of forming a laminate in which a substrate, an adhesive layer, a separation layer, and a support are laminated in this order in order to temporarily fix the substrate to the support; And a separation step of separating the substrate from the support after the body formation step. In the laminate formation step, the surface of the separation layer on the support is covered with an adhesive layer.

  That is, in the substrate processing method according to the present invention, the substrate is temporarily fixed to the support by forming a temporary support laminate including the substrate, the adhesive layer, the separation layer, and the support in this order. However, in the temporary support laminate of the substrate, the surface of the separation layer on the support is covered with the adhesive layer.

  Hereinafter, an embodiment (Embodiment 1) of the present invention will be described with reference to the drawings. In Embodiment 1, the case where the support has light permeability and the separation layer is altered by absorbing light irradiated through the support in the laminate will be described.

  As shown in FIGS. 1 and 2, in the first embodiment, the substrate processing method includes a separation layer forming step, a separation layer peripheral edge removing step, an adhesive layer forming step, an adhesive layer peripheral edge removing step, and a laminate formation. 4 includes a step, a separation step, and a cleaning step. As shown in FIG. 4, the laminate (temporary support laminate) 1 formed in the laminate formation step includes a substrate 11, an adhesive layer 13, and a separation The layer 14 and the support plate (support) 12 are laminated in this order.

  In the first embodiment, in the laminate 1 formed by the laminate formation process, the adhesive layer 13 covers the surface of the separation layer 14 on the support plate 12, particularly the outer peripheral portion of the separation layer 14 on the support plate 12. Yes. Therefore, even if a chemical that alters the separation layer 14 when a desired treatment is performed on the substrate 11 temporarily fixed to the support plate 12 using the laminate 1, the separation layer 14 is Since it is protected by the adhesive layer 13, it can be prevented that the separation layer 14 is altered and peeled off from the support plate 12.

[Separation layer forming step]
As shown in (1) and (2) of FIG. 1, the separation layer forming step is a step of forming the separation layer 14 on one surface of the support plate 12.

(Support plate)
The support plate 12 is a support that supports the substrate 11. The support plate 12 tentatively supports the substrate 11 and may have a strength necessary to prevent the substrate 11 from being damaged or deformed during processes such as thinning, transporting, and mounting of the substrate 11. .

  In the first embodiment, the support plate 12 is a light transmissive member. Therefore, when light is irradiated from the outside of the laminate 1 toward the support plate 12, the light passes through the support plate 12 and reaches the separation layer 14. Further, the support plate 12 does not necessarily need to transmit all the light, and it is sufficient if the support plate 12 can transmit the light to be absorbed by the separation layer 14 (having a predetermined wavelength).

  From the above viewpoint, in the first embodiment, the support plate 12 may be made of glass or acrylic resin.

(Separation layer)
In the first embodiment, the separation layer 14 is a layer formed of a material that changes quality by absorbing light irradiated through the support plate 12. In the present specification, the “deterioration” of the separation layer 14 is a phenomenon 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. As a result of the alteration of the separation layer 14 caused by absorbing light, the separation layer 14 loses its strength or adhesiveness prior to receiving light irradiation. Therefore, by applying a slight external force (for example, lifting the support plate 12), the separation layer 14 is broken, and the support plate 12 and the substrate 11 can be easily separated.

  Further, 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 hardening of the separation layer and degassing associated with them). , Contraction or expansion) and the like. The alteration of the separation layer 14 occurs as a result of light absorption by the material constituting the separation layer 14. Therefore, the type of alteration of the separation layer 14 can be changed according to the type of material constituting the separation layer 14.

  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.

  The thickness of the separation layer 14 is more preferably, for example, 0.05 μm or more and 50 μm or less, and further preferably 0.3 μm or more and 1 μm or less. If the thickness of the separation layer 14 is within a range of 0.05 μm or more and 50 μm or less, a desired alteration may be caused in the separation layer 14 by irradiation with light for a short time and irradiation with low energy. it can. 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 1, 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. Accordingly, a layer that imparts desirable properties to the stacked body 1 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.

  As the separation layer 14, a material that forms the separation layer 14 as described below may be used by bonding it to the support plate 12 in advance, or the separation layer 14 may be formed on the support plate 12. You may use what applied the material and solidified in the film form. The method of applying the material constituting the separation layer 14 on the support plate 12 is appropriately selected from conventionally known methods such as chemical vapor deposition (CVD) deposition according to the type of material constituting the separation layer 14. can do.

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, Libby lasers, glass lasers, YVO ₄ lasers, LD lasers, liquid lasers such as fiber lasers, liquid lasers such as dye lasers, CO ₂ lasers, and excimers. Examples thereof include a gas laser such as a 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 support plate 12), the separation layer 14 is broken, and the support plate 12 and the substrate 11 can be easily separated.

From one viewpoint, the fluorocarbon constituting the separation layer 14 can be suitably formed by a plasma CVD method. In addition, fluorocarbon includes C _x F _y (perfluorocarbon) and C _x H _y F _z (x, y, and z are integers), and is not limited thereto, but, for example, CHF ₃ , CH ₂ F ₂ , C ₂ It can be H ₂ F ₂ , C ₄ F ₈ , C ₂ F ₆ , C ₅ F ₈ or the like. Further, an inert gas such as nitrogen, helium and argon, a hydrocarbon such as alkane and alkene, and oxygen, carbon dioxide and hydrogen are added to the fluorocarbon used for constituting the separation layer 14 as necessary. May be. A mixture of a plurality of these gases may be used (a mixed gas of fluorocarbon, hydrogen, nitrogen, etc.). Further, the separation layer 14 may be composed of a single type of fluorocarbon, or may be composed of two or more types of fluorocarbon.

  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 laser such as a solid laser such as a YAG laser, Libby laser, glass laser, YVO ₄ laser, LD laser, or fiber laser, or a dye laser, depending on the wavelength that can be absorbed by the fluorocarbon. 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 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), 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, 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 1” in (a) to (e)). Yes, in formula (f), which is any one of the formulas shown in the above “Chemical Formula 1” or is 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 1” 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 has a substituent, the substituent is, for example, alkyl, aryl, halogen atom, alkoxy, nitro, aldehyde, cyano, amide, dialkylamino, sulfonamide, imide, carboxylic acid, carboxylic acid Selected from esters, sulfonic acids, sulfonate esters, alkylamino and arylamino.

Of the substituents represented by “Chemical Formula 1” 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.

  Of the substituents represented by “Chemical Formula 1” 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.

  Among the substituents represented by the above “Chemical Formula 1”, 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 1, 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 100 nm or more and 2000 nm or less. Within this range, the wavelength of light that can be absorbed by the structure is on the shorter wavelength side, and is, for example, 100 nm or more and 500 nm or less. For example, the structure can alter the polymer containing the structure by absorbing ultraviolet light, preferably having a wavelength of about 300 nm or more and 370 nm or less.

  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). , XeCl laser (wavelength: 308 nm), XeF laser (wavelength: 351 nm) or light emitted from a 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 made of an inorganic material, 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), 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, can use 1 or more types of inorganic substances selected from the group which consists of a metal, a metal compound, and carbon suitably. The metal compound refers to a compound containing a metal atom, and can be, for example, a metal oxide or a metal nitride. Exemplary of such inorganic 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, Libby laser, glass laser, YVO ₄ laser, LD laser, or fiber laser, or a dye laser depending on the wavelength that the inorganic material can absorb. For example, a liquid laser such as a CO ₂ laser, an excimer laser, an Ar laser, a He—Ne laser, or 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 substance is not particularly limited as long as it is a film thickness that can sufficiently absorb the light to be used. For example, a film thickness 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 these problems by providing an antireflection film or an antistatic film on the upper or lower side 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 adhesion 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 and alkenes (vinyl, trans, cis, vinylidene, trisubstituted, tetrasubstituted, conjugated, cumulene, ring Formula), alkyne (monosubstituted, disubstituted), monocyclic aromatic (benzene, monosubstituted, disubstituted, trisubstituted), alcohol and phenols (free OH, intramolecular hydrogen bond, intermolecular hydrogen bond, saturated Secondary, saturated tertiary, unsaturated secondary, unsaturated tertiary), acetal, ketal, aliphatic ether, aromatic ether, vinyl ether, oxirane ether, peroxide ether, ketone, dialkylcarbonyl, aromatic Carbonyl, 1,3-diketone enol, o-hydroxy aryl ketone, dialkyl aldehyde, aromatic aldehyde, carboxylic acid (dimer Carboxylate 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, Acid ester, nitrite ester, nitroso bond (aliphatic, aromatic, monomer, dimer), mercaptan and sulfur compounds such as thiophenol and thiolic acid, thiocarbonyl group, sulfoxide, sulfone, sulfonyl chloride, primary Secondary sulfonamide, secondary sulfonamide, sulfate ester, carbon-halogen bond, Si-A ¹ bond (A ¹ is H, C, O or halogen), P-A 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 the like SiF ₃ and the like. As a structure including a Si—A ¹ bond, it is particularly preferable to form a siloxane skeleton and a silsesquioxane skeleton.

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— P—O (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 a 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 solidified to form a solid layer. As long as it is possible, there is no particular limitation. 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 (1) and a repeating unit represented by the following chemical formula (2), or A resin that is a copolymer of a repeating unit represented by the following chemical formula (1) and a repeating unit derived from an acrylic compound can be used.

(In the chemical formula (2), 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, t-butylstyrene (TBST) -dimethylsiloxane copolymer, which is a copolymer of a repeating unit represented by the above chemical formula (1) and a repeating unit represented by the following chemical formula (3), is used. A polymer is more preferable, and a TBST-dimethylsiloxane copolymer containing a repeating unit represented by the above formula (1) and a repeating unit represented by the following chemical formula (3) at 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 (4) and a repeating unit represented by the following chemical formula (5) can be used. .

(In chemical formula (4), R ⁴ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and in chemical formula (5), R ⁵ is an alkyl group having 1 to 10 carbon atoms, or a phenyl group. .)
As other compounds having a silsesquioxane skeleton, Patent Document 4: JP 2007-258663 A (published October 4, 2007), Patent Document 5: JP 2010-120901 A (2010). Published on June 3, 2009), Patent Document 6: JP 2009-263316 A (published on November 12, 2009) and Patent Document 7: JP 2009-263596 A (published on November 12, 2009). Each of the disclosed silsesquioxane resins can be suitably used.

  Among these, as the compound having a silsesquioxane skeleton, a repeating unit represented by the following chemical formula (6) and a copolymer of repeating units represented by the following chemical formula (7) are more preferable. A copolymer containing 7: 3 of the repeating unit represented by the following chemical formula (7) is more preferred.

  The polymer having a silsesquioxane skeleton may have a random structure, a ladder structure, and a cage structure, but 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) chelating titanium such as di-i-propoxy bis (acetylacetonato) titanium, and propanedioxytitanium bis (ethylacetoacetate); (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 - _titanium polymers such as _{n -n-C 4 H 9;} (iv) tri -n- butoxy titanium monostearate, titanium stearate, di -i- propoxycarbonyl Xylitanium diisostearate and acylate titanium such as (2-n-butoxycarbonylbenzoyloxy) tributoxytitanium; (v) water-soluble titanium compounds such as di-n-butoxybis (triethanolaminato) titanium Etc.

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 prevent or promote the absorption of infrared rays by the above structure and the 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), 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.

[Separation layer peripheral edge removal step]
As shown in (3) of FIG. 1, the separation layer peripheral edge removing step forms the periphery of the separation layer 14 on the support plate 12 after forming the separation layer 14 on one side of the support plate 12 in the separation layer forming step. This is a step of removing the end portion. As a result, the separation layer 14 is laminated on the inner peripheral portion of the support plate 12, and the surface of the separation layer 14 on the support plate 12, particularly the support plate 12 of the separation layer 14, in a later laminated body forming step. The upper peripheral portion can be suitably covered with the adhesive layer 13. That is, in the laminated body forming process, when the substrate 11 and the support plate 12 are bonded to each other, the separation layer 14 can enter more inside than the opposing adhesive layer 13.

  In particular, in the laminate 1, the width of the adhesive layer 13 covering the outer peripheral portion of the separation layer 14 on the support plate 12 is 300 μm or more and 2000 μm or less, more preferably 300 μm or more and 500 μm or less. It is desirable to previously remove the peripheral end of the.

  When the width of the adhesive layer 13 that covers the outer peripheral portion of the separation layer 14 on the support plate 12 is 300 μm or more, the separation layer 14 can be suitably protected. Moreover, since the amount of the adhesive layer 13 that covers the outer peripheral portion on the support plate 12 to be removed in the separation step is reduced when the width is 2000 μm or less, the separation step can be performed quickly.

  A known method may be used as a method for removing the peripheral end portion of the separation layer 14 on the support plate 12, and is not particularly limited. For example, a peeling solution is sprayed on the peripheral end portion of the separation layer 14. Alternatively, the stripping solution may be supplied to the peripheral end portion of the separation layer 14 using a dispensing nozzle. Further, the stripping solution may be sprayed and supplied while rotating the support plate 12.

(Stripping solution)
The stripping solution applied to the separation layer 14 may be any solution that can remove the separation layer 14.

  The stripping solution is more preferably an alkaline solution. More preferably, the alkaline solution is an amine compound. As the amine compound, at least one compound selected from the group consisting of primary, secondary, and tertiary aliphatic amines, alicyclic amines, aromatic amines, and heterocyclic amines is used. be able to.

  Examples of the primary aliphatic amine include monomethanolamine, monoethanolamine (MEA), monoisopropanolamine, ethylenediamine, 2- (2-aminoethoxy) ethanol (DGA), and 2- (2-aminoethylamino) ethanol. Etc. Examples of secondary aliphatic amines include 2- (methylamino) ethanol (MMA), diethanolamine, iminobispropylamine, and 2-ethylaminoethanol. Examples of tertiary aliphatic amines include triethanolamine, triisopropanolamine, and diethylaminoethanol.

  Examples of alicyclic amines include cyclohexylamine and dicyclohexylamine. Examples of the aromatic amine include benzylamine, dibenzylamine, N-methylbenzylamine and the like. Examples of the heterocyclic amine include N-hydroxyethylpiperidine and 1,8-diazabicyclo [5,4,0] -7-undecene. Of these organic amine compounds, alkanolamines such as monoethanolamine, 2- (2-aminoethoxy) ethanol and 2-ethylaminoethanol, 2- (methylamino) ethanol (MMA) are particularly suitable.

  Further, the stripping solution may be used by mixing with other solvents. Examples of the solvent that may be mixed with the stripping solution described above include polar solvents such as N-methyl-2-pyrrolidone (NMP), lactones such as γ-butyrolactone, acetone, methyl ethyl ketone, cyclohexanone, and methyl-n-pentyl. Ketones, ketones such as methyl isopentyl ketone, 2-heptanone, polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene An organic solvent of a compound having an ester bond such as glycol monoacetate, and the monomethyl ether of the polyhydric alcohol or the compound having an ester bond. Derivatives of polyhydric alcohols such as monoalkyl ethers such as benzene, monoethyl ether, monopropyl ether, monobutyl ether or compounds having an ether bond such as monophenyl ether, cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), organic solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate and the like, anisole, ethylbenzyl ether, cresylmethyl Ether, diphenyl ether, dibenzyl ether, phenetol, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene, etc. An aromatic organic solvent is mentioned.

  In addition, the solvent that may be mixed with the above-described stripping solution is preferably at least one selected from polyhydric alcohols, compounds having an ester bond, or derivatives of polyhydric alcohols among them, diethylene glycol monomethyl ether, Triethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monobutyl ether, propylene glycol monopropyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoisobutyl ether, diethylene glycol dimethyl ether, propylene glycol monoethyl Ether, propylene glycol monomethyl ether (P ME), butyl diglycol, at least one selected from propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monoethyl ether acetate is more preferable.

  The mixing ratio of the alkaline solution and the solvent that may be mixed with the stripping solution is preferably 9: 1 to 1: 9, more preferably 8: 2 to 2: 8, by weight. preferable.

  Note that the support plate 12 may be washed with water or alcohol having 1 to 6 carbon atoms after removing the peripheral end portion of the separation layer 14 with the stripping solution. Thereby, it is possible to prevent the stripping solution (for example, containing amines) remaining on the support plate 12 from corroding the substrate 11.

[Adhesive layer forming step]
As shown in (4) and (5) of FIG. 1, the adhesive layer forming step is a step of forming the adhesive layer 13 on the surface of the substrate 11 on the side facing the support plate 12 in the laminate 1. Note that the adhesive layer forming step may be performed before the separating layer forming step and the separating layer peripheral edge removing step, may be performed later, or may be performed in parallel.

(substrate)
The substrate 11 is subjected to processes such as thinning and mounting in a state where the substrate 11 is supported by the support plate 12 (a state in which the laminated body 1 is configured). In one embodiment, the substrate 11 is a wafer, but the substrate included in the laminate according to the present invention is not limited to a wafer, and any substrate such as a thin film substrate or a flexible substrate can be adopted. Further, a fine structure of an electronic element such as an electric circuit may be formed on the surface of the substrate 11 on the adhesive layer 13 side.

(Adhesive layer)
The adhesive layer 13 adheres and fixes the substrate 11 to the support plate 12 and the separation layer 14. Further, the adhesive layer 13 may cover and protect the surface of the substrate 11.

  As a method for forming the adhesive layer 13, an adhesive may be applied to the substrate 11, or an adhesive tape having an adhesive applied on both sides may be attached. 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.

  The thickness of the adhesive layer may be set as appropriate according to the types of the substrate 11 and the support plate 12 to be attached, the treatment applied to the substrate 11 after being attached, etc., but within the range of 10 to 150 μm. It is preferable that it is within a range of 15 to 100 μm.

  As the adhesive, for example, various adhesives known in the art such as acrylic, novolak, naphthoxan, hydrocarbon, polyimide, and elastomer are used as the adhesive constituting the adhesive layer 13 according to the present invention. Is possible. Below, the composition of resin which the contact bonding layer 13 in this Embodiment contains is demonstrated.

  The resin contained in the adhesive layer 13 is not particularly limited as long as it has adhesiveness, 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, a cycloolefin polymer (hereinafter sometimes referred to as “resin (A)”), and at least one resin selected from the group consisting of a terpene resin, a rosin resin and a petroleum resin (hereinafter referred to as “the 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, and tetracyclododecene. Tetracycles, pentacycles such as cyclopentadiene trimer, heptacycles such as tetracyclopentadiene, or alkyl (methyl, ethyl, propyl, butyl, etc.) substituted or alkenyl (vinyl, etc.) Examples include substituted, alkylidene (such as ethylidene) substituted, aryl (such as phenyl, tolyl, naphthyl) substituted, and the like. Among these, norbornene-based monomers selected from the group consisting of norbornene, tetracyclododecene, and alkyl-substituted products thereof are 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, and α-olefin. 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 point (Tg) of the resin (A) is preferably 60 ° C. or higher, and particularly preferably 70 ° C. or higher. When the glass transition point of the resin (A) is 60 ° C. or higher, softening of the adhesive layer 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 molecular weight of resin (B) is not specifically limited, It is preferable that it is 300-3000. When the 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 molecular weight of the resin (B) is 3000 or less, the peeling rate when peeling the laminate is good. In addition, the 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). It is preferable because of excellent resistance and flexibility.

(Acrylic-styrene resin)
Examples of the acryl-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 whose 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. Males having an aliphatic hydrocarbon group such as maleimide having an alkyl group, N-cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, N-cyclooctylmaleimide Resin obtained by polymerizing aromatic maleimide having an aryl group such as imide, N-phenylmaleimide, Nm-methylphenylmaleimide, N-o-methylphenylmaleimide, Np-methylphenylmaleimide, etc. It is done.

  For example, a cycloolefin copolymer, which is a copolymer of a repeating unit represented by the following chemical formula (8) and a repeating unit represented by the following chemical formula (9), can be used as the adhesive component resin.

(In the chemical formula (9), 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, it is easy for a 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 in the above ranges, a resist solvent (eg, PGMEA, PGME, etc.), acid (hydrofluoric acid) exposed when the wafer is subjected to a resist lithography process. Etc.) and excellent resistance to 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 are 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. be able to. 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). , Ethylene-propylene terpolymer (EPT) 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- in which the styrene block is reactively crosslinked Tylene-propylene-styrene block copolymer (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.) )) And the like, and the content of the styrene unit and the weight average molecular weight are in the above-mentioned range.

  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.

  As a commercial item which can be used as an elastomer contained in the adhesive composition according to the present invention, for example, “Septon (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 composition according to the present invention is, for example, preferably 50 parts by weight or more and 99 parts by weight or less, based on 100 parts by weight of the total amount of the adhesive composition, and 60 parts by weight or more and 99 parts by weight. Part or less is more preferable, and 70 parts by weight or more and 95 parts by weight or less is most preferable. By setting it as these ranges, a wafer and a support body can be bonded together suitably, maintaining heat resistance.

  A plurality of types of elastomers may be mixed. That is, the adhesive composition according to the present invention 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 in the range of 10,000 or more and 200,000 or less. If so, it is within the scope of the present invention. Moreover, in the adhesive composition which concerns on this invention, when several types of elastomer is included, as a result of mixing, you may adjust so that content of a styrene unit may become said range. 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 on a one-to-one basis, the styrene content with respect to the total elastomer contained in the adhesive composition 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 on a one-to-one basis, the result is 35% by weight, which is within the above range. The present invention may be in such a form. Moreover, it is most preferable that the plurality of types of elastomers contained in the adhesive composition according to the present invention all contain styrene units in the above range and have a weight average molecular weight in 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). This is because the photocurable resin may remain as a residue around the minute irregularities of the substrate 11 after the adhesive layer 13 is peeled or removed. In particular, an adhesive that dissolves in a specific solvent is preferable as a material constituting the adhesive layer 13. 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)
As a diluting solvent for forming the separation layer and the adhesive layer, for example, hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, tridecane, etc., straight chain hydrocarbons, C 4-15 branch Hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, tetrahydronaphthalene and the like, p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpine, 1,8-terpine, bornin, norbornane, pinan, tujang, karan, longifolene, geraniol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, te Pinen-1-ol, terpinen-4-ol, dihydroterpinyl acetate, 1,4-cineole, 1,8-cineole, borneol, carvone, yonon, thuyon, camphor, d-limonene, l-limonene, dipentene, etc. A terpene-based solvent; 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 glycol, Polyhydric alcohols such as dipropylene glycol; ester bonds such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate A compound having an ether bond, a monoalkyl ether such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or a monophenyl ether of a compound having an ester bond, or a compound having an ether bond. 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; Jill 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 adhesive layer 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.

[Adhesive layer peripheral edge removal step]
As shown in FIG. 1 (6), in the adhesive layer peripheral edge removing step, the adhesive layer 13 is formed on one surface of the substrate 11 in the adhesive layer forming step, and then the peripheral edge portion of the adhesive layer 13 on the substrate 11 is formed. This is a step of removing. Thereby, when the board | substrate 11 and the support plate 12 are bonded together in a later laminated body formation process, it can suppress suitably that the contact bonding layer 13 protrudes from the laminated body 1. FIG.

  In one example, when the film thickness of the adhesive layer 13 is 50 μm, for example, the circumference of the adhesive layer 13 on the substrate 11 is 2 mm or less, preferably 0.5 mm or more and 0.8 mm or less from the peripheral edge of the substrate. It is preferable to remove the ends. Thereby, it can suppress suitably that the contact bonding layer 13 protrudes from the laminated body 1 in a laminated body formation process.

  As a method for removing the adhesive layer 13 formed on the peripheral edge portion on the substrate 11, a known method may be used, and is not particularly limited. For example, a solution is sprayed on the peripheral edge portion of the adhesive layer 13. Alternatively, the solution may be supplied to the peripheral end portion of the separation layer 14 using a dispensing nozzle. Further, spraying, supplying, etc. of the solution may be performed while rotating the substrate 11.

  The solution for the adhesive layer 13 may be appropriately selected according to the type of adhesive, and is not particularly limited. For example, the solvent used as the above-described dilution solvent can be used. And cyclic hydrocarbons (terpenes) such as branched hydrocarbons having 4 to 15 carbon atoms, monoterpenes and diterpenes can be preferably used.

[Laminated body formation process]
As shown in FIG. 1 (7), in the laminated body forming step, the substrate 11 and the support plate 12 having the separation layer 14 formed on the inner periphery thereof are bonded together via the adhesive layer 13. This is a step of forming a laminate 1 in which the substrate 11, the adhesive layer 13, the separation layer 14, and the support plate 12 are laminated in this order. In the laminated body forming step, bonding is performed so that the surface of the separation layer 14 on the support plate 12, particularly the outer peripheral portion of the separation layer 14 on the support plate 12 is covered with the adhesive layer 13. The surface of the separation layer 14 on the support plate 12 refers to a portion of the surface of the separation layer 14 excluding the area covered with the support plate 12.

  A method for attaching the substrate 11 and the support plate 12 is not particularly limited. For example, even if the surface of the substrate 11 on which the adhesive layer 13 is formed and the surface of the support plate 12 on which the separation layer 14 is formed are pressed against each other. Good. In one example, the substrate 11 and the support plate 12 that are stacked so that the adhesive layer 13 and the separation layer 14 face each other may be sandwiched by a pair of heated plate members in a reduced pressure environment.

  At this time, in the separation layer peripheral edge removing step, the separation layer 14 is adjusted in advance so as to be smaller than the adhesive layer 13, and the separation layer 14 is opposed to the inner peripheral portion of the adhesive layer 13, By pressing the substrate 11 and the support plate 12 together, the surface of the separation layer 14 on the support plate 12 can be easily covered with the adhesive layer 13.

  As described above, in the laminated body forming step, the substrate 11, the adhesive layer 13, the separation layer 14 and the support plate 12 are laminated in this order as shown in FIG. 4, and the separation layer 14 on the support plate 12 is formed by the adhesive layer 13. A laminate (a temporary support laminate) can be formed.

  In the laminate 1, the surface of the separation layer 14 on the support plate 12, in particular, the outer peripheral portion of the separation layer 14 on the support plate 12 is covered with the adhesive layer 13. Even if a chemical that alters the separation layer 14 when a desired treatment is performed on the substrate 11 temporarily fixed to the support plate 12, the separation layer 14 is protected by the adhesive layer 13. Therefore, it is possible to prevent the separation layer 14 from being altered and peeled off from the support plate 12. Thereby, the generation | occurrence | production of the crack and crack to a wafer resulting from the separation layer 14 peeling in the middle of a process, and an unevenness | corrugation can be prevented.

  As described above, in the laminate 1, the width of the adhesive layer 13 that covers the outer peripheral portion of the separation layer 14 on the support plate 12 is 300 μm or more and 2000 μm or less, more preferably 300 μm or more and 500 μm or less. Is preferred. When the width of the adhesive layer 13 that covers the outer peripheral portion of the separation layer 14 on the support plate 12 is 300 μm or more, the separation layer 14 can be suitably protected. Moreover, since the said width | variety is 2000 micrometers or less, since the quantity of the contact bonding layer 13 which covers the outer peripheral part on the support plate 12 which should be removed in a subsequent separation process decreases, a subsequent separation process can be performed rapidly. it can.

[Separation process]
After performing desired processing on the laminate 1 (the substrate 11 thereof), a separation step is performed. As shown in (1) to (4) of FIG. 2, the separation step is a step of separating the substrate 11 from the stacked body 1 (or the support plate 12).

  In the first embodiment, the separation step includes the removal of the adhesive layer 13 covering the outer peripheral portion of the separation layer 14 on the support plate 12 shown in (2) of FIG. 2, and the support plate 12 shown in (3) of FIG. The separation layer 14 is irradiated with light via.

(Removal of adhesive layer)
In the laminate 1, the adhesive layer 13 that covers the outer peripheral portion of the separation layer 14 on the support plate 12 directly bonds the substrate 11 and the support plate 12 (see FIG. 4). 2, it is necessary to remove the adhesive layer 13 covering the outer peripheral portion of the separation layer 14 on the support plate 12 as shown in FIG.

  The method for removing the adhesive layer 13 is not particularly limited. For example, a known dry or wet method such as plasma treatment may be used. As a wet type method, a solution for dissolving the above-described adhesive layer 13 may be sprayed on the adhesive layer 13 covering the outer peripheral portion of the separation layer 14 on the support plate 12, or a dispensing nozzle may be used. A solution may be supplied, or the laminate 1 may be immersed in the solution. Note that spraying, supplying, etc. of the solution may be performed while rotating the substrate 11.

  In addition, when the laminated body 1 is immersed in a solution, it is preferable that the substrate 11 is not separated from the support plate 12 during the immersion. Therefore, it is preferable to irradiate the separation layer 14 with light through the support plate 12 after the removal of the adhesive layer 13 covering the outer peripheral portion of the separation layer 14 on the support plate 12. This is because the substrate 11 and the support plate 12 are bonded via the separation layer 14 and the adhesive layer 13 before the light irradiation.

(Light irradiation)
In the laminate 1, the portion where the substrate 11 and the support plate 12 are bonded via the adhesive layer 13 and the separation layer 14 is separated via the support plate 12 as shown in FIG. By irradiating the layer 14 with light, the separation layer 14 can be altered and separated.

  That is, the separation layer 14 is altered by light irradiation, and the separation layer 14 is destroyed by applying a slight force (for example, lifting the support plate 12). Therefore, the support plate 12 and the substrate 11 can be easily separated by performing both the removal of the adhesive layer and the light irradiation described above.

  In addition, what is necessary is just to select suitably the wavelength of the light to irradiate with the kind of separation layer 14, as mentioned above. In addition, although the light irradiation method is not particularly limited, it is preferable to irradiate light over the entire separation layer 14. For example, laser light may be scanned over the entire separation layer 14.

[Washing process]
As shown in FIG. 2 (5), the substrate 11 separated from the support plate 12 may be cleaned after the separation step. For example, you may wash | clean so that the contact bonding layer 13 and the separation layer 14 which remain | survived on the board | substrate 11 may be removed using the solution etc. which were mentioned above. The cleaning method is not particularly limited, and a known cleaning method may be used.

<Modification>
In the separation layer forming step, if the separation layer can be formed to a desired size, the separation layer peripheral edge removing step can be omitted. Similarly, in the adhesive layer forming step, if the adhesive layer can be formed to a desired size, the adhesive layer peripheral edge removing step can be omitted.

  Moreover, in the laminated body 1, when the width | variety of the contact bonding layer 13 which covers the outer peripheral part on the support plate 12 of the isolation | separation layer 14 is slight, you may abbreviate | omit the removal of the adhesive agent in a isolation | separation process. Even in this case, the support plate 12 and the substrate 11 can be separated by applying a slight pulling force after the separation layer 14 is altered by light irradiation.

  Further, the substrate processing method according to the present invention includes forming a laminate in which the substrate, the adhesive layer, the separation layer, and the support are laminated in this order in the laminate forming step, and the adhesive layer forms the laminate on the support. Any method can be used as long as it covers the surface of the separation layer, and the method is not limited to the method described in the first embodiment. For example, after forming the adhesive layer on the support side (separation layer 14 side), the laminate may be formed by attaching the substrate to the support.

<Embodiment 2>
Next, another embodiment (Embodiment 2) of the present invention will be described with reference to the drawings. In Embodiment 2, the case where the separation layer has releasability from the adhesive layer will be described. The substrate processing method according to the second embodiment is similar to the first embodiment in the separation layer forming step, the separation layer peripheral edge removing step, the adhesive layer forming step, the adhesive layer peripheral edge removing step, the laminate forming step, and the separation step. And a washing step. Hereinafter, members similar to those of the first embodiment are denoted by the same member numbers, and description thereof is omitted. The adhesive layer forming step, the adhesive layer peripheral edge removing step, and the cleaning step may be performed in the same manner as in the first embodiment.

[Separation layer forming step]
In the second embodiment, in the separation layer forming step, a separation layer 14 ′ having releasability from the adhesive layer 13 is formed on the support plate 12 ′. In the present specification, “the separation layer 14 ′ has releasability with respect to the adhesive layer 13” means that the substrate 11 and the support plate 12 ′ are laminated via the adhesive layer 13 and the separation layer 14 ′. Sometimes, the adhesive layer 13 and the separation layer 14 ′ can be separated without damaging the substrate 11 and the support plate 12 ′ without removing the adhesive layer 13.

  In the second embodiment, as the support plate 12 ′, the support plate having the light transmittance described in the first embodiment can be used, or a support plate that does not transmit light may be used. That is, as the material of the support plate 12 ′, a material that does not transmit light, such as silicon, can be used in addition to a material made of glass, acrylic resin, or the like.

  As a material of the separation layer 14 ′, a known release agent can be used, and examples thereof include, but are not limited to, a fluorine release agent, a silicone release agent, an amide wax, a carnauba wax, and a palm wax. Examples thereof include waxes such as vegetable waxes, paraffin waxes, petroleum waxes such as petrolactam, synthetic waxes such as polyethylene waxes, and polyvinyl alcohol. Moreover, if the adhesiveness with respect to the contact bonding layer 13 is low, the fluorine-type coating etc. which are used as an antireflection film can also be used. These may be used by diluting or dispersing in a solvent.

  The separation layer 14 ′ can be formed by applying the above-described material onto the support plate 12 by, for example, a spin coating method, a dipping method, a roller blade method, a doctor blade method, a spray method, or a slit nozzle method. In addition, a release film such as a film coated with film-like polytetrafluoroethylene or silicone resin may be attached to the support plate 12.

  For example, the thickness of the separation layer 14 ′ is more preferably 1 μm or more and 10 μm or less, and further preferably 2 μm or more and 5 μm or less.

  Further, like the separation layer 14 in the first embodiment, the separation layer 14 ′ may be formed in a desired size in the separation layer forming step, or after the separation layer forming step, the separation layer peripheral edge removing step may be performed. You may adjust the size by going.

[Laminated body formation process]
In the stacked body forming step, the substrate 11 and the support plate 12 can be bonded together as in the first embodiment. Thereby, in the laminated body forming step, the substrate 11, the adhesive layer 13, the separation layer 14 ′, and the support plate 12 ′ are laminated in this order, and the surface of the separation layer 14 ′ on the support plate 12 ′ is formed by the adhesive layer 13. A covered laminate (substrate provisional support laminate) 1 ′ can be formed.

  Thus, the substrate 11 and the support plate 12 are bonded by the adhesive layer 13 that covers the outer peripheral portion of the separation layer 14 ′ on the support plate 12, and the adhesive layer 13 and the separation layer 14 can be easily separated. A laminated body 1 'can be formed. That is, in the laminated body 1 ′, the substrate 11 can be separated from the support plate 12 simply by removing the adhesive layer 13 that covers the outer peripheral portion of the separation layer 14 ′ on the support plate 12. In the laminate 1 ′, the adhesive layer 13 can be easily formed because it is not necessary to lack the central region.

  In the laminate 1 ′, the width of the adhesive layer 13 that covers the outer peripheral portion of the separation layer 14 ′ on the support plate 12 is preferably 100 μm or more and 2000 μm or less, more preferably 300 μm or more and 500 μm or less. In addition, since the width is 500 μm or less, the amount of the adhesive layer 13 covering the outer peripheral portion on the support plate 12 to be removed in the subsequent separation step is reduced, so that the subsequent separation step can be performed quickly. it can.

[Separation process]
The separation process in Embodiment 2 is shown in (1) to (3) of FIG. As shown in (1) and (2) of FIG. 3, in the second embodiment, the adhesive layer 13 covering the outer peripheral portion of the separation layer 14 ′ on the support plate 12 ′ is removed. A method similar to that of the first embodiment can be used as a method of removing the adhesive layer 13.

  Then, when the adhesive layer 13 covering the outer peripheral portion of the separation layer 14 ′ on the support plate 12 ′ is removed, the separation layer 14 ′ itself has a releasability with respect to the adhesive layer 13, so that FIG. As shown in 3), the substrate 11 and the support plate 12 'can be separated without the need to apply an external 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.

[Example 1]
(process)
Under the conditions of a flow rate of 400 sccm, a pressure of 70 Pa, a high frequency power of 2,800 W, and a film formation temperature of 240 ° C., a fluorocarbon film (thickness 1 μm) as a separation layer is supported by a CVD method using C ₄ F ₈ as a reaction gas. It was formed on a (12-inch glass substrate, thickness 700 μm) (separation layer forming step).

  Next, while the support is rotated (1500 rpm, 40 seconds), a stripping solution consisting of PGME / MMA = 7/3 (weight ratio) is supplied (10 cc / min) by the EBR nozzle, whereby the peripheral edge on the support The fluorocarbon membrane formed to a width of 0.5 to 1 mm was removed (separation layer peripheral edge removal step). Thereafter, spin drying (1500 rpm, 40 seconds) was performed.

  Next, TZNR (registered trademark) -A3007t (manufactured by Tokyo Ohka Kogyo Co., Ltd.), which is an adhesive composition, is spin-coated on a 12-inch silicon wafer and heated at 100 ° C., 160 ° C., and 200 ° C. for 3 minutes each. An adhesive layer (film thickness 50 μm) was formed (adhesive layer forming step).

  Next, while rotating the silicon wafer, the EBR nozzle supplies TZNR (registered trademark) HC thinner (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at a supply rate of 20 cc / min. The raised portion of the adhesive layer) was removed (adhesive layer peripheral edge removal step).

  Next, the support and the silicon wafer were bonded to each other under a vacuum of 220 ° C. and 4,000 kg for 3 minutes to form a laminate (laminate formation step).

  An average output 3 of the laser beam with the laser beam wavelength of 532 nm, the laser beam diameter of 180 μm, the center-to-center distance between the irradiated regions in the laser pulse of 180 μm, the scanning speed of 7200 mm / s is applied to the laminate. Laser light irradiation was performed at a repetition frequency of 40 kHz (light irradiation).

(Separation evaluation)
After the separation step by removing the adhesive and irradiating with light, it was not necessary to apply any force, and the support could be easily separated from the laminate.

[Example 2]
(process)
Under the conditions of a flow rate of 400 sccm, a pressure of 70 Pa, a high frequency power of 2,800 W, and a film formation temperature of 240 ° C., a fluorocarbon film (thickness 1 μm) as a separation layer is supported by a CVD method using C ₄ F ₈ as a reaction gas. It was formed on a (12-inch glass substrate, thickness 700 μm) (separation layer forming step).

  Next, while the support is rotated (1500 rpm, 40 seconds), a stripping solution consisting of PGME / MMA = 7/3 (weight ratio) is supplied (10 cc / min) by the EBR nozzle, whereby the peripheral edge on the support The fluorocarbon membrane formed to a width of 0.5 to 1 mm was removed (separation layer peripheral edge removal step). Thereafter, spin drying (1500 rpm, 40 seconds) was performed.

  Next, TZNR (registered trademark) -A3007t (manufactured by Tokyo Ohka Kogyo Co., Ltd.), which is an adhesive composition, is spin-coated on a 12-inch silicon wafer and heated at 100 ° C., 160 ° C., and 200 ° C. for 3 minutes each. An adhesive layer (film thickness 50 μm) was formed (adhesive layer forming step).

  Next, while rotating the silicon wafer, by supplying TZNR (registered trademark) HC thinner (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at a supply rate of 20 cc / min by the EBR nozzle, an edge bead on the silicon wafer (wafer peripheral portion) (Swelled part of the adhesive layer) was removed (adhesive layer peripheral edge removing step).

  Next, the support and the silicon wafer were bonded to each other under a vacuum of 220 ° C. and 4,000 kg for 3 minutes to form a laminate (laminate formation step).

(Separation process)
By rotating the above laminate at 1500 rpm and supplying TZNR (registered trademark) HC thinner (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at a supply rate of 10 cc / min for 5 to 15 minutes with an EBR nozzle. The adhesive layer formed up to a width of 0.5 to 1 mm at the peripheral edge was removed (removal of adhesive).

  An average output 3 of the laser beam with the laser beam wavelength of 532 nm, the laser beam diameter of 180 μm, the center-to-center distance between the irradiated regions in the laser pulse of 180 μm, the scanning speed of 7200 mm / s is applied to the laminate. Laser light irradiation was performed at a repetition frequency of 40 kHz (light irradiation).

(Separation evaluation)
After the separation step by removing the adhesive and irradiating with light, it was not necessary to apply any force, and the support could be easily separated from the laminate.

Example 3
(process)
Under the conditions of a flow rate of 400 sccm, a pressure of 70 Pa, a high frequency power of 2,800 W, and a film formation temperature of 240 ° C., a fluorocarbon film (thickness 1 μm) as a separation layer is supported by a CVD method using C ₄ F ₈ as a reaction gas. It was formed on a (12-inch glass substrate, thickness 700 μm) (separation layer forming step).

  Next, while the support is rotated (1500 rpm, 40 seconds), a stripping solution consisting of PGME / MMA = 7/3 (weight ratio) is supplied (10 cc / min) by the EBR nozzle, whereby the peripheral edge on the support The fluorocarbon membrane formed to a width of 0.5 to 1 mm was removed (separation layer peripheral edge removal step). Thereafter, spin drying (1500 rpm, 40 seconds) was performed.

  Next, TZNR (registered trademark) -A3007t (manufactured by Tokyo Ohka Kogyo Co., Ltd.), which is an adhesive composition, is spin-coated on a 12-inch silicon wafer and heated at 100 ° C., 160 ° C., and 200 ° C. for 3 minutes each. An adhesive layer (film thickness 50 μm) was formed (adhesive layer forming step).

  Next, the support and the silicon wafer were bonded to each other under a vacuum of 220 ° C. and 4,000 kg for 3 minutes to form a laminate (laminate formation step).

  Next, while rotating the laminated body, TZNR (registered trademark) HC thinner (manufactured by Tokyo Ohka Kogyo Co., Ltd.) is supplied at a supply rate of 20 cc / min by the EBR nozzle, whereby the peripheral width on the silicon wafer is reduced to 0. The adhesive layer formed up to 5 mm was removed (removal of adhesive).

  An average output 3 of the laser beam with the laser beam wavelength of 532 nm, the laser beam diameter of 180 μm, the center-to-center distance between the irradiated regions in the laser pulse of 180 μm, the scanning speed of 7200 mm / s is applied to the laminate. Laser light irradiation was performed at a repetition frequency of 40 kHz (light irradiation).

(Separation evaluation)
After the separation step by removing the adhesive and irradiating with light, it was not necessary to apply any force, and the support could be easily separated from the laminate.

  The present invention can be suitably used, for example, in the field of manufacturing miniaturized semiconductor devices.

1,1 'laminate (substrate provisional support laminate)
11 Substrate 12 Support plate (support)
13 Adhesive layer 14 Separation layer

Claims (9)

A laminate forming step of forming a laminate in which a substrate, an adhesive layer, a separation layer, and a support are laminated in this order;
A separation step of separating the substrate from the support after the laminate formation step,
In the laminated body forming step, the surface of the separation layer on the support is covered with the adhesive layer.   2. The substrate according to claim 1, wherein in the laminated body forming step, the substrate and the support body on which the separation layer is laminated on an inner periphery thereof are bonded together via the adhesive layer. Processing method. Before the laminate formation step, a separation layer formation step of forming the separation layer on the support,
A separation layer peripheral edge removing step of removing the peripheral edge of the separation layer on the support after the separation layer forming step and before the laminate forming step. Item 3. A substrate processing method according to Item 2.   3. The adhesive layer forming step of forming the adhesive layer on the surface of the substrate on the side facing the support in the laminated body before the laminated body forming step. 4. The method for processing a substrate according to 3.   5. The adhesive layer peripheral edge removing step of removing the peripheral edge portion of the adhesive layer on the substrate after the adhesive layer forming step and before the laminate forming step. The processing method of the board | substrate of description. The support has light permeability,
The separation layer is altered in the laminate by absorbing light irradiated through the support,
6. The separation step includes removing an adhesive layer covering an outer peripheral portion of the separation layer on the support, and irradiating the separation layer with light through the support. The substrate processing method according to any one of the above.   The said isolation | separation process WHEREIN: After the removal of the contact bonding layer which covers the outer peripheral part on the said support body of the said separation layer, light irradiation with respect to the said separation layer through the said support body is performed. Substrate processing method. The separation layer has releasability from the adhesive layer,
6. The substrate processing method according to claim 1, wherein in the separation step, an adhesive layer covering an outer peripheral portion of the separation layer on the support is removed. The substrate, the adhesive layer, the separation layer, and the support are laminated bodies in this order, and a temporary support laminate of the board,
A laminate for temporary support of a substrate, wherein the surface of the separation layer on the support is covered with the adhesive layer.

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