JP6162976B2 - Substrate processing method - Google Patents

Description

  The present invention relates to a substrate processing method.

  In recent years, electronic devices such as IC cards and mobile phones have been required to be thinner, smaller, and lighter. In order to satisfy these requirements, a thin semiconductor chip must be used as a semiconductor chip to be incorporated. For this reason, the thickness (film thickness) of the 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. For this reason, it takes time to separate the wafer from the holding plate without damaging it.

  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, in order to prevent the edge bond from being damaged during the manufacturing process, it is necessary to increase the width of the edge bond provided at the outer edge of the wafer. As a result, a large force is required to separate the wafer and the carrier wafer.

  Also in the technique described in Patent Document 3, a technique for more easily separating the support substrate and the substrate to be processed is required.

  The present invention has been made in view of such a problem, and more easily separates a support and a substrate from a laminate obtained by laminating a substrate, an adhesive layer, and a support in this order. The main purpose is to provide this technology.

  In order to solve the above-described problems, a substrate processing method according to the present invention includes a cooling step for cooling a laminated body in which a substrate, an adhesive layer, and a support are laminated in this order, and after the cooling step. And a support separating step of separating the support from the cooled laminate.

  According to the present invention, there is an effect that a laminated body formed by laminating a substrate, an adhesive layer, and a support in this order can be efficiently separated by the substrate and the support.

It is a figure explaining one Embodiment of each process to a laminated body formation process among the processes included by the processing method of the board | substrate which concerns on this invention. It is a figure explaining one Embodiment of a separation process among the processes included by the processing method of the substrate concerning the present invention.

<Substrate processing method>
Hereinafter, an embodiment of a substrate processing method according to the present invention will be described with reference to FIGS. 1 and 2. FIG. 1 is a diagram for explaining an embodiment of each process up to a laminate forming process among the processes included in the substrate processing method according to the present invention. FIG. 2 is a diagram for explaining an embodiment of the separation step among the steps included in the substrate processing method according to the present invention.

  1 includes a separation layer formation step ((1) and (2) in FIG. 1), a separation layer peripheral edge removal step ((3) in FIG. 1), and an adhesive layer formation. The process ((4) and (5) of FIG. 1) and the laminated body formation process ((6) of FIG. 1) are included.

  The laminated body 1 formed by the above process moves to the separation process of FIG. 2 after performing a desired treatment.

  Each process up to the adhesive removing process shown in FIG. 2 includes a light irradiation process ((1) and (2) in FIG. 2), a cooling process ((3) in FIG. 2), and a support separating process (( 4)), and an adhesive removing step ((5) in FIG. 2).

[Separation layer forming step]
As shown in FIGS. 1A and 1B, the separation layer forming step is a step of forming the separation layer 14 on one side of the support plate 12.

(Support plate)
The support plate 12 is a support body that supports the substrate 11 and has optical transparency. 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).

  Further, the support plate 12 supports the substrate 11 and may have a strength necessary for preventing the substrate 11 from being damaged or deformed during processes such as thinning, transporting, and mounting of the substrate 11. From the above viewpoint, examples of the support plate 12 include those made of glass, silicon, and 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 adhesion prior to receiving light irradiation.

  Further, the alteration of the separation layer 14 includes decomposition (exothermic or non-exothermic), cross-linking, configuration change or dissociation of functional groups (and curing of the separation layer accompanying these, degassing). , 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 short-time light irradiation and low-energy light irradiation. 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 gas lasers such as lasers, Ar lasers, and He—Ne lasers, laser beams such as semiconductor lasers and free electron lasers, and non-laser beams. 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), but is not limited to these, 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, diphenyl sulfoxide structure, diphenyl sulfone structure (bisphenyl sulfone structure), diphenyl structure or diphenylamine structure present in the side chain of the polymer.

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

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

(In the formula, l is an integer of 1 or more, m is 0 or an integer of 1 to 2, and X is any one of the formulas shown in the above “Chemical Formula 1” in (a) to (e)). Yes, in formula (f), which is any one of the formulas shown above in “Chemical Formula 1” or does not exist, 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, alkylaminos and arylaminos.

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 can be mentioned.

  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 composed of an inorganic substance, and is thereby altered by absorbing light. As a result, the separation layer 14 loses strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, lifting the support plate 12), the separation layer 14 is broken, and the support plate 12 and the substrate 11 can be easily separated.

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

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

The light applied to the separation layer 14 made of an inorganic material may be, for example, a solid-state laser such as a YAG laser, 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 them by providing an antireflection film or an antistatic film on the upper and lower sides of the separation layer 14 or one of them.

(Compound having infrared absorbing structure)
The separation layer 14 may be formed of a compound having an infrared absorbing structure. The compound is altered by absorbing infrared rays. The separation layer 14 has lost its strength or adhesiveness before being irradiated with infrared rays as a result of the alteration of the compound. Therefore, by applying a slight external force (for example, lifting the support), the separation layer 14 is broken, and the support plate 12 and the substrate 11 can be easily separated.

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

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

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

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

  The said structure can absorb the infrared rays which have the wavelength of a desired range by selection of the kind. Specifically, the wavelength of infrared rays that can be absorbed by the above structure is, for example, in the range of 1 μm or more and 20 μm or less, and more preferably in the range of 2 μm or more and 15 μm or less. Furthermore, in the case where the structure is a Si—O bond, a Si—C bond, or a Ti—O bond, it may be in the range of 9 μm or more and 11 μm or less. In addition, those skilled in the art can easily understand the infrared wavelength that can be absorbed by each structure. For example, as an absorption band in each structure, Non-Patent Document: SILVERSTEIN / BASSLER / MORRILL, “Identification method by spectrum of organic compound (5th edition) —Combination of MS, IR, NMR and UV” (published in 1992) The description on page 146 to page 151 can be referred to.

  As 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, a t-butylstyrene (TBST) -dimethylsiloxane copolymer, which is a copolymer of the repeating unit represented by the chemical formula (1) and the 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) in a ratio of 1: 1 is further preferable.

  Moreover, as the compound having a silsesquioxane skeleton, for example, a resin that is a copolymer of a repeating unit represented by the following chemical formula (4) and a repeating unit represented by the following chemical formula (5) can be used. .

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

  Among them, as the compound having a silsesquioxane skeleton, a repeating unit represented by the following chemical formula (6) and a copolymer of a repeating unit represented by the following chemical formula (7) are more preferable. More preferably, the copolymer contains a repeating unit represented by the following chemical formula (7) and a repeating unit represented by the following chemical formula (7) at 7: 3.

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

Examples of the compound containing a Ti-O bond include (i) tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, and titanium-i-propoxyoctylene glycolate. (ii) di -i- propoxy bis (acetylacetonato) titanium, and chelate titanium such as propane di oxytitanium bis (ethylacetoacetate); alkoxy titanium such as _{(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- Puropokishichi Tandiisostearate and acylate titanium such as (2-n-butoxycarbonylbenzoyloxy) tributoxytitanium; (v) water-soluble titanium compounds such as di-n-butoxy-bis (triethanolaminato) titanium Can be mentioned.

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

  Although the separation layer 14 described above contains a compound having an infrared absorbing structure, the separation layer 14 may further contain a component other than the above compound. Examples of the component include a filler, a plasticizer, and a component that can improve the peelability of the support plate 12. These components are appropriately selected from conventionally known substances or materials that do not interfere with or promote infrared absorption by the above structure and alteration of the compound.

(Infrared absorbing material)
The separation layer 14 may contain an infrared absorbing material. The separation layer 14 is configured to contain an infrared absorbing material, so that the separation layer 14 is altered by absorbing light. As a result, the strength or adhesiveness before receiving the light irradiation is lost. Therefore, by applying a slight external force (for example, lifting the support plate 12), 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.

(Surrounding edge separation layer removal process)
In the peripheral edge separation layer removing step included in the substrate processing method according to the present embodiment, the separation layer 14 is formed on one surface of the support plate 12 in the separation layer forming step, as shown in FIG. This is a step of removing the peripheral end portion of the separation layer 14 on the support plate 12 later. 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 the peripheral edge separation layer removing step, the separation layer existing in the range of 0.3 mm or more and 2 mm or less, more preferably 0.3 mm or more and 1 mm or less from the outer periphery of the support plate is removed. In other words, in this embodiment, 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 0.3 mm or more and 2 mm or less, more preferably 0.3 mm or more. It is desirable to remove in advance the peripheral end of the separation layer 14 so that the thickness is 1 mm or less.

  If the width from the outer periphery to the inner side of the support plate 12 from which the separation layer 14 is removed is 0.3 mm or more, the separation layer 14 can be suitably covered with the adhesive layer 13 in the subsequent laminated body forming step. Moreover, if the said width | variety is 2 mm or less, when the contact bonding layer 13 is cooled in the subsequent cooling process, the support plate 12 can be easily isolate | separated by the fall of the adhesive force. Moreover, in the substrate processing method according to the present invention, the adhesive layer 13 is directly present on the support plate 12 without the separation layer 14 in the above range because the adhesive layer 13 is reduced in adhesive force by performing the cooling process. Even so, the support plate 12 can be preferably separated from the substrate 11.

  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 used for removing the peripheral end portion of 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. Among these organic amine compounds, monoethanolamine, 2- (2-aminoethoxy) ethanol, 2-ethylaminoethanol, 2- (methylamino) ethanol (MMA), and other alkanolamines 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 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, ethyl benzyl ether, cresyl methyl ether , Aromatics such as diphenyl ether, dibenzyl ether, phenetol, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene Based organic solvents.

  Moreover, as a solvent that may be mixed with the above-described stripping solution, among these, at least one selected from polyhydric alcohols, compounds having an ester bond, or derivatives of polyhydric alcohols is preferable, 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 (PG E), butylene glycol, 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. The adhesive layer forming step may be performed before the separation layer forming step and the peripheral edge separation layer removing step, may be performed after, 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. Further, as shown in FIG. 2A, the adhesive layer 13 is laminated on the support plate 12 so as to cover the separation layer 14.

  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 depending on 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.

  Moreover, you may remove the peripheral edge part on the board | substrate 11 of the contact bonding layer 13 by the width | variety of the range of 2 mm or less from the peripheral edge of a board | substrate, Preferably it is 0.5 mm or more and 0.8 mm or less. Thus, when removing a peripheral edge part, the film thickness of the contact bonding layer 13 should just be about 50 micrometers, for example. Thereby, it can suppress suitably that the contact bonding layer 13 protrudes from the laminated body 1 in a laminated body formation process.

  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.

  The glass transition temperature (Tg) of the adhesive varies depending on the type and molecular weight of the resin, and a compound such as a plasticizer for the adhesive. The type and molecular weight of the resin contained in the adhesive can be appropriately selected according to the type of the substrate and the support, but the Tg of the resin used for the adhesive is in the range of −60 ° C. or higher and 200 ° C. or lower. The inside is preferable, and the inside of the range of −25 ° C. or higher and 150 ° C. or lower is more preferable. By being -25 degreeC or more and 150 degrees C or less, the adhesive force of the contact bonding layer 13 can be reduced suitably, without requiring excessive energy for cooling. Moreover, you may adjust Tg of the adhesive agent 13 by mix | blending a plasticizer, resin of a low polymerization degree, etc. suitably.

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

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

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

  Examples of the cycloolefin monomer contained in the monomer component constituting the resin (A) include bicyclic compounds such as norbornene and norbornadiene, tricyclic compounds such as dicyclopentadiene and dihydroxypentadiene, and tetracyclododecene. Tetracycles, pentacycles such as cyclopentadiene trimer, heptacycles such as tetracyclopentadiene, or polycyclic alkyl (methyl, ethyl, propyl, butyl, etc.) substituted alkenyls (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 particularly preferable.

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

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

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

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

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

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

  The glass transition temperature (Tg) of the resin (A) is preferably 60 ° C. or higher, and particularly preferably 70 ° C. or higher. When the glass transition temperature of the resin (A) is 60 ° C. or higher, softening of the adhesive layer 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). Since it is excellent in tolerance and flexibility, it is preferable.

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

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

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

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

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

(Maleimide resin)
Examples of maleimide resins include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, N-sec as monomers. -Butylmaleimide, N-tert-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide, N-laurylmaleimide, N-stearylmaleimide, etc. 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 resin of the adhesive component.

(In 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). And hydrogenated products thereof, styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (styrene-isoprene-styrene block copolymer) (SEPS), styrene-ethylene-ethylene- Propylene-styrene block copolymer (SEEPS), styrene-ethylene-ethylene-propylene-styrene block copolypropylene in which styrene block is reactively crosslinked -(Septon V9461 (manufactured by Kuraray Co., Ltd.)), a styrene block having a reactive crosslinking type styrene-ethylene-butylene-styrene block copolymer (Septon V9827 (manufactured by Kuraray Co., Ltd.) having a reactive polystyrene hard block), etc. The styrene unit content and the weight average molecular weight are in the above-mentioned ranges.

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

  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 contain a plurality of types of elastomers. It is sufficient that at least one of the plurality of types of elastomers includes a styrene unit as a constituent unit of the main chain. Further, at least one of the plurality of types of elastomers has a styrene unit content in the range of 14 wt% or more and 50 wt% or less, or a weight average molecular weight 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 at a weight ratio of 1: 1, it becomes 35% by weight and falls within the above range. The present invention may be in such a form. Moreover, it is most preferable that the plurality of types of elastomers contained in the adhesive 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 polyvalent compound such as a compound having an ether bond such as a monoalkyl ether such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether of a compound having a polyhydric alcohol or the ester bond Derivatives of 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), acetic acid Esters such as methyl, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; anisole, ethylbenzyl Ether, cresyl methyl ether, diphenyl ether, can be mentioned dibenzyl ether, phenetole, the aromatic organic solvent such as butyl phenyl ether.

(Other ingredients)
The adhesive constituting the 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.

[Laminated body formation process]
As shown in FIG. 1 (6), in the laminate forming process, 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 the 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 peripheral edge separation layer 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, The substrate 11 and the support plate 12 are pressed against each other. Thereby, 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 shown in FIG. 2A are laminated in this order, and the separation on the support plate 12 is performed by the adhesive layer 13. The laminate 1 in which the surface of the layer 14 is covered can be formed.

  In the laminate 1, 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. Thus, even when 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. Therefore, it is possible to prevent the wafer from being cracked or broken and the occurrence of irregularities due to the separation layer 14 being peeled off during the processing. In particular, in the substrate processing method according to the present invention, the adhesive force of the adhesive layer 13 can be reduced by performing the cooling step, and therefore the width of the adhesive layer 13 covering the outer peripheral portion of the separation layer 14 on the support plate 12. Can be afforded. Accordingly, the separation layer 14 can be more suitably protected by the adhesive layer 13.

[Light irradiation process]
As shown in (2) of FIG. 2, the light irradiation step is a step of altering the separation layer 14 by irradiating the separation layer 14 with light through the support plate 12. By irradiating the separation layer 14 with light, the separation layer 14 is easily destroyed. For this reason, the laminated body 1 maintains the adhesiveness between the support plate 12 and the substrate 11 only by the adhesive layer 13 covering the outer peripheral portion of the separation layer 14. For this reason, the support plate 12 can be easily separated from the laminate 1 by reducing the adhesive force of the adhesive layer 13 in the subsequent cooling step.

  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.

[Cooling process]
The cooling process included in the substrate processing method according to the present embodiment is a process of cooling the stacked body. As a cooling process, the cooling method by the liquid nitrogen 20 as shown to (3) of FIG. 2 can be mentioned, for example. Here, in the cooling step, it is sufficient that at least the adhesive layer 13 is cooled, and it is not necessary to immerse the entire laminate 1 in the liquid nitrogen 20.

  The adhesive containing the thermoplastic resin as described above used for the adhesive layer 13 tends to vary depending on the value of the glass transition temperature (Tg) specific to each adhesive, but in the case of using any adhesive In addition, the adhesive strength of the adhesive layer 13 can be reduced by performing the cooling step.

In the cooling process, the adhesive layer 13 may be cooled as much as possible. If even a little, it will be easy to peel off because the adhesive strength decreases. Further, the adhesive layer 13 may be cooled so that the adhesive strength is preferably 2.0 kgf / cm ² or less, more preferably 1.5 kgf / cm ² or less. For example, when an adhesive having a Tg of room temperature (23 ° C.) or higher is used for the adhesive layer 13, the adhesive layer 13 tends to gradually decrease in adhesive strength with cooling. In the case of such an adhesive, the adhesive strength of the adhesive layer 13 can be lowered by setting the conditions for the cooling step to a temperature at which the adhesive strength is 2.0 kgf / cm ² or less in advance. Accordingly, the support plate 12 can be easily separated from the stacked body 1 in the subsequent support separating process.

In addition, the adhesive strength of the adhesive layer varies depending on the material of the substrate and the support, in addition to the type of adhesive. For this reason, what is necessary is just to adjust cooling conditions so that adhesive strength may be 2.0 kgf / cm < ² > or less according to the conditions of a board | substrate, a support body, and an adhesive agent.

Moreover, when using the adhesive agent with Tg lower than normal temperature, the adhesive strength of these adhesive agents will fall more notably when it cools below Tg. For this reason, in the case of an adhesive whose Tg is lower than room temperature, the adhesive strength of the adhesive layer 13 can be further reduced by cooling to a temperature equal to or lower than Tg. The Tg of the adhesive varies depending on the type and molecular weight of the thermoplastic resin used and the composition of the plasticizer, but can be measured by a known method such as differential scanning calorimetry. By such a method, first, Tg of the adhesive to be used is measured, and according to the measurement result of Tg of each adhesive, the adhesive strength is 2.0 Kgf / cm ² or less, or the adhesive Tg or less. It may be determined which cooling condition of the temperature is set.

  Although the cooling method in a cooling process will not be specifically limited if the laminated body 1 can be cooled, For example, the cooling method by the refrigeration or freezing air-conditioning equipment using various refrigerant | coolants, and a coolant like liquid nitrogen, liquid helium, or dry ice It can be cooled by a cooling method. When cooling with a coolant such as liquid nitrogen, as shown in FIG. 2 (3), the laminate 1 may be placed in a container containing the coolant, and conventionally known in the case of using refrigeration or refrigeration air conditioning equipment. The laminate 1 may be stored in a freezer or the like. Further, a Peltier cooling method can also be used. These cooling processes may be performed by a cooling device provided in the substrate processing apparatus, or may be performed by a cooling device different from the substrate processing apparatus.

  By performing the cooling step, the adhesive strength of the adhesive layer 13 can be reduced to about 1/10 compared with the case of normal temperature. For this reason, in the processing of the wafer substrate, it is possible to remove the separation layer formed at the peripheral end portion of the separation layer 14 formed on the support plate 12 and increase the adhesion surface between the adhesion layer 13 and the support plate 12. it can. That is, even if the adhesion between the substrate 11 and the support plate 12 is improved, the substrate 11 and the support plate 12 can be easily separated in the support separating process by performing the cooling process.

[Support Separation Process]
The support separating process included in the substrate processing method according to this embodiment is a process of separating the support plate from the stacked body after the cooling process, as shown in FIG. In the support separating process, the support plate 12 can be separated from the laminate 1 by fixing both the substrate 11 and the support plate 12 and applying a tensile stress to the laminate 1.

  Since the adhesive strength of the adhesive layer 13 is reduced by the cooling process, the support plate 12 can be easily separated from the laminate 1 by applying a slight tensile stress. Therefore, it is not necessary to perform an operation requiring mechanical accuracy such as applying a shear stress by a blade or the like to the adhesive layer 13 having a thickness of about 10 to 150 μm between the substrate 11 and the support plate 12.

  Furthermore, in the conventional substrate processing method that does not perform the cooling step, the substrate and the support plate are separated by cohesive failure of the adhesive layer in the support separating step. For this reason, a large amount of adhesive layers remained on both the substrate and the support plate after the support plate separation step. On the other hand, in the substrate processing method according to the present invention, the adhesive layer 13 is cooled in the cooling step to reduce the adhesiveness of the adhesive layer 13, thereby separating the interface between the support plate 12 and the adhesive layer 13. Made possible. Further, also on the substrate 11, the remaining adhesive layer 13 can be easily peeled off. Therefore, the amount of the adhesive layer 13 remaining on the substrate 11 and the support plate 12 after the support separating process can be reduced.

[Adhesive removal process]
The adhesive removing step included in the substrate processing method according to the present embodiment is a step of removing the adhesive from the substrate after the support separating step, as shown in FIG. Similarly, the adhesive can be removed from the support plate.

  In the adhesive removing step, the substrate 11 separated from the support plate 12 is washed using the above-described solution so as to remove the remaining adhesive layer 13 and separation layer 14.

  The cleaning can be performed by spraying a solution on the substrate 11. Further, the substrate 11 after the separation step can also be cleaned by immersing it in a solution.

  The adhesive layer 13 of the laminated body 1 that has undergone the cooling step can be separated from the interface with the support plate 12 as described above. Moreover, since the adhesive strength of the adhesive layer 13 is lowered, it is easy to remove the adhesive layer 13 from the substrate 11. For this reason, the residue of the adhesive layer 13 on the substrate 11 and the support plate 12 can be reduced, the cleaning time in the adhesive removing step can be shortened, and the amount of the solution used can be reduced.

  Examples will be shown below, and the embodiments of the present invention will be described in more detail. Of course, the present invention is not limited to the following examples, and it goes without saying that various aspects are possible in detail. Further, the present invention is not limited to the above-described embodiments, and various modifications can be made within the scope shown in the claims, and the present invention is also applied to the embodiments obtained by appropriately combining the disclosed technical means. It is included in the technical scope of the invention. Moreover, all the literatures described in this specification are used as reference.

[Example 1]
(Preparation of adhesive)
100 parts by weight of various adhesive resins described in Table 1 below were dissolved in 800 parts by weight of decahydronaphthalene as a main solvent. Next, a butyl acetate solution containing a thermal polymerization inhibitor IRGANOX 1010 (manufactured by BASF) was prepared and added so that IRGANOX 1010 was 1 part by weight and butyl acetate was 20 parts by weight with respect to 100 parts by weight of the adhesive resin. In this way, an adhesive composition was obtained.

The adhesive resin used for each sample is as follows.
APL8008T: made by Mitsui Chemicals, Inc., cycloolefin copolymer, ethylene: tetracyclododecene = 80: 20 copolymer Septon (trade name) 2002: made by Kuraray Co., Ltd., SEPS: polystyrene-poly (ethylene / isoprene) block-polystyrene Septon (Trade name) 8007: manufactured by Kuraray Co., Ltd., SEBS: polystyrene-poly (ethylene / butylene) block-polystyrene tuftec (trade name) H1051: manufactured by Asahi Kasei Corporation, SEBS: hydrogenated styrene thermoplastic elastomer A1: styrene / di Cyclopentanyl methacrylate / stearyl methacrylate copolymer (composition ratio 20/60/20 (molar ratio), molecular weight 30,000)
(Sample preparation)
Each adhesive composition according to each sample was spin-coated on a semiconductor wafer substrate (Si). Subsequently, each layer was baked at 90 ° C., 160 ° C., and 220 ° C. for 4 minutes to form an adhesive layer on the substrate. The film thickness of the adhesive layer was set to 50 μm. A sample for evaluation was prepared by bonding to a glass support having a diameter of 10 mm at 220 ° C. for 3 minutes under vacuum.

  Each sample was immersed in liquid nitrogen for 10 seconds, and after being confirmed to be cooled to −80 ° C. by an infrared thermometer, the sample was taken out from liquid nitrogen. Then, adhesive strength measurement and separability evaluation were performed, and compared with the case where it evaluated on normal temperature (23 degreeC) conditions.

(Adhesive strength and separability evaluation)
The sample prepared as described above was pulled at a speed of 10 mm / s in the direction perpendicular to the semiconductor wafer substrate, thereby measuring the adhesive strength (Kgf / cm ² ).

  For evaluation of separability, a force was applied by hand, and an easily peeled piece was evaluated as “◯”, and an unexfoliated piece was evaluated as “x”.

(Evaluation results)
Table 1 shows the evaluation results of Samples 1 to 5 when cooled to −80 ° C. and at normal temperature. When cooled to −80 ° C., Sample 1 using an adhesive having a Tg higher than normal temperature had an adhesive strength reduced to about 1/10 compared to the adhesive strength at normal temperature (23 ° C.). Moreover, also in the samples 2-5 using the adhesive agent whose Tg is lower than normal temperature, when it cools to -80 degreeC (temperature lower than Tg of each adhesive resin), adhesive strength is approximately from the case of normal temperature (23 degreeC). It decreased to about 1/10. In the evaluation of separability, the samples that could not be peeled by hand at normal temperature in any of Samples 1 to 5 could be easily separated by cooling to -80 ° C.

[Example 2]
(Preparation of adhesive)
An adhesive was prepared using the following adhesive resin using a solvent and a thermal polymerization inhibitor so as to satisfy the same conditions as in Example 1.

The adhesive resin used for each sample is as follows.
APL8008T: made by Mitsui Chemicals Co., Ltd., cycloolefin copolymer, ethylene: tetracyclododecene = 80: 20 copolymer hybrid (trade name) 7125: made by Kuraray Co., Ltd., vinyl SEPS: polystyrene-poly (ethylene / isoprene) block Polystyrene Hibler (trade name) 5125: manufactured by Kuraray Co., Ltd., vinyl SEPS: polystyrene-poly (ethylene / isoprene) block-polystyrene S.P. O. E. 605L: Asahi Kasei Corporation, hydrogenated styrene / butadiene copolymer elastomer (sample preparation)
Each adhesive composition according to each sample was spin-coated on a semiconductor wafer substrate (Si). Subsequently, each layer was baked at 90 ° C., 160 ° C., and 220 ° C. for 4 minutes to form an adhesive layer on the substrate. The film thickness of the adhesive layer was set to 50 μm. A sample for evaluation was prepared by bonding to a glass support having a diameter of 10 mm at 220 ° C. for 3 minutes under vacuum.

  Each sample was frozen in a freezer for 1 hour, taken out from the freezer after confirming that it was cooled to -25 ° C with an infrared thermometer. Then, adhesive strength measurement and separability evaluation were performed, and compared with the case where it evaluated on normal temperature (23 degreeC) conditions. In addition, the method of adhesive strength and separability evaluation is the same as Example 1.

(Evaluation results)
Table 1 shows the evaluation results of Samples 6 to 9 when cooled to −25 ° C. and at normal temperature. When cooled to −25 ° C., Samples 6 and 9 using an adhesive having a Tg higher than normal temperature had an adhesive strength reduced to about 1/10 compared to the adhesive strength at normal temperature (23 ° C.). . Also, in Samples 2 to 5 using an adhesive whose Tg is lower than normal temperature, when cooled to -25 ° C (temperature lower than Tg of each adhesive resin), the adhesive strength is approximately higher than that at normal temperature (23 ° C). It decreased to about 1-9 to 1/12. Further, in the evaluation of separability, in any of Samples 6 to 9, those that could not be peeled by hand at normal temperature could be easily separated by cooling to -25 ° C.

[Separation evaluation]
(process)
Under the conditions of a flow rate of 400 sccm, a pressure of 700 mTorr, a high frequency power of 2,500 W, and a film forming 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 (12-inch glass substrate, thickness 700 μm). Next, while the support is rotated, a stripping solution of NMP (N-methyl-2-pyrrolidone) / MMA (2- (methylamino) ethanol) = 7/3 (weight ratio) is supplied by the EBR nozzle. Thus, the fluorocarbon film formed to a width of 1 mm at the peripheral edge on the support was removed (peripheral edge separation layer removing step). 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 was formed (film thickness 50 μm), and the substrate was bonded to the above support for 3 minutes under vacuum at 220 ° C. and 4,000 kg to obtain a laminate.

  Similarly, S. O. E. A laminate was prepared using the same adhesive as Sample 9 containing 605L (Asahi Kasei Co., Ltd.).

  The above two types of laminates have a laser beam wavelength of 532 nm, a laser beam diameter of 180 μm, a center-to-center distance between irradiated regions in a laser pulse of 180 μm, a scanning speed of 7200 mm / s, and an average output of laser beam 3 Laser light irradiation was performed at a repetition frequency of 40 kHz. Then, each laminated body was frozen in the freezer for 1 hour, and it confirmed that it was cooled to -25 degreeC with the infrared thermometer (cooling process).

(Separation evaluation)
A laminate using TZNR (registered trademark) -A3007t; O. E. In any of the laminated bodies using 605L, it was not necessary to apply a force, and the support body could be separated from the laminated body by the weight of the silicon wafer. Moreover, in each laminated body, it isolate | separated in the interface of a support body and an adhesive layer, and the residue of the adhesive agent on a support body was hardly recognized.

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

1 Laminated body 11 Substrate 12 Support plate (support)
13 Adhesive layer 14 Separation layer 20 Liquid nitrogen

Claims (7)

A cooling step for cooling a laminate formed by laminating a substrate, an adhesive layer, and a support in this order;
A support separating step for separating the support from the cooled laminate after the cooling step, and
The adhesive layer contains at least one of a cycloolefin polymer and an elastomer containing a styrene unit as a main chain constituent unit,
In the cooling step, the laminated body is adhered to the adhesive layer of the laminated body by a cooling method using a refrigeration or refrigeration air conditioning equipment using a solvent, or a cooling method using a coolant of liquid nitrogen, liquid helium or dry ice. A method for treating a substrate, comprising cooling to a glass transition temperature of the layer or lower and -25 ° C or lower .   2. The substrate processing method according to claim 1, wherein the support includes a separation layer on a surface on which the adhesive layer is laminated.   The substrate processing method according to claim 2, wherein the adhesive layer is laminated on the support so as to cover the separation layer. 4. The substrate processing method according to claim 1, wherein, in the cooling step, the adhesive layer is cooled until the adhesive strength becomes 2.0 kgf / cm ² or less. 5.   The substrate processing method according to claim 2, further comprising a peripheral edge separation layer removing step of removing the separation layer present at the peripheral edge of the support before performing the cooling step. 6. The substrate processing method according to claim 5 , wherein, in the peripheral edge separation layer removing step, the separation layer existing in a range of 2 mm or less inward from the outer periphery of the support is removed. After the support separating step, from the substrate on which the support is separated, according to any one of claims 1 to 6, characterized in that further include an adhesive removing step of removing the adhesive layer Substrate processing method.

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