WO2014050820A1 - 積層体、積層体の分離方法、および分離層の評価方法 - Google Patents

積層体、積層体の分離方法、および分離層の評価方法 Download PDF

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WO2014050820A1
WO2014050820A1 PCT/JP2013/075722 JP2013075722W WO2014050820A1 WO 2014050820 A1 WO2014050820 A1 WO 2014050820A1 JP 2013075722 W JP2013075722 W JP 2013075722W WO 2014050820 A1 WO2014050820 A1 WO 2014050820A1
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separation layer
light
substrate
laser
laminate
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PCT/JP2013/075722
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English (en)
French (fr)
Japanese (ja)
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高瀬　真治
松下　淳
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東京応化工業株式会社
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Priority to JP2014538496A priority Critical patent/JP6261508B2/ja
Publication of WO2014050820A1 publication Critical patent/WO2014050820A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B01D1/14—Evaporating with heated gases or vapours or liquids in contact with the liquid

Definitions

  • the present invention relates to a laminate, a method for separating a laminate, and a method for evaluating a separation layer.
  • the thickness (film thickness) of the wafer substrate on which the semiconductor chip is based is currently 125 ⁇ m to 150 ⁇ m, but it is said that it must be 25 ⁇ m to 50 ⁇ m 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.
  • the circuit on the wafer substrate is automatically transferred while the support plate is bonded to the wafer substrate during the manufacturing process in order to prevent damage to the thinned wafer substrate. Etc. are mounted. 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.
  • Patent Document 1 As a semiconductor chip manufacturing method in which a support is bonded to a semiconductor wafer, the semiconductor wafer is processed, and then the support is separated, a method as described in Patent Document 1 is known.
  • a light-transmitting support and a semiconductor wafer are bonded together via a photothermal conversion layer and an adhesive layer provided on the support, and the semiconductor wafer is processed and then supported.
  • the photothermal conversion layer is decomposed, and the semiconductor wafer is separated from the support.
  • the present invention has been made in view of the above-described problems.
  • the substrate and the support are easily bonded by light irradiation after the manufacturing process while realizing strong adhesion between the substrate and the support during the manufacturing process.
  • the main purpose is to provide a technique for separating and suitably preventing adverse effects of light on the substrate surface.
  • a laminate according to the present invention includes a substrate, an adhesive layer, a separation layer that is altered by absorbing light, and a light transmissive support in this order. It is a laminate, and the OD value of the separation layer is 0.20 or more and 1.00 or less.
  • the separation method of the laminate according to the present invention includes a substrate, an adhesive layer, a separation layer having an OD value of 0.20 or more and 1.00 or less and denatured by absorbing light, and a light transmitting property. And a support for separating the laminated body laminated in this order, wherein a repetition frequency and an average output value set from the OD value are set to the separation layer via the support.
  • the method includes an irradiation step of irradiating a laser beam, and a separation step of separating the substrate and the support after the irradiation step.
  • the evaluation method of the separation layer according to the present invention is a separation of a laminate in which a substrate, an adhesive layer, a separation layer that is altered by absorbing light, and a light-transmitting support are laminated in this order.
  • a method for evaluating a separation layer for evaluating a layer, comprising a measurement step of measuring an OD value of the separation layer.
  • the substrate and the support are firmly bonded during the manufacturing process, the substrate and the support are easily separated by light irradiation after the manufacturing process, and the substrate is irradiated with light. It has the effect of preventing adverse effects.
  • a laminate according to an embodiment of the present invention is a laminate in which a substrate, an adhesive layer, a separation layer that is altered by absorbing light, and a light-transmissive support are laminated in this order.
  • the OD value of the separation layer is from 0.20 to 1.00.
  • the supported substrate, the adhesive layer, the separation layer, and the support are laminated in this order, and the supported substrate is temporarily fixed to the support via the adhesive layer and the separation layer. Has been.
  • the laminated body which concerns on this embodiment is demonstrated. If the laminated body of this embodiment is used as a laminated body which temporarily fixed the to-be-supported substrate to the support body, a specific use will not be specifically limited. In the following description, a stacked body in which a semiconductor wafer (supported substrate) is temporarily fixed to a support plate (support) used in a wafer support system will be described as an example. As shown in FIG. 1 (1), the laminate 1 according to this embodiment includes a substrate 11, a support plate (support) 12, an adhesive layer 14, and a separation layer 16.
  • the substrate 11 is subjected to processes such as thinning and mounting while being supported by the support plate 12.
  • the substrate 11 is not limited to a wafer substrate, and an arbitrary substrate such as a thin film substrate or a flexible substrate can be used. 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 14 side.
  • the support plate 12 is a support body that supports the substrate 11 and has optical transparency. Therefore, when light is irradiated toward the support plate 12 from outside the stacked body 1, the light passes through the support plate 12 and reaches the separation layer 16. 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 16 (having a predetermined wavelength).
  • the separation layer 16 is a layer formed of a material that changes in quality by absorbing light irradiated through the support.
  • the “deterioration” of the separation layer 16 means a phenomenon that causes the separation layer 16 to 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 16 is reduced. Means.
  • the separation layer 16 loses its 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 16 is broken, and the support plate 12 and the substrate 11 can be easily separated.
  • the alteration of the separation layer 16 includes decomposition (exothermic or non-exothermic), cross-linking, configuration change or dissociation of functional groups due to absorbed light energy (and curing of the separation layer and degassing associated therewith). , Contraction or expansion) and the like.
  • the alteration of the separation layer 16 occurs as a result of light absorption by the material constituting the separation layer 16. Therefore, the type of alteration of the separation layer 16 can be changed according to the type of material constituting the separation layer 16.
  • the separation layer 16 is provided on the surface of the support plate 12 on the side where the substrate 11 is bonded via the adhesive layer 14. That is, the separation layer 16 is provided between the support plate 12 and the adhesive layer 14.
  • the thickness of the separation layer 16 is, for example, 0.05 to 100 ⁇ m, more preferably 0.1 to 50 ⁇ m, still more preferably 0.1 to 10 ⁇ m, and particularly preferably 0.3 to 1 ⁇ m. If the thickness of the separation layer 16 is within the range of 0.05 to 100 ⁇ m, the separation layer 16 can be altered as desired by irradiation with light for a short time and irradiation with low energy light. The thickness of the separation layer 16 is particularly preferably within a range of 1 ⁇ m or less from the viewpoint of productivity.
  • another layer may be further formed between the separation layer 16 and the support plate 12.
  • the other layer should just be comprised from the material which permeate
  • the wavelength of light that can be used differs depending on the type of material constituting the separation layer 16. 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 16.
  • the separation layer 16 is preferably formed only from a material having a structure that absorbs light, but the material does not have a structure that absorbs light as long as the essential characteristics of the present invention are not impaired. May be added to form the separation layer 16. In addition, it is preferable that the surface of the separation layer 16 on the side facing the adhesive layer 14 is flat (unevenness is not formed), whereby the formation of the separation layer 16 can be easily performed, and Even in the pasting, it is possible to paste evenly.
  • a material that forms the separation layer 16 as described below may be used by bonding it to the support plate 12 in advance, or the separation layer 16 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 16 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 16. it can.
  • CVD chemical vapor deposition
  • the separation layer 16 may be altered by absorbing light irradiated from the laser. That is, the light applied to the separation layer 16 to alter the separation layer 16 may be light emitted from a laser.
  • lasers that emit light to irradiate the separation layer 16 include YAG lasers, ruby lasers, glass lasers, YVO 4 lasers, LD lasers, fiber lasers and other solid lasers, dye lasers and other liquid lasers, CO 2 lasers, Examples thereof include gas lasers such as excimer 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 16 can be appropriately selected according to the material constituting the separation layer 16, and irradiates light having a wavelength that can alter the material constituting the separation layer 16. Select the laser to be used.
  • the separation layer 16 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 16 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 16 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 in which a polymer containing the structure as a repeating unit is altered by light absorption by the structure.
  • the structure is a chemical moiety containing a conjugated ⁇ -electron system consisting of, for example, a substituted or unsubstituted benzene ring, fused 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.
  • the structure can be represented by the following formula:
  • each R is independently an alkyl group, aryl group, halogen, hydroxyl group, ketone group, sulfoxide group, sulfone group, or N (R 1 ) (R 2 ) (where R 1 and R 2 are Each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), Z is absent or is CO—, —SO 2 —, —SO— or —NH—, and n is 0 or It is an integer from 1 to 5.
  • 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.
  • 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). , (F) is any one of the formulas shown in the above “Chemical Formula 1” or does not exist, and Y 1 and Y 2 are each independently —CO— or SO 2 —. l is preferably an integer of 10 or less.
  • Examples of the benzene ring, condensed ring and heterocyclic ring shown in the above “chemical formula 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, fluorin, substituted fluorin, fluorinone, substituted fluorin, carbazole, substituted carbazole, N-alkylcarbazole, dibenzofuran, substituted dibenzofuran, phenanthrene, substituted phenanthrene, pyrene and substituted pyrene.
  • 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.
  • 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-di Tylamino-2'-hydroxybenzophenone, 4-diethylamino-2'-hydroxybenzophenone, 4-dimethylamino-4'-methoxy-2'-hydroxy
  • the above structure can absorb light having a wavelength in a desired range by selecting the type.
  • the wavelength of light that can be absorbed by the above structure is more preferably 100 to 2000 nm. Within this range, the wavelength of light that can be absorbed by the structure is on the shorter wavelength side, for example, 100 to 500 nm.
  • the structure can alter the polymer containing the structure by absorbing ultraviolet light, preferably having a wavelength of about 300-370 nm.
  • Light that can be absorbed by the above structure is, for example, a high-pressure mercury lamp (wavelength: 254 nm to 436 nm), a KrF excimer laser (wavelength: 248 nm), an ArF excimer laser (wavelength: 193 nm), an F2 excimer laser (wavelength: 157 nm), or XeCl.
  • the separation layer 16 described above contains a polymer including the above structure as a repeating unit, but the separation layer 16 may further include a component other than the polymer.
  • 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.
  • the separation layer 16 can be made of an inorganic material.
  • the said inorganic substance is a material which changes in quality by light absorption.
  • the separation layer 16 composed of such an inorganic material is altered by absorption of light, and loses strength or adhesiveness before being irradiated with light. Since the separation layer 16 that has been irradiated with light is broken by receiving a slight external force (for example, lifting the support plate 12), the support plate 12 and the substrate 11 can be easily separated.
  • the said inorganic substance should just be a material which changes in quality by absorbing light, and the said inorganic substance can use suitably one or more types of inorganic substances selected from the group which consists of a metal, a metal compound, and carbon, for example.
  • 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 allotropes of carbon, and may be, for example, diamond, fullerene, diamond-like carbon, carbon nanotube, and the like.
  • the above inorganic substance absorbs light having a wavelength in a specific range depending on the type.
  • the inorganic material can be suitably altered.
  • YAG laser YAG laser
  • ruby laser glass laser
  • YVO 4 laser LD laser
  • fiber laser or other solid laser dye laser
  • a liquid laser such as CO 2 laser, excimer laser, Ar laser, He—Ne laser or other gas laser, semiconductor laser, free electron laser or other laser light, or non-laser light may be used as appropriate.
  • the separation layer 16 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 16 made of an inorganic material 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 to 10 ⁇ m is more preferable.
  • 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 16 and attached to the support plate 12 and the substrate 11.
  • the separation layer 16 may be formed of a compound having an infrared absorbing structure.
  • the compound is altered by absorbing infrared rays.
  • the separation layer 16 loses its strength or adhesiveness before being irradiated with infrared rays as a result of the alteration of the compound. Therefore, by applying a slight external force (for example, lifting the support plate), the separation layer 16 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 an infrared absorptive structure include alkanes, 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
  • Examples of the structure containing the carbon-halogen bond include —CH 2 Cl, —CH 2 Br, —CH 2 I, —CF 2 —, —CF 3 , —CH ⁇ CF 2 , —CF ⁇ CF 2 , fluorine Aryl chloride, and aryl chloride.
  • Examples of the structure including 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 , 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.
  • the above structure can absorb infrared rays having a wavelength in a desired range by selecting the type.
  • the wavelength of infrared rays that can be absorbed by the above structure is, for example, in the range of 1 ⁇ m to 20 ⁇ m, and the range of 2 ⁇ m to 15 ⁇ m can be more suitably absorbed.
  • the structure is a Si—O bond, a Si—C bond, or a Ti—O bond, it can be in the range of 9 ⁇ m to 11 ⁇ m.
  • the infrared wavelength that can be absorbed by each structure can be easily understood by those skilled in the art.
  • non-patent literature 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 pages 146 to 151 may be referred to.
  • a compound having an infrared absorbing structure used for forming the separation layer 16 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.
  • a resin that is a copolymer of a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), or A resin that is a copolymer of a repeating unit represented by the formula (1) and a repeating unit derived from an acrylic compound can be used.
  • R 1 is hydrogen, an alkyl group having 10 or less carbon atoms, or an alkoxy group having 10 or less carbon atoms
  • a tert-butylstyrene (TBST) -dimethylsiloxane copolymer which is a copolymer of a repeating unit represented by the above formula (1) and a repeating unit represented by the following 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 formula (3) in a ratio of 1: 1 is further preferable.
  • a resin that is a copolymer of a repeating unit represented by the following formula (4) and a repeating unit represented by the following formula (5) can be used.
  • R 2 is hydrogen or an alkyl group having 1 to 10 carbon atoms
  • R 3 is an alkyl group having 1 to 10 carbon atoms, or a phenyl group.
  • the copolymer contains a repeating unit represented by the following formula (7) in a ratio of 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.
  • chelating titanium such as (ii) di-i-propoxy bis (acetylacetonato) titanium and propanedioxytitanium bis (ethylacetoacetate), (iii) iC 3 H 7 O — [— Ti (Oi-C 3 H 7 ) 2 —O—] n—iC 3 H 7 and nC 4 H 9 O— [Ti (On—C 4 H 9 ) 2 —O— ] N- n-C 4 H 9 and other titanium polymers, (iv) tri-n-butoxytitanium monostearate, titanium stearate, di-i-propoxytitanium diiso Stearate, and acylate titanium such as (2-n-butoxycarbonylbenzoyloxy) tributoxytitanium, and (v) water-soluble titanium compounds such as di-n-butoxy-bis (triethanolaminato) titanium. .
  • 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.
  • the separation layer 16 described above contains a compound having an infrared absorbing structure
  • the separation layer 16 may further include a component other than the above compound.
  • 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.
  • the separation layer 16 can be composed of a fluorocarbon. Fluorocarbon is altered by the absorption of light.
  • the separation layer 16 made of fluorocarbon is altered by absorption of light, and loses strength or adhesiveness before being irradiated with light. Since the separation layer 16 that has been irradiated with light is broken by receiving a slight external force (for example, lifting the support plate 12), the support plate 12 and the substrate 11 can be easily separated.
  • the fluorocarbon constituting the separation layer 16 can be suitably formed by a plasma CVD method.
  • fluorocarbon includes CxFy (perfluorocarbon) and CxHyFz (x, y, and z are positive integers), but is not limited thereto, for example, CHF 3 , CH 2 F 2 , C 2 H 2 F 2 , C 4 F 8 , C 2 F 6 , C 5 F 8, etc.
  • an inert gas such as nitrogen, helium, or argon, a hydrocarbon such as oxygen, alkane, or alkene, and carbon dioxide or hydrogen are added to the fluorocarbon used to configure the separation layer 16 as necessary. May be. Further, a mixture of these gases may be used (a mixed gas of fluorocarbon, hydrogen, nitrogen, etc.).
  • the separation layer 16 may be composed of a single type of fluorocarbon, or may be composed of two or more types of fluorocarbon.
  • Fluorocarbon absorbs light having a wavelength in a specific range depending on its 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 16, the fluorocarbon can be suitably altered.
  • the light applied to the separation layer 16 is a liquid such as a solid laser such as a YAG laser, a ruby laser, a glass laser, a YVO 4 laser, an LD laser, or a fiber laser, or a dye laser depending on the wavelength that can be absorbed by the fluorocarbon.
  • a gas laser such as a laser, a CO 2 laser, an excimer laser, an Ar laser, or a He—Ne laser, a laser beam such as a semiconductor laser or a free electron laser, or a non-laser beam may be used as appropriate.
  • the wavelength at which the fluorocarbon can be altered is not limited to this, but for example, a wavelength in the range of 600 nm or less can be used.
  • the separation layer 16 may contain an infrared absorbing material.
  • An infrared absorbing material is a material that is altered by the absorption of light.
  • the separation layer 16 configured to contain an infrared absorbing material is altered by absorption of light and loses strength or adhesiveness before being irradiated with light. Since the separation layer 16 that has been irradiated with light is broken by receiving a slight external force (for example, lifting the support plate 12), the support plate 12 and the substrate 11 can be easily separated.
  • the infrared absorbing material may be any material that is altered by absorbing infrared rays, and for example, carbon black, iron particles, or aluminum particles can be suitably used as the infrared absorbing material.
  • the infrared absorbing material absorbs light having a wavelength in a specific range depending on the type. By irradiating the separation layer 16 with light having a wavelength in a range that is absorbed by the infrared absorbing material used for the separation layer 16, the infrared absorbing material can be suitably altered.
  • the separation layer 16 can be a layer formed by plasma treatment using a reactive gas.
  • the reaction gas preferably contains an organic compound having an unsaturated bond and a fluorine compound.
  • the organic compound is not particularly limited as long as it has an unsaturated bond, and examples thereof include alkenes, cycloalkenes, alkynes, and aromatic compounds.
  • alkene examples include 1,2-butadiene, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 3-methyl-1,2-butadiene, isoprene, and the like.
  • cycloalkene examples include 1,3-hexadiene, 1,4-hexadiene, cyclopentadiene, 1,5-cyclooctadiene, and the like.
  • alkyne acetylene etc. can be mentioned, for example.
  • the aromatic compound examples include benzene, toluene, xylene, styrene and the like.
  • an organic compound having an ether bond, an ester bond, a siloxy bond, or the like can be used.
  • the organic compound having an ether bond and / or a siloxy bond examples include 1-methoxy-3- (trimethylsilyloxy) -1,3-butadiene and 2-trimethylsilyloxy-1,3-butadiene.
  • Examples of the organic compound having an ester bond examples include ethyl 2,3-butadiene acid.
  • the organic compound is preferably an alkene or a cycloalkene.
  • Alkenes or cycloalkenes have a structure that is not easily destroyed by low-density plasma. For this reason, by containing alkene or cycloalkene in the reaction gas, the alkene or cycloalkene can be suitably polymerized in the plasma treatment without excessive destruction. Also, unsaturated bonds can be introduced into the separation layer 16 formed by plasma treatment. Therefore, by using alkene or cycloalkene as the organic compound, it is possible to suitably form the separation layer 16 that is altered by absorbing light.
  • the organic compound preferably has two or more unsaturated bonds.
  • the separation layer 16 that can absorb light more preferably can be formed.
  • the organic compound preferably has a boiling point in the range of 30 ° C. or more and 100 ° C. or less, more preferably in the range of 30 ° C. or more and 60 ° C. or less, and in the range of 40 ° C. or more and 50 ° C. or less. Most preferably. If the boiling point of the organic compound is in the range of 30 ° C. or higher and 100 ° C. or lower, the organic compound can be suitably used as the reaction gas under the conditions for the plasma treatment.
  • Examples of the fluorine compound contained in the reaction gas used in the method for manufacturing a laminate according to this embodiment include fluorocarbon, carbon tetrafluoride (CF 4 ), nitrogen trifluoride (NF 3 ), and sulfur hexafluoride (SF). 6 ) and the like.
  • Examples of the fluorocarbon include C 4 F 8 and the like.
  • the plasma processing apparatus used for the plasma processing is not particularly limited, and a known plasma processing apparatus can be used.
  • the electrode provided in the plasma processing apparatus is not particularly limited, and may be, for example, a dual coil antenna, a single coil antenna, or a parallel plate electrode, but a separation layer formed on a support by using a parallel plate electrode.
  • the surface area of 16 can be increased, and as a result, a laminate can be manufactured using a substrate having a larger diameter.
  • the shape of the reaction chamber of the plasma processing apparatus is not particularly limited, and may be a dome shape or other shapes such as a cylindrical shape.
  • the size of the reaction chamber may be appropriately selected according to the size of the substrate to be processed.
  • the material of the reaction chamber can be appropriately selected from known materials that do not hinder the plasma treatment and the formation of the separation layer 16.
  • the plasma generated in the plasma processing apparatus includes capacitively coupled plasma (CCP: Conductive Coupled Plasma) by an electrostatic field generated by a high frequency power applied to a coil electrode or a parallel plate electrode, and inductive coupling by an induction electric field generated by a high frequency current flowing through the coil electrode.
  • CCP Conductive Coupled Plasma
  • ICP Inductive Coupled Plasma
  • the plasma treatment in the separation layer forming step is preferably a low density plasma treatment.
  • the low density plasma is a plasma having an ion density of 1 ⁇ 10 10 cm ⁇ 3 or less, and means a plasma mainly composed of capacitive coupling.
  • FIG. 2 is a schematic diagram illustrating a separation layer manufacturing process included in the manufacturing method according to an embodiment of the present invention.
  • the plasma processing apparatus 100 used in the separation layer forming process included in the laminate manufacturing method according to the present embodiment has a pair of parallel plate electrodes 102 and a support plate 12 placed in a reaction chamber 101. Stage 103 is provided.
  • the plasma processing apparatus 100 communicates with the container 111 storing the organic compound so as to pass through the liquid mass flow controller 112 and the vaporizer 113 through the pipe 116a, and passes through the mass flow controller 115 through the pipe 116b.
  • the fluorine compound cylinder 114 communicates. Further, the pipes 116 a and 116 b merge with the pipe 116.
  • the reaction chamber 101 is used for forming the separation layer 16 from the reaction gas by plasma treatment. Moreover, the reaction chamber 101 can adjust the pressure in the reaction chamber 101 by a vacuum pump (not shown).
  • the pair of parallel plate electrodes 102 are provided in the reaction chamber 101 and generate plasma using a reaction gas by applying high-frequency power.
  • the stage 103 includes one of the pair of parallel plate electrodes 102 so that the support plate 12 can be placed thereon.
  • the container 111 stores an organic compound used for the reaction gas, and supplies the organic compound to the liquid mass flow controller 112 via the pipe 116a by pressurizing with nitrogen.
  • the liquid mass flow controller 112 is a device that adjusts the flow rate of the organic compound, and adjusts the flow rate of the organic compound supplied to the vaporizer 113 via the pipe 116a.
  • the fluorine compound cylinder 114 is a cylinder storing a fluorine compound used as a reaction gas, and supplies the fluorine gas to the mass flow controller 115 through the pipe 116b.
  • the mass flow controller 115 is a device that adjusts the flow rate of the fluorine gas, and adjusts the flow rate of the fluorine gas supplied through the pipe 116b.
  • the piping 116 can be prevented from being liquefied by being heated.
  • the support plate 12 is placed on the stage 103 provided with one of the pair of parallel plate electrodes 102 in the reaction chamber 101.
  • a preheating step of preheating the inside of the reaction chamber 101 and the support plate 12 may be performed.
  • the surface of the support plate 12 may be cleaned by adding oxygen gas to the pretreatment gas.
  • a reaction gas that becomes the separation layer 16 is supplied into the reaction chamber 101, and the separation layer 16 is formed on the support plate 12 by plasma treatment.
  • the organic compound contained in the reaction gas is supplied from the container 111, the flow rate is adjusted by the liquid mass flow controller 112, and the vaporizer 113 vaporizes the organic compound.
  • the fluorine compound is supplied from the fluorine compound cylinder 114 and the flow rate is adjusted by the mass flow controller 115. Thereafter, the vaporized organic compound and fluorine compound are mixed in the pipe 116 and supplied into the reaction chamber 101 while being heated.
  • the volume ratio of the organic compound and the fluorine compound contained in the reaction gas can be adjusted by adjusting the flow rates of the organic compound and the fluorine gas with the liquid mass flow controller 112 and the mass flow controller 115.
  • the volume ratio of the organic compound to the fluorine compound is 6: 4 to 9: 1
  • the separation layer 16 having no chemical resistance and good brittleness can be formed.
  • the separation layer 16 that can be suitably removed by the cleaning liquid can be formed.
  • the volume ratio of the organic compound and the fluorine compound can be adjusted during the separation layer forming step.
  • inert gases such as nitrogen, helium and argon, and additional gases such as hydrogen and oxygen may be added to the reaction gas.
  • the target temperature in the reaction chamber 101 is not particularly limited, and a known temperature can be used, but it is more preferably in the range of 100 ° C. or higher and 300 ° C. or lower, and the range of 200 ° C. or higher and 250 ° C. or lower. It is particularly preferred that By setting the temperature in the reaction chamber to such a range, the plasma treatment can be suitably performed.
  • the thickness of the separation layer 16 formed in the separation layer forming step is not particularly limited as long as it is a film thickness that can sufficiently absorb the light to be used.
  • the range is 0.5 ⁇ m or more and 2.0 ⁇ m or less.
  • the film thickness is more preferably within the range of 1.0 ⁇ m or more and 1.5 or less. What is necessary is just to set the formation time of the separation layer 16 in a separation layer formation process according to the film thickness to form.
  • the separation layer 16 can include a first separation layer 16 a and a second separation layer 16 b.
  • the laminate 20 has the same configuration as that of the laminate 1 except that the separation layer 16 has two layers.
  • the first separation layer 16a is formed by the plasma processing apparatus 100 of FIG. 2 using a reactive gas containing an organic compound having an unsaturated bond and a fluorine compound.
  • the second separation layer 16b is a layer that does not correspond to the first separation layer 16a and is formed of a material that is altered by the light irradiation exemplified in this specification.
  • the first separation layer 16a and the second separation layer 16b are formed on the support.
  • the first separation layer 16a has chemical resistance in various chemical treatments
  • the second separation layer 16b has good separation properties after irradiation with light.
  • the first separation layer 16a can prevent the second separation layer 16b from being altered by chemical treatment.
  • the second separation layer 16b is on the first separation layer 16a
  • the first separation layer 16a functions as a separation layer even if the second separation layer 16b is altered by chemical treatment. It can be secured.
  • the separation layer can be suitably altered and the substrate can be easily separated from the laminate.
  • optical density In general, the optical density (hereinafter referred to as OD value) is obtained by the following equation (1).
  • D ⁇ log (I / I 0 ) (1)
  • D is the OD value
  • I is the intensity of incident light
  • I 0 is the intensity of transmitted light.
  • the OD value of the separation layer 16 is evaluated based on the OD value measured using an X-Rite 310 (OD value measuring machine: manufactured by X-Rite).
  • the OD value of the separation layer 16 of the laminate 1 is preferably 0.20 or more and 1.00 or less, and more preferably 0.30 or more and 1.00 or less. In the range where the OD value of the separation layer 16 is 0.20 or more and 1.00 or less (particularly, the range of 0.30 or more and 1.00 or less, and so on), the laser beam is applied so that the substrate 11 is not damaged. The present inventors have found that irradiation time can be reduced and the film formation time of the separation layer 16 can be shortened.
  • damage to the substrate 11 can be suitably prevented under the following conditions.
  • the OD value of the separation layer 16 is set to 0.20 or more and 1.00 or less, it is preferable to set the irradiation condition of the laser light as follows.
  • the average output value of the laser beam is preferably in the range of 1.0 W or more and 5.0 W or less, and more preferably in the range of 3.0 W or more and 4.0 W or less.
  • the repetition frequency of the laser light is preferably in the range of 20 kHz or more and 60 kHz or less, and more preferably in the range of 30 kHz or more and 50 kHz or less.
  • the wavelength of the laser light is preferably 300 nm or more and 700 nm or less, and more preferably 450 nm or more and 650 nm or less. According to such conditions, the energy of the pulsed light applied to the separation layer 16 can be set to an appropriate condition for altering the separation layer 16 while preventing damage to the substrate 11.
  • the beam spot diameter of the pulsed light used in the separation step of the separation layer 16 is preferably 100 ⁇ m or more and 250 ⁇ m or less, and more preferably 120 ⁇ m or more and 230 ⁇ m or less.
  • the irradiation pitch of the pulsed light may be any pitch that does not overlap adjacent beam spots and can change the separation layer 16, but is preferably 110 ⁇ m or more and 250 ⁇ m or less, preferably 160 ⁇ m or more, More preferably, it is 220 ⁇ m or less.
  • the irradiation speed of the pulse light may be any speed that can change the separation layer 16, but is preferably 4000 mm / s or more and 10000 mm / s or less, preferably 5000 mm / s or more and 8000 mm / s or less. It is more preferable that
  • the pulse width of the pulsed light applied to the separation layer 16 is preferably 20 nanoseconds or more. More preferably, it is 40 nanoseconds or more, More preferably, it is 70 nanoseconds or more.
  • the upper limit of the pulse width of the pulsed light applied to the separation layer 16 is preferably 200 nanoseconds, and more preferably 150 nanoseconds.
  • the OD value of the separation layer 16 varies depending on the type of material constituting the separation layer 16. Further, for example, when the separation layer 16 is formed by a chemical vapor deposition (CVD) method, the thickness varies depending on the density of the material constituting the separation layer 16. In this case, the density of the separation layer 16 can be adjusted by changing the film formation time of the separation layer 16 by chemical vapor deposition (CVD), the injection rate of the source gas, and the like.
  • CVD chemical vapor deposition
  • the separation layer 16 is preferably formed only from a material having a structure that absorbs light, but the material does not have a structure that absorbs light as long as the essential characteristics of the present invention are not impaired. Can also be added to adjust the OD value.
  • the adhesive layer 14 is configured to adhere and fix the substrate 11 to the support plate 12 and at the same time to cover and protect the surface of the substrate 11. Therefore, the adhesive layer needs to have adhesiveness and strength for maintaining the fixing of the substrate 11 to the support plate 12 and the covering of the surface to be protected of the substrate 11 when the substrate 11 is processed or transported. . On the other hand, when it becomes unnecessary to fix the substrate 11 to the support plate 12, it needs to be easily peeled or removed from the substrate 11.
  • the adhesive layer 14 usually has strong adhesiveness, and the adhesive layer 14 is composed of an adhesive whose adhesiveness is reduced by some treatment or has solubility in a specific solvent.
  • the thickness of the adhesive layer 14 is more preferably 1 to 200 ⁇ m, and further preferably 10 to 150 ⁇ m.
  • the adhesive layer 14 can be formed by applying an adhesive material as described below onto the substrate 11 by a conventionally known method such as spin coating.
  • adhesive for example, various adhesives known in the art such as acrylic, novolak, naphthoxan, hydrocarbon, polyimide, and elastomer are adhesives that constitute the adhesive layer 14 according to the present embodiment. It can be used. Below, the composition of resin which the contact bonding layer 14 in this embodiment contains is demonstrated.
  • the resin contained in the adhesive layer 14 may be any resin as long as it has adhesiveness, for example, a hydrocarbon resin, an acrylic-styrene resin, a maleimide resin, an elastomer resin, or a combination thereof.
  • the hydrocarbon resin is a resin that has a hydrocarbon skeleton and is obtained by polymerizing a monomer composition.
  • cycloolefin polymer hereinafter sometimes referred to as “resin (A)”
  • resin (A) cycloolefin polymer
  • resin (B) at least one resin selected from the group consisting of terpene resin, rosin resin and petroleum resin
  • Resin (A) may be a resin obtained by polymerizing a monomer component containing a cycloolefin monomer.
  • Specific examples of the resin (A) 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. Can be mentioned.
  • 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.
  • 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 monomer, and preferably contains, for example, an alkene monomer.
  • alkene monomer examples include ethylene, propylene, 1-butene, isobutene, 1-hexene, ⁇ -olefin, and the like.
  • the alkene monomer may be linear or branched.
  • a cycloolefin monomer is contained as a monomer component constituting the resin (A) from the viewpoint of high heat resistance (low thermal decomposability, low thermal weight reduction).
  • 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.
  • 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.
  • a linear or branched alkene monomer may be contained as a monomer component constituting the 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 component are not particularly limited and may be appropriately set according to a conventional method.
  • 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.
  • Tg glass transition point
  • Resin (B) is at least one resin selected from the group consisting of terpene resins, rosin resins and petroleum resins.
  • terpene resin examples include terpene resins, terpene phenol resins, modified terpene resins, hydrogenated terpene resins, hydrogenated terpene phenol resins, and the like.
  • rosin resin examples 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.
  • the softening point of the resin (B) is not particularly limited, but is preferably 80 to 160 ° C.
  • the softening point of the resin (B) is 80 ° C. or higher, the adhesive laminate can be suppressed from being softened when exposed to a high temperature environment, and adhesion failure does not occur.
  • the softening point of the resin (B) is 160 ° C. or less, the resin (B) exhibits a good peeling rate when peeling the adhesive laminate.
  • the molecular weight of the resin (B) is not particularly limited, but is preferably 300 to 3000. When the molecular weight of the resin (B) is 300 or more, the resin (B) exhibits sufficient heat resistance 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 resin (B) exhibits a good peeling rate when peeling the adhesive laminate.
  • the molecular weight of resin (B) in this embodiment means the molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC).
  • the mixture may use what mixed resin (A) and resin (B) as resin.
  • the mixture exhibits good heat resistance and peel rate.
  • the mixture has a peeling rate and a high temperature environment. It is preferable because of its excellent heat resistance and flexibility.
  • acryl-styrene resin examples 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. .
  • acrylic long-chain alkyl ester examples include acrylic acid 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.
  • alkyl esters examples include alkyl esters.
  • the alkyl group may be branched.
  • acrylic alkyl ester having an alkyl group having 1 to 14 carbon atoms examples include known acrylic alkyl esters used in existing acrylic adhesives.
  • esters 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.
  • 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.
  • the aromatic ring may have a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, phenoxyethyl acrylate is preferable.
  • maleimide resins include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, N-sec as monomers.
  • 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 Resins obtained by polymerizing aromatic maleimides having an aryl group such as imide, N-phenylmaleimide, Nm-methylphenylmaleimide, No-methylphenylmaleimide, and Np-methylphenylmaleimide It is done.
  • aryl group such as imide, N-phenylmaleimide, Nm-methylphenylmaleimide, No-methylphenylmaleimide, and Np-methylphenylmaleimide It is done.
  • a cycloolefin copolymer that 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.
  • n is 0 or an integer of 1 to 3.
  • APL 8008T, APL 8009T, APL 6013T (all manufactured by Mitsui Chemicals, Inc.) and the like can be used.
  • the adhesive layer 14 it is preferable to form the adhesive layer 14 using a resin other than a photocurable resin (for example, a UV curable resin).
  • a resin other than a photocurable resin for example, a UV curable resin
  • the photocurable resin may remain as a residue around the minute irregularities of the substrate 11 after the adhesive layer 14 is peeled or removed.
  • an adhesive that dissolves in a specific solvent is preferable as a material constituting the adhesive layer 14. This is because the adhesive layer 14 can be removed by dissolving it in a solvent without applying a physical force to the substrate 11. When the adhesive layer 14 is removed, the adhesive layer 14 can be easily removed without damaging or deforming the substrate 11 even from the substrate 11 whose strength has decreased.
  • hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, tridecane, and other linear hydrocarbons, having 3 to 15 carbon atoms are used.
  • hydrocarbons eg), p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpine, 1,8-terpin, bornane, norbornane, pinane, tujang, kalan, longifolene, geraniol , Nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, ⁇ -terpineol, ⁇ -terpineol, ⁇ -terpineol, terpinen-1-ol, terpinen-4-ol, dihydroterpinyl acetate, 1,4 -Cineol, 1,8-Cineol Terpene solvents such as borneol, carvone, yonon, thuyon, camphor, d-limonene, l-limonene, dipentene; lactones such as ⁇ -butyrol
  • the elastomer preferably contains a styrene unit as a constituent unit of the main chain.
  • the elastomer used as the adhesive preferably has a styrene unit content in the range of 14% by weight to 50% by weight.
  • the elastomer preferably has a weight average molecular weight in the range of 10,000 to 200,000.
  • elastomers examples include polystyrene-poly (ethylene / propylene) block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), and styrene-butadiene-butylene-styrene block.
  • SEP polystyrene-poly (ethylene / propylene) block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • SBS styrene-butadiene-styrene block copolymer
  • styrene-butadiene-butylene-styrene block examples include polystyrene-poly (ethylene / propylene) block copolymer (SEP), styrene-isoprene-s
  • SBBS ethylene-propylene terpolymer
  • EPT ethylene-propylene terpolymer
  • SEBS styrene-ethylene-butylene-styrene block copolymer
  • SEPS styrene-ethylene-propylene-styrene block copolymer
  • SEEPS styrene-ethylene-ethylene-propylene-styrene block copolymer
  • the adhesive material may further contain other miscible substances as long as the essential characteristics of the present invention are not impaired.
  • various conventional additives such as additional resins, plasticizers, adhesion aids, stabilizers, colorants, antioxidants and surfactants for improving the performance of the adhesive may be further used. it can.
  • the separation layer 16 is irradiated with pulsed laser light through the support plate 12 (irradiation process). . At this time, the irradiated laser light passes through the light-transmitting support plate 12 and reaches the separation layer 16.
  • the separation layer 16 is altered as shown in (2) in FIG. 1 by absorbing the laser beam that has arrived. Thereby, the adhesion between the substrate 11 and the support plate 12 is weakened, and the support plate 12 is easily separated from the substrate 11 as shown in FIG.
  • the separation layer 16 In order to separate the support plate 12 from the laminate 1, when the separation layer 16 is irradiated with laser light from the support plate 12 side, the laser light may leak from the separation layer 16.
  • the leaked light reaches the substrate 11, and the substrate 11 itself or an electronic element such as an electronic circuit to be protected formed on the substrate 11 may be adversely affected by the leaked light.
  • adverse effects of leaked light include disassembly of electronic circuits mounted on the substrate 11, damage to the substrate 11, and the like.
  • an OD value of the separation layer 16 may be selected from 0.20 to 1.00. Such selection of the OD value in the separation layer 16 makes it possible to change the separation layer 16 in a desired manner without damaging the substrate 11 with the transmitted light of the laser light by irradiation with the laser beam.
  • damage to the substrate 11 can be suitably prevented under the following conditions.
  • the OD value of the separation layer 16 is set to 0.20 or more and 1.00 or less, it is preferable to set the irradiation condition of the laser light as follows.
  • the average output value of the laser beam is preferably in the range of 1.0 W or more and 5.0 W or less, and more preferably in the range of 3.0 W or more and 4.0 W or less.
  • the repetition frequency of the laser light is preferably in the range of 20 kHz or more and 60 kHz or less, and more preferably in the range of 30 kHz or more and 50 kHz or less.
  • the wavelength of the laser light is preferably 300 nm or more and 700 nm or less, and more preferably 450 nm or more and 650 nm or less. According to such conditions, the energy of the pulsed light applied to the separation layer 16 can be set to an appropriate condition for altering the separation layer 16 while preventing damage to the substrate 11.
  • the beam spot diameter of the pulsed light used in the separation step of the separation layer 16 is preferably 100 ⁇ m or more and 250 ⁇ m or less, and more preferably 120 ⁇ m or more and 230 ⁇ m or less.
  • the irradiation pitch of the pulsed light may be any pitch that does not overlap adjacent beam spots and can change the separation layer 16, but is preferably 110 ⁇ m or more and 250 ⁇ m or less, preferably 160 ⁇ m or more, More preferably, it is 220 ⁇ m or less.
  • the irradiation speed of the pulse light may be any speed that can change the separation layer 16, but is preferably 4000 mm / s or more and 10000 mm / s or less, preferably 5000 mm / s or more and 8000 mm / s or less. It is more preferable that
  • the pulse width of the pulsed light applied to the separation layer 16 is preferably 20 nanoseconds or more. More preferably, it is 40 nanoseconds or more, More preferably, it is 70 nanoseconds or more.
  • the upper limit of the pulse width of the pulsed light applied to the separation layer 16 is preferably 200 nanoseconds, and more preferably 150 nanoseconds.
  • the irradiation apparatus for irradiating pulsed light in the method for separating the laminate is not particularly limited as long as the separation layer 16 can be irradiated with pulsed light having a pulse width of 20 nanoseconds or more.
  • An oscillator appropriately selected from laser oscillators and the like can be used.
  • the irradiation device can be selected as appropriate according to the material constituting the separation layer 16, and a laser that irradiates light capable of altering the material constituting the separation layer 16 may be selected.
  • the frequency of the laser beam is preferably 300 nm to 700 nm. When the frequency of the laser light is within the range, it becomes easy to alter the separation layer 16 without damaging the substrate 11 and the electronic device formed on the substrate 11 with the laser light applied to the separation layer.
  • the irradiation step it is preferable to uniformly irradiate the entire laminate 1 with pulsed light.
  • the separation layer 16 can be altered so that the substrate 11 and the support plate 12 can be easily separated, the laminate can be used. 1 may be partially irradiated with pulsed light.
  • the separation method of the laminate by adjusting the OD value of the separation layer 16 to 0.20 or more and 1.00 or less, an appropriate repetition frequency and average output of the pulsed laser light can be set. is there. Therefore, since the laser light set appropriately is irradiated, even if the light leaked without being absorbed in the separation layer 16 reaches the substrate 11, it may damage the substrate 11 and the electronic elements formed on the substrate 11. Absent. In addition, since the separation layer 16 can be irradiated with light having an energy intensity necessary for altering the separation layer 16, the substrate 11 and the support plate 12 can be easily separated.
  • the substrate 11 and the support plate 12 can be easily separated by light irradiation after the manufacturing process while realizing strong adhesion between the substrate 11 and the support plate 12 during the manufacturing process. In addition to being possible, there is an effect that the adverse effect on the substrate 11 by light can be prevented.
  • the present invention provides a method for evaluating a separation layer including a measurement step of measuring the OD value of the separation layer. That is, as described above, if the OD value of the separation layer is within a predetermined range, damage to the substrate surface can be prevented. Therefore, by measuring the OD value of the separation layer, it can be evaluated whether or not the separation layer does not transmit light that damages the substrate surface.
  • the separation layer evaluation method when the OD value of the separation layer measured in the measurement step is 0.20 or more, it is determined that the separation layer does not transmit light that damages the substrate surface. it can. More preferably, when the OD value of the separation layer measured in the measurement step is 0.20 or more and 1.00 or less, it can be determined that the separation layer does not transmit light that causes damage to the substrate surface. In this way, it is possible to avoid the manufacture of defective products due to damage received on the substrate surface in the irradiation step. In addition, it is preferable that the average output value of the laser beam in the irradiation process at this time is 1.0 W or more and 5.0 W or less, and more preferably 3.0 W or more and 4.0 W or less. .
  • the repetition frequency of the laser light is preferably in the range of 20 kHz to 60 kHz, and more preferably in the range of 30 kHz to 50 kHz.
  • the wavelength of the laser beam is preferably 300 nm or more and 700 nm or less, and more preferably 450 nm or more and 650 nm or less.
  • the beam spot diameter of the pulsed light is preferably 100 ⁇ m or more and 250 ⁇ m or less, and more preferably 120 ⁇ m or more and 230 ⁇ m or less.
  • the irradiation pitch of the pulsed light may be any pitch that does not overlap adjacent beam spots and can change the separation layer 16, but is preferably 110 ⁇ m or more and 250 ⁇ m or less, preferably 160 ⁇ m or more, More preferably, it is 220 ⁇ m or less.
  • the irradiation speed of the pulse light may be any speed that can change the separation layer 16, but is preferably 4000 mm / s or more and 10000 mm / s or less, preferably 5000 mm / s or more and 8000 mm / s or less. It is more preferable that Furthermore, the pulse width of the pulsed light applied to the separation layer 16 is preferably 20 nanoseconds or more. More preferably, it is 40 nanoseconds or more, More preferably, it is 70 nanoseconds or more.
  • the upper limit of the pulse width of the pulsed light applied to the separation layer 16 is preferably 200 nanoseconds, and more preferably 150 nanoseconds.
  • the conditions of the reaction chamber provided with the parallel plate electrodes for manufacturing the laminate were adjusted to an output power of a high-frequency power source of 1.0 kW, a pressure of 67 Pa, and a film formation temperature of 220 ° C.
  • a high-frequency power source of 1.0 kW
  • a pressure of 67 Pa a pressure of 67 Pa
  • isoprene adjusted to a flow rate of 200 sccm was supplied as a reaction gas, and plasma treatment by plasma CVD was performed.
  • a reaction gas containing isoprene adjusted to a flow rate of 100 sccm and sulfur hexafluoride (SF 6 ) adjusted to a flow rate of 100 sccm in a ratio of 1: 1 is supplied, and a plasma CVD method is performed. Plasma treatment was performed. Thereby, a separation layer (film thickness: 0.5 ⁇ m) formed from isoprene and sulfur hexafluoride (SF 6 ) was formed on a 12-inch bare glass. The separation layer is referred to as an “isoprene membrane” for convenience.
  • an adhesive composition (TZNR-A3007, manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied to a 12-inch silicon wafer (substrate), and baked at 100 ° C., 160 ° C., and 200 ° C. for 3 minutes, respectively, to form an adhesive layer (film) (Thickness 50 ⁇ m) was formed (adhesive layer forming step). And it bonded together with the glass support body which formed the fluorocarbon film
  • the laser light wavelength was 532 nm
  • the laser light diameter was 180 ⁇ m
  • the center-to-center distance between irradiated regions in the laser pulse was 180 ⁇ m
  • the scanning speed was 7200 mm / s
  • the average output and repetition frequency of the laser light were changed.
  • Laser light irradiation was performed under conditions to determine whether the separation layer could be peeled off.
  • a fluorocarbon film was formed on a 12-inch bare glass (support plate) by plasma CVD using C 4 F 8 as a reaction gas under the conditions of a flow rate of 400 sccm, a pressure of 700 mTorr, a high-frequency power of 2500 W, and a film formation temperature of 240 ° C. Separation layer forming step). At this time, the thickness of the separation layer was set to 2000 mm (0.2 ⁇ m), 4500 mm (0.45 ⁇ m), and 7000 mm (0.7 ⁇ m), respectively, and the film formation time was changed under three conditions.
  • OD value measuring machine manufactured by X-Rite Co., Ltd.
  • the OD value was measured at a certain distance from the center position of each separation layer. The results are shown in Table 2 and FIG.
  • OD value was measured in each position where the distance from the center in the separated layer on a support plate differs as shown in Table 2 and FIG. 4 (a) and (b).
  • the distance from the center of the separation layer to 120 mm was 6 mm, and the distance from the center to 120 mm to 150 mm was 3 mm.
  • an adhesive composition (TZNR-A3007, Tokyo Ohka Kogyo Co., Ltd.) was placed on the Sn-Ag plate of a 12-inch silicon wafer (substrate) equipped with a Sn-Ag plate (tin-silver plate, 0.3 to 0.4 ⁇ m). Company) was applied and baked at 100 ° C., 160 ° C., and 200 ° C. for 3 minutes each to form an adhesive layer (film thickness 50 ⁇ m) (adhesive layer forming step).
  • the Sn—Ag plate was used in place of an element mounted on the wafer substrate, an electric circuit, or the like. And it bonded together with the glass support body which formed the fluorocarbon film
  • the wavelength of the laser beam is 532 nm
  • the diameter of the laser beam is 180 ⁇ m
  • the distance between the centers of the irradiated regions in the laser pulse is 180 ⁇ m
  • the scanning speed is 7200 mm / s
  • the average output of the laser beam is 3.42 W
  • the repetition frequency Laser light irradiation was performed at 40 kHz.
  • the damage received by the Sn-Ag plate was visually confirmed with a microscope.
  • damage was indicated, and when no laser beam spot was formed, no damage was indicated.
  • Target: 2000A where the OD value was entirely lower than 0.30 damage was observed on the Sn-Ag plate in both positions (1) and (2).
  • Target: 4500A slight damage was observed on the Sn-Ag plate at the position where the OD value of both (3) and (4) was 0.29, but the OD value was 0.30 or more and 1.00. No damage was observed on the Sn-Ag plate at the following positions.
  • Target: 7000A with an OD value of 0.30 or more and 1.00 or less over the entire surface, no damage was observed on the Sn-Ag plate in both positions (5) and (6).
  • each of the laminates using 12-inch silicon wafers (substrates) loaded with various materials was prepared, and the deposition time of the separation layer by the CVD method
  • the CVD method By creating a support plate that forms separation layers showing different OD values, creating a laminate that combines the conditions, and irradiating laser light, the effect of laser light on each material was compared with the case of Sn-Ag plate.
  • Materials used in place of the elements and electric circuits were Cu (1 ⁇ m), SiO 2 (1 ⁇ m), Al (0.2 ⁇ m), and polyimide (0.1 ⁇ m), and these were formed on a 12-inch silicon wafer (substrate). The attached one was used for evaluation. The same evaluation was performed on the bare silicon wafer and compared with the case of the Sn—Ag plate.
  • a fluorocarbon film was formed on a 12-inch bare glass (support plate) by plasma CVD using C 4 F 8 as a reaction gas under the conditions of a flow rate of 400 sccm, a pressure of 700 mTorr, a high-frequency power of 2500 W, and a film formation temperature of 240 ° C. Separation layer forming step).
  • the film thickness of the separation layer was set to 2000 mm (0.2 ⁇ m), 4500 mm (0.45 ⁇ m), and 7000 mm (0.7 ⁇ m), respectively, and the film formation time was changed under three conditions.
  • a support plate (“direct” in Table 3 below) that does not form a separation layer was also prepared.
  • an OD value at a fixed distance from the center position of each separation layer was measured using an X-Rite 310 (OD value measuring device, manufactured by X-Rite).
  • the thickness target of the separation layer is 2000 mm
  • the OD value is about 0.15
  • the film thickness target is 4500 mm
  • the OD value is about 0.30
  • the film thickness target is 7000 mm
  • the OD value is about It became 0.45.
  • an adhesive composition (TZNR-A3007, manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied onto a 12-inch silicon wafer (substrate) with or without various materials, and 100 ° C. and 160 ° C. Then, each layer was baked at 200 ° C. for 3 minutes to form an adhesive layer (film thickness 50 ⁇ m) (adhesive layer forming step).
  • the various substrates were bonded to various glass supports (having a fluorocarbon film) for 3 minutes under conditions of 220 ° C. and 4000 Kg under vacuum to form a laminate (lamination step).
  • the wavelength of the laser beam is 532 nm
  • the diameter of the laser beam is 180 ⁇ m
  • the distance between the centers of the irradiated regions in the laser pulse is 180 ⁇ m
  • the scanning speed is 7300 mm / s
  • the average output of the laser beam is 3.42 W
  • the repetition frequency Laser light irradiation was performed at 40 kHz.
  • the results differed depending on the type of material mounted on the substrate. That is, the OD value necessary for avoiding damage to elements, electrical circuits, and the like on the substrate by the laser light differs depending on the substrate. However, by selecting an appropriate OD value according to the type of material mounted on the substrate, in any case, it is shown that damage to elements, electrical circuits, etc. on the substrate due to laser light can be avoided. It was done.
  • the present invention can be suitably used, for example, in a manufacturing process of a miniaturized semiconductor device.

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  • Inorganic Chemistry (AREA)
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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
PCT/JP2013/075722 2012-09-28 2013-09-24 積層体、積層体の分離方法、および分離層の評価方法 WO2014050820A1 (ja)

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JP2015217566A (ja) * 2014-05-15 2015-12-07 東京応化工業株式会社 積層体の製造方法および積層体
JP2016092079A (ja) * 2014-10-30 2016-05-23 東京応化工業株式会社 支持体分離方法
WO2020080276A1 (ja) * 2018-10-16 2020-04-23 富士フイルム株式会社 レーザ剥離用の積層体、組成物およびキット
WO2022210154A1 (ja) * 2021-04-01 2022-10-06 東レ株式会社 積層体および半導体装置の製造方法

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JP6437805B2 (ja) * 2014-12-03 2018-12-12 東京応化工業株式会社 積層体の製造方法、封止基板積層体の製造方法及び積層体
JP6486735B2 (ja) * 2015-03-17 2019-03-20 東芝メモリ株式会社 半導体製造方法および半導体製造装置

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JP2011076767A (ja) * 2009-09-29 2011-04-14 Dainippon Printing Co Ltd 積層体、準備用支持体、積層体の製造方法、及びデバイスの製造方法
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JP2011076767A (ja) * 2009-09-29 2011-04-14 Dainippon Printing Co Ltd 積層体、準備用支持体、積層体の製造方法、及びデバイスの製造方法
WO2012056969A1 (ja) * 2010-10-29 2012-05-03 東京応化工業株式会社 積層体、およびその積層体の分離方法
JP2012124467A (ja) * 2010-11-15 2012-06-28 Tokyo Ohka Kogyo Co Ltd 積層体、および分離方法

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Publication number Priority date Publication date Assignee Title
JP2015217566A (ja) * 2014-05-15 2015-12-07 東京応化工業株式会社 積層体の製造方法および積層体
JP2016092079A (ja) * 2014-10-30 2016-05-23 東京応化工業株式会社 支持体分離方法
WO2020080276A1 (ja) * 2018-10-16 2020-04-23 富士フイルム株式会社 レーザ剥離用の積層体、組成物およびキット
WO2022210154A1 (ja) * 2021-04-01 2022-10-06 東レ株式会社 積層体および半導体装置の製造方法

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