JP2019125646A - Substrate processing device and substrate processing method - Google Patents

Abstract

To provide a substrate processing device and a substrate processing method, capable of reducing an effect on subsequent processing and further preventing residue from scattering from a substrate and contaminating the surrounding environment, by certainly removing residue adhering to a substrate.SOLUTION: A substrate processing device 1 includes: a light irradiation unit 2 which irradiates a laminate 50 with light to alter a reaction layer 20, the laminate including a support 10, a substrate 40, and the reaction layer 20 interposed between the support 10 and the substrate 40; a peeling unit 3 for peeling the substrate 40 from the support 10; a first cleaning unit 4 for cleaning, with a liquid, the substrate 40 peeled from the support 10; and a second cleaning unit 5 for processing, with plasm, the substrate 40 peeled from the support 10.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a substrate processing apparatus and a substrate processing method.

  In recent years, as an example of a method of manufacturing an electronic device, a method called a so-called fan-out type PLP (Fan-out Panel Level Package) technology is known. In the fan-out type PLP technology, for example, a reaction layer which is altered by light absorption or heating is formed on a support such as a wafer or a glass plate, and a substrate having electronic components is laminated thereon to form a laminate. . Thereafter, light or heat is applied to the reaction layer to separate the substrate from the support, and the substrate is washed, and then the substrate is cut into electronic components to obtain an electronic device (see, for example, Patent Document 1).

JP, 2010-3748, A

  In the above-mentioned fan-out type PLP technology, light or heat is applied to the reaction layer of the laminate to separate the substrate from the support, but the residue of the reaction layer sometimes adheres to the substrate. The residue may be degraded by light or heat, and the residue may be difficult to remove even if it is washed with a solvent. If the residue remains attached, the residue may affect the subsequent processing. In addition, when the substrate is transported to another place in a state where the residue is attached, the residue may be scattered from the substrate surface, which may contaminate the surrounding environment.

  The present invention can reliably remove the residue adhering to the substrate to reduce the influence on the subsequent processing, and further prevents the residue from scattering from the substrate and contaminating the surrounding environment. It is an object of the present invention to provide a substrate processing apparatus and a substrate processing method that can be performed.

  In the first aspect of the present invention, light is applied to a laminate including a support, a substrate, and a reaction layer interposed between the support and the substrate, whereby the light is used to alter the reaction layer. An irradiation unit, a peeling unit for peeling the substrate from the support, a first cleaning unit for washing the substrate peeled from the support with a liquid, and a plasma from the substrate peeled from the support And a second cleaning unit for processing.

  In the second aspect of the present invention, light irradiation is performed to alter the reaction layer by irradiating the laminate with a support, a substrate, and a reaction layer interposed between the support and the substrate. A step of peeling the substrate from the support, a liquid washing step of washing the substrate peeled from the support with a liquid, and plasma treating the substrate peeled from the support And a substrate cleaning method.

  According to the present invention, the influence on the subsequent processing is reduced by reliably removing the residue adhering to the substrate by the liquid cleaning step by the first cleaning unit and the plasma cleaning step by the second cleaning unit substrate. Further, it is possible to prevent the residue from scattering from the substrate and contaminating the surrounding environment.

It is a figure which shows an example of the substrate processing apparatus regarding 1st Embodiment by a functional block. An example of the laminated body processed with a substrate processing apparatus is shown, (A) is a figure of the laminated body containing an adhesive layer, (B) is a figure of the laminated body which does not contain an adhesive layer. An example of the holding tool holding a laminated body is shown, (A) is a perspective view of the holding tool holding a laminated body, (B) is sectional drawing in alignment with the AA of (A). It is a flowchart which shows an example of the substrate processing method regarding embodiment. An example of a light irradiation unit and a light irradiation process is shown, (A) is a figure in the case of irradiating light to the whole surface of a layered product, (B) is a figure in the case of scanning light to a layered product. An example of a peeling unit and a peeling process is shown, (A) is a figure before peeling a support body, (B) is a figure after peeling a support body. An example of a 1st washing | cleaning unit and a liquid washing | cleaning process is shown, (A) is a figure of the state which wash | cleans a board | substrate with a liquid, (B) is a figure which shows the board | substrate after a liquid washing process. 7A and 7B show an example of a second cleaning unit and a plasma cleaning step, in which FIG. 7A shows a state in which the substrate is cleaned by plasma, and FIG. 7B shows a substrate after the plasma cleaning step. . An example of a 3rd washing | cleaning unit and a liquid washing | cleaning process is shown, (A) is a figure of the state which wash | cleans a board | substrate with a liquid, (B) is a figure which shows the board | substrate after a liquid washing process. FIGS. 9A and 9B show another example of the second cleaning unit and the plasma cleaning step, in which FIG. 9A shows a state in which the substrate is cleaned by plasma, and FIG. 9B shows the substrate after the plasma cleaning step. It is. 10A and 10B show another example of the first cleaning unit and the liquid cleaning process, in which (A) shows a state in which the substrate is cleaned with liquid, and (B) shows the substrate after the liquid cleaning process. It is. The other example of a 2nd cleaning unit and a plasma cleaning process is shown, (A) is a figure of the state which is washing | cleaning the board | substrate by plasma, (B) is a figure which shows the board | substrate after a plasma cleaning process. FIG. 12 shows another example of the first cleaning unit and the liquid cleaning process, in which (A) shows the state in which the substrate is cleaned with a liquid, and (B) shows the substrate after the liquid cleaning process. It is. It is a figure which shows the other example of the board | substrate after a liquid washing | cleaning process and a plasma washing | cleaning process. FIGS. 14A and 14B show another example of the second cleaning unit and the plasma cleaning step, in which FIG. 14A shows a state in which the substrate is cleaned by plasma, and FIG. 14B shows the substrate after the plasma cleaning step. It is. It is a figure which shows an example of arrangement | positioning of each unit of a substrate processing apparatus. It is a flowchart which shows the other example of the substrate processing method regarding embodiment. The other example of a light irradiation unit and a light irradiation process is shown, (A) is a figure in the case where light is irradiated to the whole surface of a layered product, (B) is a figure in the case of scanning light to a layered product. The other example of a peeling unit and a peeling process is shown, (A) is a figure before peeling a support body, (B) is a figure after giving a support body. The other example of a 3rd washing | cleaning unit and a liquid washing | cleaning process is shown, (A) is a figure of the state which wash | cleans a board | substrate with a liquid, (B) is a figure which shows the board | substrate after a liquid washing process. FIGS. 20A and 20B show another example of the second cleaning unit and the plasma cleaning step, in which FIG. 20A shows a state in which the substrate is cleaned by plasma, and FIG. 20B shows the substrate after the plasma cleaning step. It is. (A) is a figure which shows the other example of the board | substrate after a liquid washing | cleaning process and a plasma washing | cleaning process, (B) is a figure of the state which is washing | cleaning the board | substrate by a liquid following (A). It is a figure which shows the other example of arrangement | positioning of each unit of a substrate processing apparatus.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the drawings, in order to make each configuration easy to understand, there is a portion in which a part is emphasized or a part is represented in a simplified manner, which may differ from the actual structure or shape, scale, etc. is there.

<Substrate processing apparatus>
FIG. 1 is a diagram showing an example of the substrate processing apparatus 1 according to the first embodiment by functional blocks. The substrate processing apparatus 1 shown in FIG. 1 performs various processes on the stacked body 50 to form a substrate 40. The laminate 50 includes a support 10, a reaction layer 20, an adhesive layer 30, and a substrate 40. Although not shown, the support 10 separated from the laminate 50 may be taken out of the substrate processing apparatus 1 as appropriate, or after being stored in the substrate processing apparatus 1 until a predetermined number of sheets are reached, the substrate processing is collectively performed. It may be removed from the device 1. As shown in FIG. 1, the substrate processing apparatus 1 includes a light irradiation unit 2, a peeling unit 3, a first cleaning unit 4, a second cleaning unit 5, a third cleaning unit 6, and a transport unit 7. Have.

  The light irradiation unit 2 changes the reaction layer 20 by irradiating the laminate 50 with light. The light irradiation unit 2 has, for example, a mounting table (not shown) for mounting the stacked body 50, and an irradiation device (not shown) for irradiating light of a wavelength that can alter the reaction layer 20. The light from the irradiation device may be emitted from the support 10 side of the laminate 50 or may be emitted from the substrate 40 side of the laminate 50. Details of the light source provided in the irradiation device and the light emitted from the light source will be described later. Moreover, the light from an irradiation apparatus may be irradiated from both the support body 10 side of the laminated body 50, and the board | substrate 40 side. Further, the irradiation of light from the irradiation device may be performed by a method of scanning a spot light, a method of irradiating light to the entire surface of the laminate 50, or a step of irradiating light while irradiating a part of the laminate 50 with light. It may be any method of shifting.

  The light irradiation unit 2 is accommodated and disposed, for example, in a chamber dedicated to the light irradiation unit 2 in the substrate processing apparatus 1. This chamber can prevent light emitted from the irradiation device from leaking out of the chamber in the substrate processing apparatus 1.

  The peeling unit 3 peels the substrate 40 from the support 10. The laminate 50 in a state in which the reaction layer 20 is altered by the light irradiation unit 2 is carried into the peeling unit 3. The peeling unit 3 has, for example, a fixing base (not shown) for fixing the stacked body 50 and an adsorption device (not shown) for adsorbing the support 10. The peeling unit 3 fixes the stacked body 50 to the fixing base with the support 10 on the upper side, and in this state, adsorbs the adsorption device to the support 10 and pulls up the support 10 or lowers the fixing base. The substrate 40 is peeled off.

  The first cleaning unit 4 cleans the substrate 40 peeled off from the support 10 with a liquid. The first cleaning unit 4 is a liquid cleaning device. The first cleaning unit 4 includes, for example, a mounting table (not shown) for mounting the substrate 40, a liquid supply device (not shown) for supplying a liquid to the substrate 40 mounted on the mounting table, and the substrate 40. And a discharge unit (not shown) for discharging the cleaned liquid. The first cleaning unit 4 uses a liquid to remove the adhesive layer 30 attached to the substrate 40 peeled off from the support 10.

The liquid used in the first cleaning unit 4 contains one or more selected from a hydrocarbon-based organic solvent, a nitrogen-containing organic solvent, an ether-based solvent, and an ester-based solvent. Examples of the hydrocarbon-based organic solvent include linear hydrocarbons such as hexane, heptane, octane, nonane, methyl octane, decane, undecane, dodecane, tridecane and the like; branched hydrocarbons having 4 to 15 carbon atoms; Cyclic hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene and tetrahydronaphthalene; p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpin, 1,8-terpin, bornane , Norbornane, pinane, tujan, carang, longiphorene, geraniol, nerolol, linalool, linalool, citral, citralonerol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, te Terpene solvents such as pinene-4-ol, dihydroterpinyl acetate, 1,4-cineole, 1,8-cineole, borneol, carvone, yonone, touyon, camphor, d-limonene, l-limonene, dipentene; anisole Aromatic organic solvents such as ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether and the like. The nitrogen-containing organic solvent is, for example, a solvent having an amide bond such as N-methylpyrrolidone, NN-dimethylacetamide, dimethylformamide or the like. Examples of ether solvents include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; and ester bonds such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate A compound having a cyclic ether such as dioxane; a monoalkyl ether such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether of monohydric alcohol or monoethyl ether of monohydric alcohol or a compound having the ester bond It is a derivative of polyhydric alcohols such as a compound having an ether bond. As ester solvents, for example, esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate and the like It is kind.
In addition, as a highly readily available solvent, TZNR (registered trademark) -HC thinner or the like manufactured by Tokyo Ohka Kogyo Co., Ltd. can be used.

  The first cleaning unit 4 is accommodated and disposed, for example, in a chamber dedicated to the first cleaning unit 4 in the substrate processing apparatus 1. This chamber can prevent the liquid supplied from the liquid supply device from leaking out of the chamber in the substrate processing apparatus 1.

The second cleaning unit 5 processes the substrate 40 peeled off from the support 10 by plasma. The second cleaning unit 5 is a plasma cleaning device. The second cleaning unit 5 has, for example, a mounting table (not shown) for mounting the substrate 40, and a plasma generator (not shown) for generating plasma. By applying the plasma generated by the plasma generator to the substrate 40 mounted on the mounting table, the residue of the reaction layer 20 altered by the light irradiation unit 2 described above is removed. The second cleaning unit 5 processes the substrate 40 by oxygen plasma, for example. The second cleaning unit 5 may use a plasma using a gas such as N ₂ , NH ₃ , or CF ₄ instead of the oxygen plasma.

  The second cleaning unit 5 is accommodated and disposed, for example, in a chamber dedicated to the second cleaning unit 5 in the substrate processing apparatus 1. This chamber can prevent the plasma generated by the plasma cleaning apparatus from leaking out of the chamber in the substrate processing apparatus 1.

  The third cleaning unit 6 cleans the substrate 40 peeled off from the support 10 with a liquid. The third cleaning unit 6 is a liquid cleaning device. For example, the third cleaning unit 6 includes a mounting table (not shown) for mounting the substrate 40, a liquid supply device (not shown) for supplying a liquid to the substrate 40 mounted on the mounting table, and the substrate 40. And a discharge unit (not shown) for discharging the cleaned liquid. The third cleaning unit 6 removes and cleans with the liquid the degraded portion (altered layer 20 a described later) of the reaction layer 20 adhering to the substrate 40 peeled off from the support 10. The liquid used in the third cleaning unit 6 includes one or more selected from a hydrocarbon-based organic solvent, a nitrogen-containing organic solvent, an ether-based solvent, and an ester-based solvent. The hydrocarbon-based organic solvent, the nitrogen-containing organic solvent, the ether-based solvent, or the ester-based solvent is the same as the liquid used in the first cleaning unit 4. The liquid used in the third cleaning unit 6 may be water.

  The third cleaning unit 6 is accommodated and disposed, for example, in a chamber dedicated to the third cleaning unit 6 in the substrate processing apparatus 1. This chamber can prevent the liquid supplied from the liquid supply device from leaking out of the chamber in the substrate processing apparatus 1.

  The peeling unit 3, the first cleaning unit 4, the second cleaning unit 5, and the third cleaning unit 6 described above are disposed in the same space formed by a plurality of panels. In this space, a carrier 10 or a carrier unit 7 for carrying the substrate 40 peeled from the carrier 10 is disposed. The transport unit 7 has a transport device 7a. The transfer device 7 a includes, for example, a holding unit (not shown) that holds the stacked body 50 or the substrate 40 and a traveling unit that travels along a guide or the like laid in the substrate processing apparatus 1. The holding unit and the traveling unit are driven by a drive device (not shown). The transfer device 7 a transfers the stacked body 50 carried into the substrate processing apparatus 1 to the light irradiation unit 2. Further, the transport device 7 a transports the stacked body 50 irradiated with the light by the light irradiation unit 2 to the peeling unit 3. Further, the transfer device 7 a transfers the substrate 40 after the support 10 is separated by the separation unit 3 between the first cleaning unit 4, the second cleaning unit 5, and the third cleaning unit 6. Further, the transfer device 7 a may transfer the support 10 separated by the peeling unit 3.

  The operation of each unit described above is also described in the substrate processing method described later.

<Laminate>
The laminate 50 processed by the substrate processing apparatus 1 will be described. FIG. 2 shows an example of a laminate processed by the substrate processing apparatus 1. FIG. 2 (A) is a view of the laminate 50 including the adhesive layer 30, and FIG. 2 (B) is a laminate without the adhesive layer 30. It is a figure of 50A. That is, the laminated body 50 shown to FIG. 2 (A) is provided with the support body 10, the reaction layer 20, the contact bonding layer 30, and the board | substrate 40. FIG. In addition, a laminate 50A shown in FIG. 2B includes a support 10, a reaction layer 20, and a substrate 40.

  The substrate processing apparatus 1 may include, for example, a laminate forming unit that forms the laminates 50 and 50A, or may be connected to the laminate forming unit and disposed. The laminate forming unit includes, for example, a reaction layer forming apparatus for forming the reaction layer 20 on the support 10, an adhesive layer forming apparatus for forming the adhesive layer 30 on the reaction layer 20, and the adhesive layer 30 or on the reaction layer 20. And a substrate forming apparatus for disposing the electronic component 41 thereon to form the mold. Below, the element used by each part of the above-mentioned laminated body formation unit is demonstrated.

(Support)
The support 10 is, for example, a circular or substantially circular semiconductor wafer having a thickness of 50 to 500 μm. The thickness of the semiconductor wafer is arbitrary. Further, as the support 10, a glass plate having a thickness of 500 to 1500 μm may be used instead of the semiconductor wafer, for example. The support 10 is not limited to a circular shape or a substantially circular shape, and may have another shape such as, for example, a rectangular shape, an elliptical shape, or a polygonal shape.

(Reaction layer)
The reaction layer 20 is formed of, for example, a material that changes in quality by absorbing light. In the present embodiment, the alteration of the reaction layer 20 means that the reaction layer 20 can be broken by receiving a slight external force or the adhesion to the layer in contact with the reaction layer 20 is lowered. The reaction layer 20 absorbs light and deteriorates, so that the strength or the adhesion to the support 10 is reduced compared to before the deterioration. Therefore, the reaction layer 20 after the alteration is broken or peeled off from the support 10 by applying a slight external force (for example, lifting the support 10).

  Deterioration of the reaction layer 20 is caused by the energy of the absorbed light (pyrogenic or non-pyrogenic) decomposition, cross-linking, change of configuration or dissociation of functional groups (and curing of the reaction layer 20 accompanying these, degassing, And the like. Degeneration of the reaction layer 20 occurs as a result of the absorption of light by the material comprising the reaction layer 20. Thus, the type of alteration of the reaction layer 20 may change depending on the type of material that constitutes the reaction layer 20. In addition, the reaction layer 20 is not limited to a material that changes in quality by absorbing light. For example, it may be a material which is denatured by absorbing heat given without light, or a material which is denatured by another solvent or the like.

  The thickness of the reaction layer 20 is more preferably, for example, 0.05 to 50 μm, and still more preferably 0.3 to 1 μm. If the thickness of the reaction layer 20 is within the range of 0.05 to 50 μm, the irradiation of light for a short time and the irradiation of light of low energy, or heating for a short time, immersion in a solvent for a short time, etc. The reaction layer 20 can be made to produce desired degeneration. Further, the thickness of the reaction layer 20 is particularly preferably within the range of 1 μm or less from the viewpoint of productivity.

  Hereinafter, the reaction layer 20 which is denatured by the energy of the absorbed light will be described. The reaction layer 20 is preferably formed of only a material having a light absorbing structure, but a material having no light absorbing structure is added to the extent that the essential characteristics are not impaired. The reaction layer 20 may be formed. Moreover, it is preferable that the surface on the side facing the adhesive layer 30 in the reaction layer 20 be flat (no unevenness is formed), whereby the adhesive layer 30 can be easily formed, and even when attached. It becomes possible to paste uniformly.

The reaction layer 20 may be altered by absorbing the light emitted from the laser. That is, the light irradiated to the reaction layer 20 (the light emitted from the irradiation device of the light irradiation unit 2 described above) to deteriorate the reaction layer 20 may be irradiated from a laser. Examples of lasers for emitting light to be applied to the reaction layer 20 include solid lasers such as YAG laser, ruby laser, glass laser, YVO ₄ laser, LD laser, fiber laser, liquid lasers such as dye laser, CO ₂ laser, Examples thereof include gas lasers such as excimer lasers, Ar lasers, and He-Ne lasers, semiconductor lasers, laser lights such as free electron lasers, and non-laser lights. The laser for emitting the light to be applied to the reaction layer 20 can be appropriately selected according to the material constituting the reaction layer 20, and irradiation with light of a wavelength capable of degrading the material constituting the reaction layer 20 It is sufficient to select the desired laser.

(Fluorocarbon)
The reaction layer 20 may be made of fluorocarbon. The reaction layer 20 is made of a fluorocarbon so as to be altered by absorbing light, and as a result, loses its strength or adhesiveness before being irradiated with light. Thus, by applying a slight external force (e.g., lifting the support 10), the reaction layer 20 can be broken and the support 10 and the substrate 40 can be easily separated. The fluorocarbon constituting the reaction layer 20 can be suitably formed by plasma CVD (chemical vapor deposition) method.

  Fluorocarbons absorb light having a wavelength range that is unique to their type. By irradiating the light of the wavelength of the range which the fluorocarbon used for the reaction layer 20 absorbs in the reaction unit 20 in the light irradiation unit 2, the fluorocarbon can be suitably degraded. In addition, it is preferable that the absorption factor of the light in the reaction layer 20 is 80% or more.

The light to be applied to the reaction layer 20 may be, for example, a solid laser such as YAG laser, ruby laser, glass laser, YVO 4 laser, LD laser, fiber laser, or liquid laser such as dye laser according to the wavelength that fluorocarbon can absorb. A laser such as a gas laser such as a CO ₂ laser, an excimer laser, an Ar laser, or a He—Ne laser, a semiconductor laser, a free electron laser, or a non-laser light may be used as appropriate. The wavelength at which the fluorocarbon can be altered is not limited to this, but for example, one having a wavelength of 600 nm or less can be used.

(A polymer containing a light absorbing structure in its repeating unit)
The reaction layer 20 may contain a polymer having a light absorbing structure in its repeating unit. The polymer is irradiated with light in the light irradiation unit 2 to deteriorate. Deterioration of the polymer occurs when the above structure absorbs the irradiated light. The reaction layer 20 loses its strength or adhesiveness before being irradiated with light as a result of the degeneration of the polymer. Thus, by applying a slight external force (e.g., lifting the support 10), the reaction layer 20 can be broken and the support 10 and the substrate 40 can be easily separated.

  The above-mentioned structure having a light absorbing property is a chemical structure which absorbs light and denatures a polymer containing the structure as a repeating unit. The structure is, for example, an atomic group containing a conjugated π electron system consisting of a substituted or unsubstituted benzene ring, a fused ring or a heterocycle. More specifically, the structure may be a cardo structure, or a benzophenone structure, a diphenyl sulfoxide structure, a diphenyl sulfone structure (bisphenylsulfone structure), a diphenyl structure or a diphenylamine structure which is present in the side chain of the polymer.

  When the above structure is present in the side chain of the above polymer, the structure may be represented by the following formula.

(Wherein, R is each independently an alkyl group, an aryl group, a halogen, a hydroxyl group, a ketone group, a sulfoxide group, a sulfone group or an N (R ¹ ) (R ² ) group, where R ¹ and R ² is each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), Z is absent or is -CO-, -SO _2- , -SO- or -NH-, n Is an integer of 0 or 1 to 5.)
In addition, the polymer contains, for example, a repeating unit represented by any of the following formulas (a) to (d), or represented by (e), or (f) The structure is included in its main chain.

(Wherein, l is an integer of 1 or more, m is an integer of 0 or 1 to 2, and X is any of the compounds represented by the chemical formula [Chemical formula 1] in (a) to (e) And (f) is any of the formulas shown above in Chemical Formula 1 or is absent, 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, the condensed ring and the heterocyclic ring represented by the above chemical formula [Chemical formula 1] include phenyl, substituted phenyl, benzyl, substituted benzyl, naphthalene, substituted naphthalene, anthracene, substituted anthraquinone, anthraquinone, substituted anthraquinone, acridine, Examples include substituted acridine, azobenzene, substituted azobenzene, fluorene, substituted fluorene, substituted fluorenone, carbazole, substituted carbazole, N-alkylcarbazole, dibenzofuran, substituted dibenzofuran, phenanthrene, substituted phenanthrene, pyrene and substituted pyrene. When the exemplified substituent further has a substituent, the substituent is, for example, alkyl, aryl, halogen atom, alkoxy, nitro, aldehyde, cyano, amido, dialkylamino, sulfonamide, imide, carboxylic acid, It is selected from carboxylic esters, sulfonic acids, sulfonic esters, alkylaminos and arylaminos.

Among the substituents represented by the above chemical formula [Formula 1], a fifth substituent having two phenyl groups, in which Z is —SO ₂ —, is exemplified by bis (2 4-dihydroxyphenyl) sulfone, bis (3,4-dihydroxyphenyl) sulfone, bis (3,5-dihydroxyphenyl) sulfone, bis (3,6-dihydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfone, Examples include bis (3-hydroxyphenyl) sulfone, bis (2-hydroxyphenyl) sulfone, and bis (3,5-dimethyl-4-hydroxyphenyl) sulfone.

  Among the substituents represented by the above chemical formula [Formula 1], a fifth substituent having two phenyl groups, wherein Z is -SO-, is exemplified by bis (2,2, 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 (2,2, 3,4-Trihydroxyphenyl) sulfoxide, bis (2,3,4-trihydroxy-6-methyl) Phenyl) -sulfoxide, bis (5-chloro-2,3,4-trihydroxyphenyl) sulfoxide, bis (2,4,6-trihydroxyphenyl) sulfoxide, bis (5-chloro-2,4,6-triphenyl) sulfoxide And hydroxyphenyl) sulfoxide and the like.

  Examples of the fifth substituent having two phenyl groups among the substituents represented by the above chemical formula [Formula 1], in which Z is -C (= O)-, 2,4-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 Dimethylamino-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 above structure is present in the side chain of the above polymer, the ratio of the repeating unit containing the above structure to the above polymer is that the light transmittance of the reaction layer 20 is 0.001% or more, 10 It is in the range which becomes less than%. If the polymer is prepared such that the ratio falls within such a range, the reaction layer 20 can sufficiently absorb light and can be denatured surely and rapidly. That is, removal (or separation, peeling) of the support 10 from the laminate 50 is easy, and the light irradiation time required for the removal can be shortened.

  The above structure, by choice of its type, can absorb light having a desired range of wavelengths. For example, the wavelength of light that can be absorbed by the structure is more preferably in the range of 100 nm or more and 2,000 nm or less. Within this range, the wavelength of light that can be absorbed by the above-described structure is on the shorter wavelength side, and for example, in the range of 100 nm or more and 500 nm or less. For example, the structure may degrade the polymer comprising the structure by absorbing ultraviolet light, preferably having a wavelength in the range 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 and 436 nm or less), KrF excimer laser (wavelength: 248 nm), ArF excimer laser (wavelength: 193 nm), F2 excimer laser (wavelength: 157 nm) Or light emitted from an XeCl laser (wavelength: 308 nm), an XeF laser (wavelength: 351 nm) or a solid state UV laser (wavelength: 355 nm), or g-ray (wavelength: 436 nm), h-ray (wavelength: 405 nm) or i-ray Wavelength: 365 nm) and the like.

  Although the reaction layer 20 mentioned above contains the polymer which contains the said structure as a repeating unit, the reaction layer 20 may further contain components other than the said polymer. Examples of such components include fillers, plasticizers, and components capable of improving the releasability of the support 10. These components are appropriately selected from conventionally known substances or materials which do not prevent or promote the absorption of light by the above structure and the deterioration of the polymer.

(Inorganic substance)
The reaction layer 20 may be made of an inorganic material. The reaction layer 20 is made of an inorganic substance, and is denatured by absorbing light, and as a result, loses its strength or adhesiveness before being irradiated with light. Thus, by applying a slight external force (e.g., lifting the support 10), the reaction layer 20 can be broken and the support 10 and the substrate 40 can be easily separated.

The inorganic substance only needs to be configured to be denatured by absorbing light, and, for example, one or more inorganic substances selected from the group consisting of metals, metal compounds and carbon can be suitably used. The metal compound refers to a compound containing a metal atom, and may be, for example, a metal oxide or a metal nitride. Exemplary of such inorganic include, but are not limited to, gold, silver, copper, iron, nickel, aluminum, titanium, _{chromium, SiO 2, SiN, Si 3} N 4, TiN, and carbon And one or more types of inorganic substances selected from the group consisting of In addition, carbon is a concept which may also include an allotrope of carbon, and may be, for example, diamond, fullerene, diamond-like carbon, carbon nanotube and the like.

  The above-mentioned inorganics absorb light having a wavelength range unique to the type. By irradiating the light of the wavelength of the range which the inorganic substance used for the reaction layer 20 absorbs to a separation layer, the above-mentioned inorganic substance can be changed suitably.

The light irradiated to the reaction layer 20 made of an inorganic substance in the light irradiation unit 2 may be, for example, a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, or a fiber laser according to the wavelength that can be absorbed by the inorganic substance. Laser such as solid laser such as dye laser, liquid laser such as dye laser, CO ₂ laser, gas laser such as Ar laser, He-Ne laser, semiconductor laser, free electron laser, or non-laser light Just do it.

  The reaction layer 20 made of an inorganic substance can be formed on the support 10 by a known technique such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, spin coating and the like. The thickness of the reaction layer 20 made of an inorganic substance is not particularly limited as long as it can sufficiently absorb the light to be used. For example, the thickness should be in the range of 0.05 μm to 10 μm. Is more preferred. Alternatively, an adhesive may be applied in advance to both sides or one side of an inorganic film (for example, a metal film) made of an inorganic material that constitutes the reaction layer 20, and may be attached to the support 10 and the substrate 40.

  When a metal film is used as the reaction layer 20, depending on the film quality of the reaction layer 20, the type of the laser light source, the laser output, etc., reflection of the laser or charging of the film may occur. Therefore, it is preferable that measures be taken by providing an antireflective film or an antistatic film on the upper and lower sides or one of the reaction layers 20.

(Compound having an infrared absorbing structure)
The reaction layer 20 may be formed of a compound having an infrared absorbing structure. The compound degrades by absorbing infrared radiation. The reaction layer 20 loses its strength or adhesiveness before being irradiated with infrared radiation as a result of the deterioration of the compound. Thus, by applying a slight external force (e.g., lifting the support, etc.), the reaction layer 20 can be broken and the support 10 and the substrate 40 can be easily separated.

Examples of the compound having a structure having infrared absorptivity or a structure having an infrared absorptivity include alkanes and alkenes (vinyl, trans, cis, vinylidene, trisubstituted, tetrasubstituted, conjugated, cumulene, Cyclic), alkynes (monosubstituted, disubstituted), monocyclic aromatics (benzene, monosubstituted, disubstituted, trisubstituted), alcohols and phenols (free OH, intramolecular hydrogen bond, intermolecular hydrogen bond, saturated Secondary, saturated tertiary, unsaturated secondary, unsaturated tertiary), acetals, ketals, aliphatic ethers, aromatic ethers, vinyl ethers, oxirane ring ethers, peroxide ethers, ketones, dialkyl carbonyls, Aromatic carbonyl, enol of 1,3-diketone, o-hydroxy aryl ketone, dialkyl aldehyde, aromatic aldehyde, carboxylic acid (dimer, Rubonic acid anion), formate ester, acetate ester, conjugated ester, nonconjugated 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), primary Tertiary amines (aliphatic, aromatic), primary amine salts, secondary amine salts, tertiary amine salts, ammonium ions, aliphatic nitriles, aromatic nitriles, carbodiimides, aliphatic isonitriles, aromatic isonitriles, Isocyanate ester, thiocyanate ester, aliphatic isothiocyanate ester, aromatic isothiocyanate ester, aliphatic nitro compound, aromatic nitro compound, nitroamine, nitrosamine, nitrate Esters, nitrites, nitroso bonds (aliphatic, aromatic, monomers, dimers), mercaptans and sulfur compounds such as thiophenols and thiol acids, thiocarbonyl groups, sulfoxides, sulfones, sulfonyl chlorides, primary Sulfonamide, secondary sulfonamide, sulfuric 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 bond.

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 And aryl chlorides and the like.

Examples of the structure containing the Si-A ¹ bond include SiH, SiH ₂ , SiH ₃ , Si-CH ₃ , Si-CH _2- , Si-C ₆ H ₅ , SiO-aliphatic, Si-OCH ₃ , Si- _{OCH 2 CH 3, Si-OC} 6 H 5, Si-O-Si, Si-OH, SiF, SiF 2, and SiF _3, and the like. As a structure containing a Si-A ¹ bond, it is particularly preferable to form a siloxane skeleton and a silsesquioxane skeleton.

As the structure containing the above-mentioned PA ² bond, PH, PH ₂ , P-CH ₃ , P-CH _2- , P-C ₆ H ₅ , A ³ ₃ -PO (A ³ is aliphatic or aromatic Group), (A ⁴ O) ₃ -P-O (A ⁴ is alkyl), P-OCH ₃ , P-OCH ₂ CH ₃ , P-OC ₆ H ₅ , P-O-P, P-OH, and O = P-OH etc. are mentioned.

  The above structure, by choice of its type, can absorb infrared radiation having a desired range of wavelengths. Specifically, the wavelength of infrared light that can be absorbed by the above-described structure is, for example, in the range of 1 μm to 20 μm, and can more preferably absorb in the range of 2 μm to 15 μm. Furthermore, when the said structure is a Si-O bond, a Si-C bond, and a Ti-O bond, it can be in the range of 9 micrometers or more and 11 micrometers or less. The wavelength of infrared light that can be absorbed by each structure can be easily understood by those skilled in the art. For example, as an absorption band in each structure, Non-Patent Document: SILVERSTEIN · BASSLER · MORRILL "Spectroscopic identification method of organic compounds by spectrum (fifth edition)-combined use of MS, IR, NMR, UV-" (issued in 1992) The description on pages 146 to 151 can be referred to.

  Among the compounds having a structure as described above, the compound having a structure having an infrared absorbing property, which is used to form the reaction layer 20, can be dissolved in a solvent for coating, and is solidified and solidified. It is not particularly limited as long as it can form a layer. However, in order to effectively change the compound in the reaction layer 20 and to facilitate the separation of the support 10 and the substrate 40, the absorption of infrared rays in the reaction layer 20 is large, that is, the reaction layer by the light irradiation unit 2 It is preferable that the transmittance of infrared rays when the infrared rays are irradiated to 20 be low. Specifically, the transmittance of infrared light in the reaction layer 20 is preferably lower than 90%, and more preferably lower than 80%.

  For example, the compound having a siloxane skeleton is a copolymer of a repeating unit represented by the following chemical formula [Chemical formula 3] and a repeating unit represented by the following chemical formula [chemical formula 4]. It is possible to use a certain resin or a resin which is a copolymer of a repeating unit represented by the following chemical formula [Chemical formula 4] and a repeating unit derived from an acrylic compound.

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

  Further, as a compound having a silsesquioxane skeleton, for example, a resin which is a copolymer of a repeating unit represented by the following chemical formula [Chemical formula 6] and a repeating unit represented by the following chemical formula [chemical formula 7] It can be used.

(In the above chemical formula [Chemical formula 6], R ⁴ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and in the above chemical formula [chemical formula 7], R ⁵ has 1 or more carbon atoms and 10 or less) It is an alkyl group or a phenyl group.)
As compounds having a silsesquioxane skeleton, JP-A-2007-258663 (released on October 4, 2007), JP-A-2010-120901 (released on June 3, 2010), and the like can also be mentioned. Preferably, the silsesquioxane resins disclosed in JP2009-263316A (released on November 12, 2009) and JP2009-263596A (released on November 12, 2009) are preferably used. Can.

  Among them, as the compound having a silsesquioxane skeleton, a copolymer of a repeating unit represented by the following chemical formula [Chemical formula 8] and a repeating unit represented by the following chemical formula [Chemical formula 9] is more preferable, and the following The copolymer containing the repeating unit represented by the chemical formula [Chemical formula 8] and the repeating unit represented by the following chemical formula [chemical formula 9] at 7: 3 is more preferable.

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

Moreover, as a compound containing a Ti-O bond, for example, (i) tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, and titanium-i-propoxy octylene glycolate Etc .; (ii) di-i-propoxy.bis (acetylacetonato) titanium and chelate titanium such as propanedioxytitanium bis (ethylacetoacetate); (iii) i-C ₃ H ₇ O-[- _{Ti (O-i-C 3} H 7) 2 -O-] n -i-C 3 H 7, and _{n-C 4 H 9 O -} [- Ti (O-n-C 4 H 9) 2 -O A titanium polymer such as _n- n-C ₄ H ₉ ; (iv) tri-n-butoxytitanium monostearate, titanium stearate, di-i-propoxytitanium di- Acylate titanium such as isostearate and (2-n-butoxycarbonylbenzoyloxy) tributoxytitanium; (v) water-soluble titanium compounds such as di-n-butoxy bis (triethanolaminato) titanium etc. Be

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 preferable.

  Although the reaction layer 20 mentioned above contains the compound which has an infrared absorptive structure, the reaction layer 20 may further contain components other than the said compound. Examples of such components include fillers, plasticizers, and components capable of improving the releasability of the support 10. These components are appropriately selected from conventionally known substances or materials which do not prevent or promote absorption of infrared rays and deterioration of compounds due to the above-mentioned structure.

(Infrared absorbing material)
The reaction layer 20 may contain an infrared absorbing material. The reaction layer 20 is configured to contain an infrared absorbing material, so that the reaction layer 20 is degraded by absorbing light, and as a result, the strength or adhesiveness before being irradiated with light is lost. Thus, by applying a slight external force (e.g., lifting the support 10), the reaction layer 20 can be broken and the support 10 and the substrate 40 can be easily separated.

  The infrared ray absorbing material may be any structure as long as it is denatured by absorbing infrared rays, and for example, carbon black, iron particles or aluminum particles can be suitably used. Infrared absorbing materials absorb light having a wavelength in a specific range depending on their type. By irradiating the light of the wavelength of the range which the infrared rays absorbing material used for the reaction layer 20 absorbs to the reaction layer 20 in the light irradiation unit 2, the infrared rays absorbing material can be suitably degraded.

  The reaction layer 20 is formed by disposing a liquid containing the above-described material on one surface (a reaction layer formation surface) 110 of the support 10. For example, while the support 10 is placed on a stage such as a coating apparatus, and the slit nozzle for discharging the liquid and the support 10 are relatively moved, the liquid from the slit nozzle is formed on the reaction layer forming surface 110 Let it discharge. Thus, the reaction layer 20 is formed on the entire surface of the reaction layer forming surface 110 of the support 10. In addition, as a coating method of the reaction layer 20, it is not limited to the above slit nozzle method, For example, even if it carries out by the coating method by a spin coat method, dipping method, roller blade method, doctor blade method, spray method etc. Good.

(Adhesive layer)
The resin contained in the adhesive layer 30 may be any one having adhesiveness, and, for example, a hydrocarbon resin, an acryl-styrene resin, a maleimide resin, an elastomer resin, or a combination thereof may be used. It can be mentioned.

  The glass transition temperature (Tg) of the adhesive changes depending on the type and molecular weight of the above-mentioned resin, and the compounding of the plasticizer to 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 in the adhesive is in the range of -60 ° C. or more and 200 ° C. or less The inside is preferable, and the inside of the range of -25 degreeC or more and 150 degrees C or less is more preferable. When the Tg of the resin used for the adhesive is in the range of −60 ° C. or more and 200 ° C. or less, the adhesion of the adhesive layer 30 can be suitably reduced without requiring excessive energy for cooling. In addition, the Tg of the adhesive layer 30 may be adjusted by appropriately blending a plasticizer, a resin having a low degree of polymerization, or the like. The glass transition temperature (Tg) can be measured, for example, using a known differential scanning calorimeter (DSC).

(Hydrocarbon resin)
The hydrocarbon resin is a resin having a hydrocarbon backbone and formed by polymerizing a monomer composition. As a hydrocarbon resin, at least one resin selected from the group consisting of cycloolefin polymers (hereinafter sometimes referred to as "resin (A)"), terpene resins, rosin resins and petroleum resins (hereinafter referred to as " Resin (B) and the like), 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. Specifically, a ring-opened (co) polymer of a monomer component containing a cycloolefin monomer, a resin obtained by addition (co) polymerization of a monomer component containing a cycloolefin monomer, and the like can be mentioned.

  Examples of the cycloolefin-based monomer contained in the monomer component constituting the resin (A) include dicyclic substances such as norbornene and norbornadiene, tricyclic substances such as dicyclopentadiene and dihydroxypentadiene, tetracyclododecene and the like. Tetracycle, pentacycle such as cyclopentadiene trimer, heptacycle such as tetracyclopentadiene, or alkyl (methyl, ethyl, propyl, butyl, etc.) substituents of these polycyclic bodies, alkenyl (vinyl, etc.) Examples thereof include substituted products, substituted alkylidene (such as ethylidene), and substituted aryl (such as phenyl, tolyl and naphthyl). Among these, norbornene-based monomers selected from the group consisting of norbornene, tetracyclododecene or alkyl-substituted products thereof are particularly preferable.

  The monomer component which comprises resin (A) may contain the other monomer copolymerizable with the cycloolefin type monomer mentioned above, for example, it is preferable to contain 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, as a monomer component which comprises resin (A), it is preferable from a viewpoint of high heat resistance (low thermal decomposition, thermal weight reduction property) to contain a cycloolefin monomer. The ratio of the cycloolefin monomer to the entire 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 entire monomer component constituting the resin (A) is not particularly limited, but is preferably 80 mol% or less from the viewpoint of solubility and stability with time in a solution, It is more preferable that 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 entire 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. And 30 to 80 mol% are more preferable.

  In addition, resin (A) is a resin which does not have a polar group like the resin formed by polymerizing the monomer component which consists of a cycloolefin type monomer and an alkene monomer, for example, under high temperature. In order to suppress the generation of the

  The polymerization method and polymerization conditions for polymerizing the monomer components 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” manufactured by Nippon Zeon Co., Ltd., and “ZEONEX” And “ARTON” manufactured by JSR Corporation.

  The glass transition temperature (Tg) of the resin (A) is preferably 60 ° C. or more, and particularly preferably 70 ° C. or more. When the laminated body is exposed to a high temperature environment as the glass transition temperature of the resin (A) is 60 ° C. or more, the softening of the adhesive layer 30 can be further suppressed.

  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 resin, terpene phenol resin, modified terpene resin, hydrogenated terpene resin, hydrogenated terpene phenol resin and the like. Examples of rosin-based resins include rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, modified rosin and the like. 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 more, the laminate can be suppressed from being softened when exposed to a high temperature environment, and no adhesion failure occurs. On the other hand, when the softening point of the resin (B) is 160 ° C. or less, the peeling speed when peeling the laminate is good.

  Although the weight average molecular weight of resin (B) is not specifically limited, It is preferable that it is 300-3,000. When the weight average molecular weight of the resin (B) is 300 or more, the heat resistance becomes sufficient, and the amount of degassing decreases in a high temperature environment. On the other hand, when the weight average molecular weight of the resin (B) is 3,000 or less, the peeling speed when peeling the laminate is good. In addition, the weight average molecular weight of resin (B) in this embodiment means the molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC).

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

(Acrylic-styrenic resin)
As an acryl- styrene-type resin, the resin which superposed | polymerized using the derivative of styrene or a styrene, (meth) acrylic acid ester etc. as a monomer is mentioned, for example.

  Examples of (meth) acrylic acid esters include (meth) acrylic acid alkyl esters having a chain structure, (meth) acrylic acid esters having an aliphatic ring, and (meth) acrylic acid esters having an aromatic ring . Examples of the (meth) acrylic acid alkyl ester having a chain structure include acrylic long-chain alkyl esters having an alkyl group having 15 to 20 carbon atoms, acrylic alkyl esters having an alkyl group having 1 to 14 carbon atoms, and the like. . As acrylic long-chain alkyl ester, 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-eikosyl group etc. Alkyl ester is mentioned. The alkyl group may be branched.

  As an acryl-type alkyl ester which has a C1-C14 alkyl group, the well-known acryl-type alkyl ester used for the existing acryl-type adhesive agent is mentioned. For example, an alkyl of acrylic acid or methacrylic acid in which the alkyl group is methyl, ethyl, propyl, butyl, 2-ethylhexyl, isooctyl, isononyl, isodecyl, dodecyl, lauryl, tridecyl etc. Ester is mentioned.

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

  The (meth) acrylic acid ester having an aromatic ring is not particularly limited, but as the aromatic ring, for example, a phenyl group, a benzyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthracenyl group , Phenoxymethyl group, phenoxyethyl group and the like. The aromatic ring may have a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, phenoxyethyl acrylate is preferred.

(Maleimide resin)
As the maleimide resin, for example, as a monomer, N-methyl maleimide, N-ethyl maleimide, N-n-propyl maleimide, N-isopropyl maleimide, N-n-butyl maleimide, N-isobutyl maleimide, N-sec -Butyl maleimide, N-tert-butyl maleimide, N-n-pentyl maleimide, N-n-hexyl maleimide, N-n-heptyl maleimide, N-n-octyl maleimide, N-lauryl maleimide, N-stearyl maleimide, etc. Of an aliphatic hydrocarbon group such as N-cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide, N-cyclohexyl maleimide, N-cycloheptyl maleimide, N-cyclooctyl maleimide, etc. Resins obtained by polymerizing an aromatic maleimide having an aryl group such as N-phenyl maleimide, N-m-methylphenyl maleimide, N-o-methylphenyl maleimide, N-p-methylphenyl maleimide, etc. Be

  For example, a cycloolefin copolymer which is a copolymer of a repeating unit represented by the following chemical formula [Chem. 10] and a repeating unit represented by the following chemical formula [Chem. 11] can be used as a resin of the adhesive component.

(In the above chemical formula [Chemical formula 11], n is an integer of 0 or 1 to 3.)
As such cycloolefin copolymer, APL 8008T, APL 8009T, and APL 6013T (all manufactured by Mitsui Chemicals, Inc.) 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. As a substituent, a C1-C5 alkyl group, a C1-C5 alkoxy group, a C1-C5 alkoxyalkyl group, an acetoxy group, a carboxyl group etc. are mentioned, for example. Moreover, it is more preferable that content of the said styrene unit exists in the range of 14 weight% or more and 50 weight% or less. Furthermore, the elastomer preferably has a weight average molecular weight of 10,000 or more and 200,000 or less.

  If the content of the styrene unit is in the range of 14 wt% or more and 50 wt% 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, hydrocarbon solvents described later The adhesive layer 30 can be removed more easily and quickly. In addition, when the content of the styrene unit and the weight average molecular weight are in the above ranges, the resist solvent (eg, PGMEA, PGME, etc.) to which the wafer is exposed when it is subjected to the resist lithography process, acid (hydrogen fluoride) It exhibits excellent resistance to acids, etc.) and alkalis (TMAH, etc.).

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

  Further, the content of the styrene unit is more preferably 17% by weight or more, and more preferably 40% by weight or less.

  The more preferable range of the weight average molecular weight is 20,000 or more, and the more preferable range is 150,000 or less.

  As the elastomer, various elastomers can be used as long as the styrene unit content is in the range of 14% by weight to 50% by weight and the weight average molecular weight of the elastomer is in the range of 10,000 to 200,000. Can be used. For example, polystyrene-poly (ethylene / propylene) block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene-butylene-styrene block copolymer (SBBS) And these hydrogenated substances, 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 block-reacted styrene-ethylene-ethylene-propylene-styrene block copoly -(Septon V9461 (Kuraray Co., Ltd.)), styrene-ethylene-butylene-styrene block copolymer of reaction crosslinkable type (Septon V 9827 (Kuraray Co., Ltd.) having a reactive polystyrene-based hard block), etc. And those having a styrene unit content and a weight average molecular weight within the ranges described above can be used.

  Among the elastomers, a hydrogenated substance is more preferable. If it is a hydrogenated substance, the stability to heat is improved, and degradation such as decomposition or polymerization hardly occurs. Moreover, it is more preferable from the viewpoint of the solubility to a hydrocarbon solvent and the resistance to a resist solvent.

  Further, among the elastomers, those having block polymers of styrene at both ends are more preferable. By blocking styrene having high heat stability at both ends, higher heat resistance is exhibited.

  More specifically, the elastomer is more preferably a hydrogenated product of a block copolymer of styrene and a conjugated diene. The stability to heat is improved, and degradation such as decomposition or polymerization hardly occurs. Moreover, higher heat resistance is shown by blocking highly thermally stable styrene 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 adhesives which constitute adhesion layer 30, for example, Kuraray Co., Ltd. "septon (brand name)", Kuraray Co., Ltd. "hybler (trade name)", Asahi Kasei Corporation "Tuftec (trade name)" manufactured by JSR Corporation, "Dynaron (trade name)" manufactured by JSR Corporation, and the like.

  The content of the elastomer contained in the adhesive constituting the adhesive layer 30 is, for example, preferably 50 parts by weight or more and 99 parts by weight or less, 60 parts by weight or more, based on 100 parts by weight of the total amount of the adhesive composition. 99 weight parts or less are more preferable, and 70 weight parts or more and 95 weight parts or less are most preferable. By setting it in these ranges, the wafer and the support can be suitably bonded together while maintaining the heat resistance.

  Moreover, an elastomer may mix multiple types. That is, the adhesive constituting the adhesive layer 30 may contain a plurality of types of elastomers. At least one of the plurality of types of elastomers may contain a styrene unit as a constituent unit of the main chain. In addition, at least one of a plurality of types of elastomers has a styrene unit content in the range of 14 wt% or more and 50 wt% or less, or a weight average molecular weight of 10,000 or more and 200,000 or less If it is in the range, it is a category of the present invention. Moreover, in the adhesive agent which comprises the contact bonding layer 30, as a result of mixing when you contain several types of elastomers, you may adjust so that content of a styrene unit may become in said range. For example, the weight ratio 1 of Septon 4033 of Septon (trade name) manufactured by Kuraray Co., Ltd., in which the content of styrene unit is 30% by weight, and Septon 2063 of Septon (trade name), in which the content of styrene unit is 13% by weight When mixed in a one-to-one manner, the styrene content with respect to the total elastomer contained in the adhesive is 21 to 22% by weight, and thus 14% by weight or more. Further, for example, when 10 wt% of styrene units and 60 wt% of styrene units are mixed at a weight ratio of 1: 1, the ratio is 35 wt%, which falls within the above range. The present invention may be in such a form. The plurality of types of elastomers contained in the adhesive constituting the adhesive layer 30 all contain styrene units within the above range, and most preferably have a weight average molecular weight within the above range.

  In addition, it is preferable to form adhesion layer 30 using resin other than photocurable resin (for example, UV curable resin). By using a resin other than the photocurable resin, it is possible to prevent the residue from remaining around the minute unevenness of the substrate 40 after the peeling or the removal of the adhesive layer 30. In particular, the adhesive constituting the adhesive layer 30 is preferably one that does not dissolve in any solvent but dissolves in a specific solvent. This is because the adhesive layer 30 can be removed by dissolving it in a solvent without applying physical force to the substrate 40. When removing the adhesive layer 30, the adhesive layer 30 can be easily removed without damaging or deforming the substrate 40, even from the substrate 40 with reduced strength.

(Dilution solvent)
Examples of dilution solvents to be used when forming the adhesive layer 30 include linear hydrocarbons such as hexane, heptane, octane, nonane, methyl octane, decane, undecane, dodecane, tridecane and the like, and having 4 to 15 carbon atoms. Branched hydrocarbons, for example, cyclic hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, tetrahydronaphthalene, p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpine 1,8-Terpin, Bornan, norbornane, Pinan, Tujan, Callan, Longiphorene, Geraniol, Nerol, Linalol, Citralello, Citralellol, Menthol, Isomenthol, Neomenthol, α-Terpineol, β-Terpineol, γ-Terpineol , Terpinen-1-ol, terpinen-4-ol, dihydroterpinyl acetate, 1,4-cineole, 1,8-cineole, borneol, carvonone, yonone, touyon, camphor, d-limonene, l-limonene, dipentene Terpene solvents such as: lactones such as γ-butyrolactone; acetone, methyl ethyl ketone, cyclohexanone (CH), methyl n-pentyl ketone, methyl isopentyl ketone, ketones such as 2-heptanone; ethylene glycol, diethylene glycol, propylene glycol , Polyhydric alcohols such as dipropylene glycol; esthetic agents such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate Such as a compound having an alkyl bond, the monohydric ether of the compound having the polyvalent alcohol or the ester bond, a compound having an ether bond such as a monoalkyl ether such as monoethyl ether, monopropyl ether or monobutyl ether, or monobutyl ether; Derivatives of polyhydric alcohols (in these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred); Cyclic ethers such as dioxane; methyl lactate, ethyl lactate (EL) Esters such as methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; anisole, ethyl ben Jill ether, cresyl methyl ether, diphenyl ether, can be mentioned dibenzyl ether, phenetole, the aromatic organic solvent such as butyl phenyl ether.

(Other ingredients)
The adhesive constituting the adhesive layer 30 may further contain other miscible materials as long as the essential properties are not impaired. For example, various commonly used additives such as additional resins, plasticizers, adhesion aids, stabilizers, colorants, thermal polymerization inhibitors and surfactants for improving the performance of adhesives may be used. it can.

  The adhesive layer 30 is formed by disposing a liquid containing the above-described material on the reaction layer 20. For example, the support 10 is placed on a stage such as a coating apparatus, and the slit nozzle for discharging the liquid and the support 10 are relatively moved, and the liquid is discharged from the slit nozzle onto the reaction layer 20 Let Thereby, the adhesive layer 30 is formed on the entire surface of the reaction layer 20. The coating method of the adhesive layer 30 is not limited to the slit nozzle method as described above, and may be performed by, for example, a spin coating method, a dipping method, a roller blade method, a doctor blade method, a spray method, or the like. Good. In addition, after the adhesive layer 30 is applied on the reaction layer 20, it may be dried by heating or the like.

(substrate)
The substrate 40 has an electronic component 41 and a mold 42. The electronic component 41 includes, for example, a chip or the like formed using a semiconductor or the like. In the laminate 50 shown in FIG. 2A, the electronic component 41 is disposed on the adhesive layer 30. Further, in the laminate 50A shown in FIG. 2B, the electronic component 41 is disposed on the reaction layer 20.

  The mold 42 holds the electronic component 41. In the laminate 50 shown in FIG. 2A, the mold 42 is formed so as to cover the entire surface of the substrate forming surface 130 of the adhesive layer 30 including the electronic component 41. In the laminate 50A shown in FIG. 2B, the mold 42 is formed to cover the entire surface of the substrate forming surface 120 of the reaction layer 20 including the electronic component 41. The mold 42 holds the electronic component 41 buried in the mold 42. The mold 42 may be formed to expose a part (e.g., the upper surface) of the electronic component 41. Also, the mold 42 may be formed using, for example, a material capable of transmitting light that degrades the reaction layer 20. As such a material, glass, silicon, an acrylic resin etc. are mentioned, for example. The electronic component 41 may not be disposed on the substrate 40. When the electronic component 41 is not disposed, for example, the mold 42 may be simply formed on the adhesive layer 30, or an electronic circuit rewired in the mold 42 may be formed. That is, the substrate 40 to be formed may not include the electronic component 41.

  In the case of manufacturing the substrate 40, first, the plurality of electronic components 41 are disposed on the adhesive layer 30. The arrangement number of the electronic components 41 is arbitrary. In the case of the laminated body 50 shown in FIG. 2A, the electronic component 41 is adhered and fixed by the adhesive layer 30. Thereafter, a mold 42 is formed to cover the entire surface of the adhesive layer 30 including the electronic component 41. In the stacked body 50A shown in FIG. 2B, a plurality of electronic components 41 are disposed on the reaction layer 20. Thereafter, a mold 42 is formed to cover the entire surface of the reaction layer 20 including the electronic component 41.

  In addition, a part (for example, upper surface) of the electronic component 41 can be exposed by removing a part of the mold 42 by grinding etc. from the state in which the electronic component 41 was embedded in the mold 42. Also, the substrate 40 is not limited to a single layer in which the electronic component 41 is disposed. For example, the mold 42 may be formed by further arranging the electronic component 41 on the mold 42 in which the electronic component 41 is arranged. Two or more layers in which such an electronic component 41 is disposed may be stacked. In addition, the stacked electronic components 41 may be electrically connected by a wiring or the like formed by a patterning method or the like.

<Holder>
FIG. 3 shows an example of a holder for holding the stack 50, 50A (or the substrate 40) configured as described above, and FIG. 3A is a perspective view of the holder holding the stack 50, 50A. FIG. 3 (B) is a cross-sectional view taken along the line A-A of FIG. 3 (A). In FIG. 3, the holder 60 is shown as an example in the case of holding the stacked body 50, and the same applies to the stacked body 50A. Further, the holder 60 holds the substrate 40 in which the support 10 is peeled off from the stacks 50 and 50A. The form of the holder 60 for holding the substrate 40 is shown in FIG. 6 (B).

  The holder 60 holds the laminate 50 in a state where the substrate 40 side is attached in the peeling unit 3, for example, and the substrate 40 after peeling the support 10 from the laminate 50 by the treatment with the peeling unit 3. Hold. The holder 60 is used, for example, in processing and transport of the substrate 40 after the peeling unit 3. The holding (adhesion) of the laminate 50 or the substrate 40 to the holder 60 may be performed by the peeling unit 3 or may be performed by the light irradiation unit 2 other than the peeling unit 3 or the like. Moreover, you may provide the unit for exclusive use for peeling the support body 10 from the laminated body 50. FIG. The dedicated unit may be included in the substrate processing apparatus 1.

  In addition, the stacked body 50 may be transported to the substrate processing apparatus 1 while being held by the holder 60, for example. That is, a unit dedicated to holding the stacked body 50 in the holder 60 may be disposed separately from the substrate processing apparatus 1. The holder 60 has a film 61 and a ring 62 as shown in FIGS. 3 (A) and 3 (B). The film 61 is formed using an elastically deformable material such as a resin. The film 61 is formed in a disk shape so as to conform to the outer peripheral shape of the ring 62, for example.

  The ring 62 is annular, and is formed using a highly rigid material such as resin, metal or the like. The ring 62 is fixed to the surface 61 a of the film 61 with an adhesive or the like so as not to be easily detached from the film 61. In addition, the laminate 50 is held in a state of being attached by an adhesive or the like to substantially the center of the area surrounded by the ring 62 in the surface 61 a of the film 61. The laminate 50 is attached to the surface 61 a of the film 61 on the substrate 40 side. As the adhesive used here, for example, an adhesive having an adhesive force capable of peeling the substrate 40 from the film 61 is applied.

  Since the substrate 40 after peeling the support 10 from the laminate 50 is thinner than the laminate 50 and the rigidity of the support 10 is lost, breakage such as cracking occurs during various processes or during transportation. It may occur. Accordingly, in the peeling unit 3 for peeling the support 10 from the laminate 50, the laminate 50 is held by the holder 60 in advance before peeling the support 10, and the support 10 is peeled from the substrate 10 in this state. The substrate 40 can be held by the holder 60 to prevent the substrate 40 from being damaged or the like. In addition, after the support 10 is peeled from the substrate 40 from the laminate 50, the substrate 40 may be attached to the holder 60. Since the substrate 40 is surrounded by the ring 62 of the highly rigid holder 60 and further supported by the elastically deformable film 61, shocks or vibrations are alleviated in the subsequent processing or transport, resulting in breakage or the like. Can be avoided. Further, in various processes or transport, the holder 60 may be gripped or the like, so that direct contact of the arm or the like with the substrate 40 can be avoided.

  The substrate 40 (laminated body 50) is not limited to being held by the holder 60 as shown in FIG. For example, the substrate 40 may be processed by the first cleaning unit 4, the second cleaning unit 5, or the third cleaning unit 6 as it is without being held by the holder or the like in the substrate processing apparatus 1 or from the peeling unit 3 It may be transported by the transport unit 7. In addition, when the substrate 40 is carried out of the substrate processing apparatus 1, the substrate 40 may be housed in, for example, a case or the like and carried out while being held by the holder 60, or the holder 60 is removed. It may be carried out in a state of

<Substrate processing method for laminate 50>
Next, a substrate processing method according to the present embodiment will be described. FIG. 4 is a flowchart showing an example of the substrate processing method according to the embodiment. This substrate processing method is performed in the substrate processing apparatus 1. As shown in FIG. 4, the substrate processing method includes a light irradiation step S10, a peeling step S20, and a substrate cleaning step S30. Each process of the light irradiation process S10, the peeling process S20, and the substrate cleaning process S30 is performed in the substrate processing apparatus 1. In the following example, first, a laminate 50 (see FIG. 2A) including the adhesive layer 30 will be described as an example.

(Light irradiation process)
In the light irradiation step S10, the laminate 50 is irradiated with light to deteriorate the reaction layer 20. The light irradiation step S10 is performed in the light irradiation unit 2 of the substrate processing apparatus 1. FIG. 5 shows an example of the light irradiation unit 2 and the light irradiation step S10, and FIG. 5 (A) is a view in the case of irradiating light to the entire surface of the laminate 50, and FIG. Is a diagram in the case of scanning the light. In addition, conveyance of the laminated body 50 to the light irradiation unit 2 is performed by the conveyance unit 7.

  As shown in FIG. 5A, the light irradiation unit 2 is attached to the reaction layer 20 from the side opposite to the substrate 40, that is, from the bottom surface 10b of the support 10 to the stacked body 50 mounted on the mounting table 2a. The light L is irradiated by the irradiation device 2a. The irradiation apparatus 2a irradiates the light L of the wavelength which can change the reaction layer 20 as mentioned above. In the light irradiation step S10, the reaction layer 20 is altered to form an altered layer (or an altered portion) 20a (see, for example, FIG. 6A). The deteriorated layer 20 a has lower strength or adhesion to the support 10 than the reaction layer 20. As shown in FIG. 5A, the altered layer 20a does not have to be formed over the entire depth direction, and if it is formed in at least a region of the reaction layer 20 in contact with the support 10. Good. FIG. 5A shows an example in which the altered layer 20 a is formed in a part of the reaction layer 20 in contact with the support 10.

  The irradiation device 2 a includes an optical element (not shown) so that the entire surface of the laminate 50 is irradiated with the light L. The irradiation device 2a can be configured to be capable of irradiating the entire surface of the reaction layer 20 with the light L, but is not limited thereto. For example, the irradiation device 2a irradiates the light L to an area such as a fraction of the whole surface of the laminate 50 instead of the entire surface of the laminate 50, and makes the irradiation position of the light L step. A method of irradiating the entire surface with the light L may be used. Moreover, as shown to FIG. 5 (B), the irradiation apparatus 2b which can irradiate a spot light as the light L on the surface of the laminated body 50 may be used, for example. The irradiation device 2b can scan and irradiate the light L over the entire surface of the reaction layer 20 by relatively moving the light L, which is spot light, and the laminate 50. Although the structure which scans the light L by rocking the irradiation apparatus 2b is mentioned as an example in FIG. 5 (B), it is not limited to this structure. For example, the irradiation device 2b may be configured to slide and scan the light L, or may be configured to scan the light L by using an optical element such as a galvano mirror.

  After the light irradiation step S10 is performed, a transfer step of transferring the laminate 50 in which the degenerated layer 20a is formed in the reaction layer 20 by the transfer device 7a of the transfer unit 7 from the light irradiation unit 2 to the peeling unit 3 is performed. In the peeling unit 3, the laminated body 50 conveyed by the conveying device 7a is held by the holder 60 shown in FIG. For example, the laminated body 50 is conveyed by the conveying device 7a onto the holder 60 previously disposed on the fixing stand 3b of the peeling unit 3, and is attached to the film 61 by being mounted on the holder 60 by the conveying device 7a. It may be done.

(Peeling process)
In the peeling step S20, the substrate 40 is peeled from the support 10. The peeling step S20 is performed in the peeling unit 3 of the substrate processing apparatus 1. FIG. 6 shows an example of the peeling unit 3 and the peeling step, and FIG. 6 (A) is a view before peeling the support 10 and FIG. 6 (B) is a view after peeling the support 10.

  In the peeling step S20, first, the holder 60 is fixed to the fixing stand 3b disposed in the peeling unit 3 by vacuum suction or the like. Since the stack 50 is attached to the holder 60, the stack 50 is held by the fixing stand 3b. After fixing the holder 60, as shown in FIG. 6A, the bottom surface 10b of the support 10 on the opposite side to the reaction layer forming surface 110 is vacuum-adsorbed by the adsorption device 3a. By moving the adsorption device 3a upward in this state, as shown in FIG. 6B, the support 10 is lifted from the substrate 40 with the reaction layer 20 as the separation surface. The deteriorated layer 20a in the reaction layer 20 is lowered in strength due to the irradiation of the light L, or is lowered in adhesion, and is easily broken by the upward movement of the adsorption device 3a, or the adhesion surface is It will peel off easily. Thereby, the support 10 is easily peeled off from the substrate 40. In the peeling step S20, the support 10 is peeled from the reaction layer 20 of the laminate 50.

  After performing the peeling step S20, the substrate 40 from which the support 10 has been peeled is held by the holder 60 and is conveyed from the peeling unit 3 to the first washing unit 4 and the second washing by the conveyance device 7a of the conveyance unit 7. A conveyance step of conveying to the unit 5 or the third cleaning unit 6 is performed.

(Substrate cleaning process)
The substrate cleaning step S30 includes a liquid cleaning step and a plasma cleaning step. In the liquid cleaning step, the substrate 40 peeled off from the support 10 is cleaned with a liquid. In the plasma cleaning process, the substrate 40 peeled off from the support 10 is treated with plasma. In the substrate cleaning step S30, the liquid cleaning step and the plasma cleaning step can be performed in a predetermined order. Specifically, in the substrate cleaning step S30, any one of the following lines A to D can be performed. Line A is a case where the liquid cleaning step S31 is performed, and then the plasma cleaning step S32 is performed. The line B performs the liquid cleaning step S33, then performs the plasma cleaning step S34, and then performs the liquid cleaning step S35. The line C performs a plasma cleaning step S36, and then performs a liquid cleaning step S37. The line D performs a plasma cleaning step S38, a liquid cleaning step S39, and then a plasma cleaning step S40. Hereinafter, line A to line D will be described in order.

(Line A)
In the line A, after the liquid cleaning step S31 is performed, the plasma cleaning step S32 is performed. When carrying out each step of line A, in the transport step after the stripping step S20, the substrate 40 from which the support 10 has been stripped is transferred from the stripping unit 3 to the first cleaning unit 4 by the transport device 7a of the transport unit 7. Transport to After transporting the substrate 40 to the first cleaning unit 4, the liquid cleaning step S 31 is performed in the first cleaning unit 4. FIG. 7 shows an example of the first cleaning unit 4 and the liquid cleaning step S31, and FIG. 7 (A) shows a state in which the substrate 40 is cleaned with liquid, and FIG. 7 (B) shows the state after the liquid cleaning step S31. FIG. 2 is a diagram showing a substrate 40.

  As shown in FIG. 7A, in the liquid cleaning step S31, first, with the ring 62 held at a predetermined height, the substrate 40 is lifted from below the film 61 by the lifting device 4a, The substrate 40 is in a state of projecting upward. In this case, the substrate 40 can be easily protruded above the ring 62 by supporting the upper portion of the ring 62 by the support portion 4 b. The film 61 is elastically deformed and extended. Alternatively, the ring 62 may be pressed downward by the support portion 4b while holding the substrate 40 at a predetermined height, as shown in FIG. 7A. Further, in the liquid cleaning step S31 and the first cleaning unit 4, whether or not the substrate 40 is lifted with respect to the ring 62 is optional, and the process may be performed without lifting the substrate 40 with respect to the ring 62.

  Subsequently, in a state where the substrate 40 is lifted, the cleaning liquid R1 is discharged to the reaction layer 20 from the cleaning liquid nozzle 4c. As described above, as the cleaning solution R1, for example, one or more solvents selected from hydrocarbon-based organic solvents, nitrogen-containing organic solvents, ether-based solvents, and ester-based solvents in which the reaction layer 20 and the adhesive layer 30 are dissolved are selected. It can be used. The cleaning solution R1 discharged from the cleaning solution nozzle 4c flows toward the film 61 while melting the reaction layer 20 and the adhesive layer 30, and drops from the ring 62. The cleaning solution R1 dropped from the ring 62 is recovered by a recovery unit (not shown).

  The cleaning liquid R1 dissolves and removes the non-deteriorated portion of the reaction layer 20 and the adhesive layer 30. In the reaction layer 20, the altered layer 20a is not dissolved in the cleaning solution R1, but is flowed by the cleaning solution R1 and most of it is removed from the substrate 40. The cleaning solution R1a for dissolving the reaction layer 20 and the cleaning solution R1b for dissolving the adhesive layer 30 may be switched and discharged from the cleaning solution nozzle 4c. In this case, first, after the cleaning solution R1a for dissolving the reaction layer 20 is discharged, the cleaning solution R1b for dissolving the adhesive layer 30 may be discharged. Alternatively, only the cleaning liquid R1b for dissolving the adhesive layer 30 may be discharged from the cleaning liquid nozzle 4c. In this case, the adhesive layer 30 is dissolved by the cleaning liquid R1b, so that the reaction layer 20 on the adhesive layer 30 is also removed from the substrate 40 by the flow of the cleaning liquid R1b.

  For example, as shown in FIG. 7B, a part of the altered layer 20a (the reaction layer 20) may remain without being flowed on the substrate 40 after the liquid cleaning step S31 is performed. Therefore, the substrate 40 is transported to the second cleaning unit 5 in the transport process after the liquid cleaning process S31 is performed. After the substrate 40 is transported to the second cleaning unit 5, the plasma cleaning step S 32 is performed on the substrate 40 in the second cleaning unit 5. In the plasma cleaning step S32, a part of the altered layer 20a (the reaction layer 20) remaining on the substrate 40 is removed.

  FIG. 8 shows an example of the second cleaning unit 5 and the plasma cleaning step S32, FIG. 8 (A) shows a state in which the substrate 40 is cleaned by plasma, and FIG. 8 (B) shows the substrate after the plasma cleaning step. FIG. As shown in FIG. 8A, in the plasma cleaning step S32, in a state where the holder 60 is mounted on the stage 5b, plasma 5a is generated in a space above the substrate 40 from a plasma generator (not shown). The plasma 5a is, for example, oxygen plasma. As shown in FIG. 8B, a part of the deteriorated layer 20a (the reaction layer 20) remaining on the substrate 40 is treated with the plasma 5a and removed from the substrate 40. In line A, the substrate 40 is processed in this manner.

(Line B)
In the line B, the liquid cleaning step S33 is performed, and after the plasma cleaning step S34 is performed, the liquid cleaning step S35 is performed. When performing each step of line B, in the transport step after the stripping step S20, the substrate 40 from which the support 10 has been stripped is subjected to the third cleaning from the stripping unit 3 by the transport device 7a of the transport unit 7. Transport to unit 6 The liquid cleaning step S33 is performed in the third cleaning unit 6. FIG. 9 shows an example of the third cleaning unit 6 and the liquid cleaning step S33. FIG. 9 (A) shows a state in which the substrate 40 is cleaned with liquid, and FIG. 9 (B) shows the state after the liquid cleaning step S33. FIG. 2 is a diagram showing a substrate 40.

  As shown in FIG. 9A, in the liquid cleaning step S33, as in the liquid cleaning step S31 of line A, the upper side of the ring 62 is supported at a predetermined height by the support portion 6b, and the lifting device 6a The substrate 40 is lifted from the lower side, and the substrate 40 protrudes upward with respect to the ring 62. Alternatively, the ring 62 may be pressed downward by the support portion 6b while holding the substrate 40 at a predetermined height, as shown in FIG. 9A. Further, in the liquid cleaning step S33 and the third cleaning unit 6, whether or not the substrate 40 is lifted with respect to the ring 62 is optional, and the processing may be performed without lifting the substrate 40 with respect to the ring 62.

  Subsequently, in a state where the substrate 40 is lifted, the cleaning liquid R2 is discharged to the reaction layer 20 from the cleaning liquid nozzle 6c. The cleaning solution R2 is used for the purpose of causing the altered layer 20a of the reaction layer 20 to flow from above the reaction layer 20. As the cleaning liquid R2, for example, water or the like may be used in addition to the same liquid as the cleaning liquid R1 described above. The cleaning solution R2 discharged from the cleaning solution nozzle 6c flows through the reaction layer 20 and falls to the film 61 side. As shown in FIG. 9B, the altered layer 20a of the reaction layer 20 is flowed and removed by the cleaning liquid R2, and a non-altered portion of the reaction layer 20 remains on the adhesive layer 30. .

  After the liquid cleaning step S33, the substrate 40 is transferred from the third cleaning unit 6 to the second cleaning unit 5 by the transfer device 7a in the transfer step. After the substrate 40 is transported to the second cleaning unit 5, the plasma cleaning step S 34 is performed in the second cleaning unit 5. FIG. 10 shows another example of the second cleaning unit 5 and the plasma cleaning step S34, and FIG. 10 (A) is a view in a state where the substrate 40 is cleaned by the plasma 5a, and FIG. 10 (B) is a plasma cleaning step. It is a figure which shows the board | substrate 40 after S34.

  As shown in FIG. 10A, in the plasma cleaning step S34, in a state where the holder 60 is mounted on the stage 5b, the plasma 5a is generated from the plasma generator (not shown) in the space above the adhesive layer 30. The plasma 5a is, for example, oxygen plasma. As shown in FIG. 10B, the non-denatured portion of the reaction layer 20 remaining on the adhesive layer 30 is treated with the plasma 5 a and removed from the substrate 40. In addition, the powder 20b produced when processing the reaction layer 20 with the plasma 5a may slightly remain on the adhesive layer 30.

  After performing the plasma cleaning step S34, the substrate 40 is transferred from the second cleaning unit 5 to the first cleaning unit 4 by the transfer device 7a in the transfer step. After transporting the substrate 40 to the first cleaning unit 4, the first cleaning unit 4 performs a liquid cleaning step S35. FIG. 11 shows another example of the first cleaning unit 4 and the liquid cleaning step S35, and FIG. 11 (A) shows a state in which the substrate 40 is cleaned with liquid, and FIG. 11 (B) shows the liquid cleaning step S35. It is a figure which shows the board | substrate 40 after.

  As shown in FIG. 11A, in the liquid cleaning step S35, the upper side of the ring 62 is supported at a predetermined height by the support portion 4b as in the liquid cleaning step S33 described above, and the film 61 is lowered by the lifting device 4a. Then, the substrate 40 is lifted up so that the substrate 40 protrudes upward with respect to the ring 62. Note that the ring 62 may be pressed downward by the support portion 6b while holding the substrate 40 at a predetermined height, as shown in FIG. 11A. Further, in the liquid cleaning step S35 and the first cleaning unit 4, whether or not the substrate 40 is lifted with respect to the ring 62 is optional, and the process may be performed without lifting the substrate 40 with respect to the ring 62.

  Subsequently, in a state where the substrate 40 is lifted, the cleaning solution R3 is discharged from the cleaning solution nozzle 4c to the adhesive layer 30. As described above, an organic solvent or the like capable of dissolving the adhesive layer 30 can be used as the cleaning solution R3. The cleaning solution R3 discharged from the cleaning solution nozzle 4c flows on the adhesive layer 30 and falls to the film 61 side. As shown in FIG. 11B, the adhesive layer 30 is dissolved and removed by the cleaning liquid R3. Further, the powder 20b of the reaction layer 20 remaining on the adhesive layer 30 is caused to flow and be removed by the cleaning liquid R3 as the adhesive layer 30 is removed. At line B, the substrate 40 is processed in this manner.

(Line C)
In the line C, after the plasma cleaning step S36 is performed, the liquid cleaning step S37 is performed. When carrying out each step of line C, the substrate 40 from which the support 10 has been peeled in the carrying step after the peeling step S20 is carried out from the peeling unit 3 to the second cleaning unit 5 by the carrying device 7a of the carrying unit 7. Transport to After the substrate 40 is transported to the second cleaning unit 5, the plasma cleaning step S 36 is performed in the second cleaning unit 5. FIG. 12 shows another example of the second cleaning unit 5 and the plasma cleaning step S36, and FIG. 12 (A) is a view of the state in which the substrate 40 is cleaned by the plasma 5a, and FIG. 12 (B) is the plasma cleaning step. It is a figure which shows the board | substrate 40 after S36.

  As shown in FIG. 12A, in the plasma cleaning step S36, as in the plasma cleaning step S34 in line B, plasma is not shown in the space above the adhesive layer 30 with the holder 60 mounted on the stage 5b. The generator 5 generates plasma 5a. The plasma 5a is, for example, oxygen plasma. A part of the reaction layer 20 is processed by the plasma 5 a and removed from the substrate 40 as shown in FIG. 12 (B). The powder 20b of the reaction layer 20 or the altered layer 20a may slightly remain on the adhesive layer 30.

  After the plasma cleaning step S36, the substrate 40 is transferred from the second cleaning unit 5 to the first cleaning unit 4 by the transfer device 7a in the transfer step. After transporting the substrate 40 to the first cleaning unit 4, the first cleaning unit 4 performs a liquid cleaning step S37. FIG. 13 shows another example of the first cleaning unit 4 and the liquid cleaning step S37, and FIG. 13 (A) shows the state in which the substrate 40 is cleaned with a liquid, and FIG. 13 (B) shows the liquid cleaning step S37. It is a figure which shows the board | substrate 40 after.

  As shown in FIG. 13A, in the liquid cleaning step S37, the upper portion of the ring 62 is supported at a predetermined height by the support portion 4b as in the liquid cleaning step S37 described above, and from below the film 61 by the lifting device 4a. The substrate 40 is lifted so that the substrate 40 protrudes upward with respect to the ring 62. The state shown in FIG. 13A may be obtained by pushing the ring 62 downward with the support portion 6b while holding the substrate 40 at a predetermined height. In the liquid cleaning step S37 and the first cleaning unit 4, whether or not the substrate 40 is lifted with respect to the ring 62 is optional, and the process may be performed without lifting the substrate 40 with respect to the ring 62.

  Subsequently, in a state where the substrate 40 is lifted, the cleaning solution R4 is discharged from the cleaning solution nozzle 4c to the adhesive layer 30. As described above, the cleaning solution R4 may use one or more solvents selected from hydrocarbon organic solvents capable of dissolving the adhesive layer 30, nitrogen-containing organic solvents, ether solvents, and ester solvents. it can. The cleaning solution R4 discharged from the cleaning solution nozzle 4c flows on the adhesive layer 30 and falls to the film 61 side. As shown in FIG. 13B, the adhesive layer 30 is dissolved and removed by the cleaning liquid R4. Also, with the removal of the adhesive layer 30, the powder 20b of the reaction layer 20 or the altered layer 20a remaining on the adhesive layer 30 is caused to flow and be removed by the cleaning liquid R4. At line C, the substrate 40 is processed in this manner.

(Line D)
In the line D, the plasma cleaning step S38 is performed, and after the liquid cleaning step S39 is performed, the plasma cleaning step S40 is performed. When carrying out each step of line D, the substrate 40 from which the support 10 has been peeled in the carrying step after the peeling step S20 is transferred from the peeling unit 3 to the second cleaning unit 5 by the carrying device 7a of the carrying unit 7. Transport to After the substrate 40 is transported to the second cleaning unit 5, the plasma cleaning step S 38 is performed in the second cleaning unit 5. In the plasma cleaning step S38, as in the plasma cleaning step S36 in the line C, the plasma 5a is generated in the space above the adhesive layer 30 with the holder 60 mounted on the stage 5b (see FIG. 12A). . A part of the reaction layer 20 is processed by the plasma 5 a and removed from the substrate 40 (see FIG. 12B).

  After performing the plasma cleaning step S38, the substrate 40 is transferred from the second cleaning unit 5 to the first cleaning unit 4 by the transfer device 7a in the transfer step. After the substrate 40 is transported to the first cleaning unit 4, the liquid cleaning step S39 is performed in the first cleaning unit 4. In the liquid cleaning step S39, the upper portion of the ring 62 is supported by the support portion 4b as in the liquid cleaning step S37 in the line C, and the substrate 40 is lifted from below the film 61 by the lifting device 4a. It is assumed that 40 protrudes upward (see FIG. 13A).

  Subsequently, in a state where the substrate 40 is lifted, the same cleaning liquid as the cleaning liquid R4 is discharged from the cleaning liquid nozzle 4c to the adhesive layer 30. The cleaning solution R4 discharged from the cleaning solution nozzle 4c flows on the adhesive layer 30 and falls to the film 61 side. The adhesive layer 30 is dissolved and removed by the cleaning liquid (see FIG. 13B). Also, with the removal of the adhesive layer 30, the powder 20b of the reaction layer 20 or the altered layer 20a remaining on the adhesive layer 30 is caused to flow and be removed by the cleaning liquid R4.

  FIG. 14 is a diagram showing another example of the substrate 40 after the plasma cleaning step S38 and the liquid cleaning step S39 are performed in the line D. As shown in FIG. 14, after the plasma cleaning step S38 and the liquid cleaning step S39 are performed, the powder 20b of the reaction layer 20 or the altered layer 20a may slightly remain on the substrate 40. Therefore, after the liquid cleaning step S39 is performed, the substrate 40 is transferred to the second cleaning unit 5 in the transfer step. After the substrate 40 is transported to the second cleaning unit 5, the plasma cleaning step S 40 is performed on the substrate 40 in the second cleaning unit 5. FIG. 15 shows another example of the second cleaning unit 5 and the plasma cleaning step S40, and FIG. 15 (A) shows a state in which the substrate 40 is cleaned by plasma, and FIG. 15 (B) shows the plasma cleaning step S40. It is a figure which shows the board | substrate 40 after.

  As shown in FIG. 15A, in the plasma cleaning step S40, as in the plasma cleaning step S38, in a state where the holder 60 is mounted on the stage 5b, the space on the adhesive layer 30 is not shown The plasma 5a is generated. The plasma 5a is, for example, oxygen plasma. As shown in FIG. 15B, the powder 20 b of the reaction layer 20 or the altered layer 20 a remaining on the adhesive layer 30 is treated with the plasma 5 a and removed from the substrate 40. In the line D, the substrate 40 is thus formed.

  As described above, according to the substrate processing apparatus 1 and the substrate processing method according to the present embodiment, the plasma cleaning by the first cleaning unit 4 performs the liquid cleaning steps S31, S33, S35, S37, S39, and the second cleaning unit 5. By reliably removing the reaction layer 20 or the altered layer 20a (residue) remaining on the substrate 40 by the steps S32, S34, S36, S38, and S40, the influence on the subsequent processing can be reduced. Thus, it is possible to prevent the residue from scattering from the substrate 40 and contaminating the surrounding environment.

<Arrangement of Unit of Substrate Processing Apparatus for Processing Laminate 50>
FIG. 16 is a view showing an example of the arrangement of each unit of the substrate processing apparatus 1. In FIG. 16, the directions in the figure will be described using an XYZ coordinate system. In this XYZ coordinate system, the vertical direction is taken as the Z direction, and the horizontal direction is taken as the X direction and the Y direction. In each of the X, Y, and Z directions, the direction indicated by the arrow is referred to as the + direction (for example, the + X direction), and the opposite direction is referred to as the − direction (for example, the −X direction). The substrate processing apparatus 1 shown in FIG. 16 processes the laminate 50 including the adhesive layer 30. The substrate processing apparatus 1 includes the light irradiation unit 2, the peeling unit 3, the first cleaning unit 4, the second cleaning unit 5, the third cleaning unit 6, and the transport unit 7 described above. The substrate processing apparatus 1 further includes a load port 8 on which a container (for example, FOUP etc.) for housing the plurality of stacked bodies 50 or the substrate 40 is placed, and a load port for carrying in or out the stacked body 50 or the substrate 40. And 9.

  The substrate processing apparatus 1 has a rectangular shape that is long in one direction (Y direction) in plan view. In the substrate processing apparatus 1, the peeling unit 3, the light irradiation unit 2, the first cleaning unit 4, and the second cleaning unit 5 are disposed on the + X side in the + Y direction. In the substrate processing apparatus 1, the third cleaning unit 6 and the second cleaning unit 5 are disposed on the −X side in the + Y direction. The light irradiation unit 2 is disposed between the peeling unit 3 and the first cleaning unit 4 in plan view on the + X side in the substrate processing apparatus 1. The first cleaning unit 4 is disposed between the light irradiation unit 2 and the second cleaning unit 5 in a plan view on the + X side in the substrate processing apparatus 1.

  Further, in the substrate processing apparatus 1 shown in FIG. 16, two second cleaning units 5 are arranged. In this case, for example, when the plasma cleaning process takes time, the processing efficiency can be improved by alternately using the two second cleaning units 5. In addition, one of the two second cleaning units 5 may be used as a main, and the other may be used as a sub used when the main failure occurs.

  In the substrate processing apparatus 1, load ports 8 and 9 are disposed on the −Y side. The load ports 8 and 9 are arranged in the X direction on the −Y side of the substrate processing apparatus 1. The transport unit 7 includes a transport device 7 a that transports the stacked body 50 or the substrate 40, and a transport path 7 b that is a moving path of the transport device 7 a. The transport device 7a is movable between the units or between the load ports 8 and 9 and each unit by rails or the like (not shown) provided on the transport path 7b. The transfer device 7 a has an arm (not shown) capable of holding the stack 50 or the substrate 40. The transport path 7 b is provided in the X direction on the −Y side in the substrate processing apparatus 1, and is provided in the Y direction between the row of units on the + X side and the row of units on the −X side. The transport path 7b is formed in a T-shape. The transfer device 7a transfers the stack 50 or the substrate 40 between the units or between the load ports 8 and 9 and each unit by moving the transfer path 7b.

  According to the substrate processing apparatus 1 configured as described above, the stacked unit 50 or the substrate 40 is efficiently transported to each unit by the transport unit 7, and thus the light irradiation step S10, the peeling step S20, and the substrate cleaning step S30 described above. Can be performed efficiently. Further, in the substrate cleaning step S30, the liquid cleaning steps S31, S33, S35, S37 and S39 and the plasma cleaning steps S32, S34, S36, S38 and S40 can be efficiently performed. Further, in the substrate processing apparatus 1, the area CON is an area in which a control base and the like are accommodated.

<Substrate processing method for laminate 50A>
Next, a substrate processing method for the laminate 50A not including the adhesive layer 30 will be described. FIG. 17 is a flowchart showing another example of the substrate processing method according to the embodiment. This substrate processing method is performed in the substrate processing apparatus 1 in the same manner as the laminate 50. As shown in FIG. 17, the substrate processing method for the laminate 50A not including the adhesive layer 30 includes a light irradiation step S50, a peeling step S60, a liquid cleaning step S70, and a plasma cleaning step S80. The liquid cleaning step S90 may be performed after the plasma cleaning step S80.

(Light irradiation process)
In the light irradiation step S50, the laminate 50A is irradiated with light to alter the reaction layer 20. The light irradiation step S50 is performed in the light irradiation unit 2 of the substrate processing apparatus 1. FIG. 18 shows an example of the light irradiation unit 2 and the light irradiation step S50, and FIG. 18 (A) shows the case where the entire surface of the laminate 50A is irradiated with light, and FIG. 18 (B) shows the laminate 50A. It is a figure in the case of scanning light. The conveyance of the stacked body 50A to the light irradiation unit 2 is performed by the conveyance unit 7.

  As shown in FIG. 18A, the light irradiation unit 2 is the side opposite to the substrate 40 with respect to the laminate 50A mounted on the mounting table 2a, as in the light irradiation step S10 for the laminate 50 described above. From the bottom surface 10b of the support 10, the reaction layer 20 is irradiated with the light L by the irradiation device 2a. The light L is the same as the light irradiation step S10 described above. In the light irradiation step S50, the reaction layer 20 is altered to form an altered layer (or altered portion) 20a. As for the deteriorated layer 20a, the strength or the adhesion to the support 10 is lower than that of the reaction layer 20, as in the light irradiation step S10 described above. Note that, as shown in FIG. 18A, the altered layer 20a does not have to be formed over the entire depth direction, and if it is formed in a partial region of the reaction layer 20 in contact with the support 10. Good. FIG. 18A shows an example in which the altered layer 20 a is formed in a partial region of the reaction layer 20 in contact with the support 10.

  The configuration of the light irradiation unit 2 is the same as the above, and thus the description will be simplified. However, as shown in FIG. 18A, even if the entire surface of the laminate 50 is irradiated with the light L by the irradiation device 2a. As shown in FIG. 18B, after performing the light irradiation step S50 which may be performed by scanning the light L which is spot light by the irradiation device 2b, the altered layer 20a is formed on the reaction layer 20. The conveying step of conveying the stacked body 50A from the light irradiation unit 2 to the peeling unit 3 by the conveying device 7a of the conveying unit 7 is performed. In the peeling unit 3, the laminated body 50A conveyed by the conveying device 7a is held by the holder 60 shown in FIG. For example, the laminated body 50A is conveyed by the conveying device 7a onto the holder 60 previously disposed on the fixing stand 3b of the peeling unit 3, and is attached to the film 61 by being mounted on the holder 60 by the conveying device 7a. It may be done.

(Peeling process)
In the peeling step S60, the substrate 40 is peeled from the support 10. The peeling process S60 is performed in the peeling unit 3 of the substrate processing apparatus 1. FIG. 19 shows an example of the peeling unit 3 and the peeling step S60, FIG. 19 (A) is a view before peeling the support 10, and FIG. 19 (B) is a view after peeling the support 10.

  In the peeling step S60, first, the holder 60 is fixed to the fixing stand 3b disposed in the peeling unit 3 by vacuum suction or the like. Since the stacked body 50A is attached to the holder 60, the stacked body 50A is held by the fixing stand 3b. After fixing the holder 60, as shown in FIG. 19A, the bottom surface 10b of the support 10 on the opposite side to the reaction layer forming surface 110 is adsorbed by the adsorption device 3a. By moving the adsorption device 3a upward in this state, as shown in FIG. 19B, the support 10 is lifted from the substrate 40 with the reaction layer 20 as the separation surface. As described above, the deteriorated layer 20a in the reaction layer 20 has a reduced strength due to the irradiation of the light L, or a reduced adhesion, and is easily destroyed by the upward movement of the adsorption device 3a. Or, the adhesive surface is easily peeled off. Thereby, the support 10 is easily peeled off from the substrate 40. In the peeling step S60, the support 10 is peeled from the reaction layer 20 of the laminate 50A.

  After performing the peeling step S50, the substrate 40 from which the support 10 is peeled is conveyed by the conveying device 7a of the conveying unit 7 from the peeling unit 3 to the third cleaning unit 6 while being held by the holder 60 Perform the process.

(Liquid washing process)
After transporting the substrate 40 to the third cleaning unit 6, the liquid cleaning step S 70 is performed in the third cleaning unit 6. FIG. 20 shows an example of the third cleaning unit 6 and the liquid cleaning step S70, and FIG. 20 (A) shows a state in which the substrate 40 is cleaned with liquid, and FIG. 20 (B) is after the liquid cleaning step S70. FIG. 2 is a diagram showing a substrate 40.

  As shown in FIG. 20A, in the liquid cleaning step S70, the upper side of the ring 62 is supported at a predetermined height by the support portion 6b as in the liquid cleaning step S33 for the laminate 50 described above, and the lifting device 6a Thus, the substrate 40 is lifted from the lower side of the film 61 so that the substrate 40 protrudes upward with respect to the ring 62. Note that the ring 62 may be pressed downward by the support portion 6b while holding the substrate 40 at a predetermined height, as shown in FIG. 20A. Further, in the liquid cleaning step S70 and the third cleaning unit 6, whether or not the substrate 40 is lifted with respect to the ring 62 is optional, and the processing may be performed without lifting the substrate 40 with respect to the ring 62.

  Subsequently, in a state where the substrate 40 is lifted, the cleaning solution R5 is discharged from the cleaning solution nozzle 6c to the reaction layer 20. The cleaning solution R <b> 5 is used for the purpose of causing the altered layer 20 a of the reaction layer 20 to flow from above the reaction layer 20. As the cleaning solution R5, for example, water or the like may be used as in the above-described cleaning solution R2. The cleaning solution R5 discharged from the cleaning solution nozzle 6c flows through the reaction layer 20 and falls to the film 61 side. As shown in FIG. 20B, the degraded layer 20a of the reaction layer 20 is flowed and removed by the cleaning liquid R5, and the non-altered portion of the reaction layer 20 remains on the substrate 40. After the liquid cleaning step S70, the substrate 40 which has been transferred by the transfer device 7a is transferred from the third cleaning unit 6 to the second cleaning unit 5 in the transfer step.

(Plasma cleaning process)
After the substrate 40 is transported to the second cleaning unit 5, the plasma cleaning step S80 is performed in the second cleaning unit 5. The plasma cleaning step S80 is performed in the second cleaning unit 5. FIG. 21 shows another example of the second cleaning unit 5 and the plasma cleaning step S80, and FIG. 21 (A) is a diagram of the state in which the substrate 40 is cleaned by plasma 5a, and FIG. 21 (B) is a plasma cleaning step. It is a figure which shows the board | substrate 40 after S80.

  As shown in FIG. 21A, in the plasma cleaning step S80, the plasma generating apparatus (not shown) generates plasma 5a in the space above the reaction layer 20 in a state where the holder 60 is mounted on the stage 5b. The plasma 5a is, for example, oxygen plasma. As shown in FIG. 21B, the non-denatured portion of the reaction layer 20 remaining on the substrate 40 is treated with the plasma 5 a and removed from the substrate 40.

  FIG. 22A is a view showing another example of the substrate 40 after the liquid cleaning step S70 and the plasma cleaning step S80 are performed. As shown in FIG. 22A, the powder 20b of the reaction layer 20 may slightly remain on the substrate 40 after the plasma cleaning step S80. Therefore, after performing the plasma cleaning step S80, in the transfer step, the substrate 40 is transferred from the second cleaning unit 5 to the third cleaning unit 6 by the transfer device 7a, and the liquid cleaning step S90 is performed in the third cleaning unit 6 It is also good.

(Liquid washing process)
FIG. 22B is a view showing a state in which the substrate 40 shown in FIG. 22A is being cleaned with a liquid. As shown in FIG. 22B, in the liquid cleaning step S90, the upper side of the ring 62 is supported at a predetermined height by the support portion 6b, and the lifting device 6a lowers the film 61 as in the liquid cleaning step S70 described above. Then, the substrate 40 is lifted up so that the substrate 40 protrudes upward with respect to the ring 62. Note that the ring 62 may be pressed downward by the support portion 6b while holding the substrate 40 at a predetermined height, as shown in FIG. 22B. In the liquid cleaning step S90 and the third cleaning unit 6, whether or not the substrate 40 is lifted with respect to the ring 62 is optional, and the process may be performed without lifting the substrate 40 with respect to the ring 62.

  Subsequently, in a state where the substrate 40 is lifted, the cleaning solution R6 is discharged from the cleaning solution nozzle 6c to the adhesive layer 30. The cleaning solution R5 is used to flow the powder 20b remaining on the substrate 40 from above the substrate 40. As the cleaning solution R6, water or the like may be used as in the case of the cleaning solution R5 described above. The cleaning solution R6 discharged from the cleaning solution nozzle 6c flows on the substrate 40 and drops to the film 61 side. The powder 20b remaining on the substrate 40 is flowed and removed by the cleaning liquid R6. Thus, the substrate 40 is formed. Note that whether or not the liquid cleaning step S90 is performed is optional, and the liquid cleaning step S90 may not be performed.

  As described above, according to the substrate processing apparatus 1 and the substrate processing method according to the present embodiment, the substrate 40 is subjected to the liquid cleaning steps S 70 and S 90 by the third cleaning unit 6 and the plasma cleaning step S 80 by the second cleaning unit 5. By removing the remaining reaction layer 20 or the altered layer 20a (residue) reliably, the influence on the subsequent processing can be reduced, and furthermore, the residue scatters from the substrate 40 and contaminates the surrounding environment. Can be prevented.

<Arrangement of Unit of Substrate Processing Apparatus for Processing Laminate 50A>
FIG. 23 is a view showing an example of the arrangement of each unit of the substrate processing apparatus 1A. In FIG. 23, the directions in the figure will be described using an XYZ coordinate system similar to FIG. When the laminate 50A not including the adhesive layer 30 is processed, the substrate processing apparatus 1 shown in FIG. 16 may be used, but since the laminate 50A does not have the adhesive layer 30, 1 Cleaning unit 4 is unnecessary. Therefore, when processing laminated body 50A, substrate processing apparatus 1A shown in FIG. 23 can also be used. The substrate processing apparatus 1A shown in FIG. 23 processes the stacked body 50A not including the adhesive layer 30. The substrate processing apparatus 1 </ b> A includes the light irradiation unit 2, the peeling unit 3, the second cleaning unit 5, the third cleaning unit 6, and the transport unit 7 described above. The substrate processing apparatus 1 also has a load port 8 for mounting a container for accommodating a plurality of stacks 50 or substrates 40, and a load port 9 for carrying in or out the stacks 50 or substrates 40 or temporarily storing them.

  The substrate processing apparatus 1A has a rectangular shape that is long in one direction (Y direction) in plan view. In the substrate processing apparatus 1A, the peeling unit 3, the light irradiation unit 2, and the second cleaning unit 5 are arranged on the + X side in the + Y direction. In the substrate processing apparatus 1A, the third cleaning unit 6 is disposed on the −X side. The light irradiation unit 2 is disposed so as to be sandwiched between the peeling unit 3 and the second cleaning unit 5 in a plan view.

  In the substrate processing apparatus 1A, the load ports 8 and 9 are the same as those of the substrate processing apparatus 1 shown in FIG. The transport unit 7 includes a transport device 7a that transports the stacked body 50A or the substrate 40, and a transport path 7b that is a movement path of the transport device 7a. The transport device 7a is movable between the units or between the load ports 8 and 9 and each unit by rails or the like (not shown) provided on the transport path 7b. The transfer device 7a has an arm (not shown) capable of holding the stacked body 50A or the substrate 40. The transport path 7b is provided in the X direction on the −Y side in the substrate processing apparatus 1A, and is provided in the Y direction between the row of units on the + X side and the row of units on the −X side. The transport path 7b is formed in a T-shape. The transfer device 7a transfers the stack 50 or the substrate 40 between the units or between the load ports 8 and 9 and each unit by moving the transfer path 7b.

  According to the substrate processing apparatus 1A configured as described above, the stack unit 50A or the substrate 40 is efficiently transported to each unit by the transport unit 7. Therefore, the light irradiation step S50, the stripping step S60, the liquid cleaning step S70, Each process of plasma washing process S80 and liquid washing process S90 can be performed efficiently. Further, in the substrate processing apparatus 1A, the area CON is an area in which a control base and the like are accommodated.

  As mentioned above, although embodiment and an Example were described, this invention is not limited to the description mentioned above, A various change is possible in the range which does not deviate from the summary of this invention. For example, although the substrate 40 is cut for each electronic component 41, the above-described substrate processing apparatus 1 or 1A may include such a cutting unit, or the cutting unit may be connected to the substrate processing apparatus 1 or 1A. It may be arranged.

R1, R2, R3, R4, R5, R6: cleaning solution 1, 1A: substrate processing device 2: light irradiation unit 2a, 2b: irradiation device 3: peeling unit 3a: adsorption Device 4 ... first cleaning unit 5 ... second cleaning unit 6 ... third cleaning unit 7 ... transport unit 7 a ... transport device 8, 9 ... load port 10 ... support Body 20 ... reactive layer 20a ... altered layer 30 ... adhesive layer 40 ... substrate 50, 50A ... laminated body 60 ... holder

Claims (15)

A light irradiation unit for degrading the reaction layer by irradiating light to a laminate including a support, a substrate, and a reaction layer interposed between the support and the substrate;
A peeling unit for peeling the substrate from the support;
A first cleaning unit for cleaning the substrate separated from the support with a liquid;
A second cleaning unit configured to process the substrate separated from the support with plasma. The laminate further has an adhesive layer between the reaction layer and the substrate,
The substrate processing apparatus according to claim 1, wherein the first cleaning unit removes the adhesive layer attached to the substrate peeled from the support with a liquid.   The liquid according to claim 1 or 2, wherein the liquid used in the first cleaning unit includes one or more selected from a hydrocarbon-based organic solvent, a nitrogen-containing organic solvent, an ether-based solvent, and an ester-based solvent. Substrate processing equipment.   The substrate processing apparatus according to any one of claims 1 to 3, wherein the second cleaning unit processes the substrate by oxygen plasma.   The substrate according to any one of claims 1 to 4, wherein the first cleaning unit, the second cleaning unit, and the peeling unit are disposed in the same space formed by a plurality of panels. Processing unit.   The substrate processing apparatus according to claim 5, further comprising a transfer device configured to transfer the support or the substrate peeled off from the support in the space. A light irradiation step of changing the reaction layer by irradiating the laminate with a support, a substrate, and a reaction layer interposed between the support and the substrate;
A peeling step of peeling the substrate from the support;
A liquid cleaning step of cleaning the substrate peeled off from the support with a liquid;
And D. a plasma cleaning step of processing the substrate separated from the support with plasma.   The substrate processing method according to claim 7, wherein the liquid used in the liquid cleaning step contains one or more selected from a hydrocarbon-based organic solvent, a nitrogen-containing organic solvent, an ether-based solvent, and an ester-based solvent.   The substrate processing method according to claim 7, wherein the plasma cleaning process processes the substrate by oxygen plasma.   The substrate processing method according to any one of claims 7 to 9, wherein the plasma cleaning step is performed after the liquid cleaning step is performed on the substrate peeled off from the support.   The substrate processing method according to any one of claims 7 to 9, wherein the liquid cleaning step is performed after the plasma cleaning step is performed on the substrate peeled off from the support.   The substrate processing method according to claim 11, wherein one or more liquid cleaning steps are further performed before the plasma cleaning step separately from the liquid cleaning step performed after the plasma cleaning step.   The liquid used in the liquid cleaning step performed before the plasma cleaning step includes one or more selected from a hydrocarbon-based organic solvent, a nitrogen-containing organic solvent, an ether-based solvent, and an ester-based solvent. The substrate processing method as described in.   The substrate processing method according to any one of claims 7 to 13, wherein the laminate further has an adhesive layer between the reaction layer and the substrate.   15. The method according to claim 7, further comprising a transfer step of transferring the support or the substrate peeled from the support between the liquid cleaning step, the plasma cleaning step, and the peeling step. The substrate processing method as described in any one.

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