TWI779153B - Substrate processing apparatus and substrate processing method - Google Patents

Abstract

The residue attached to the substrate can be reliably removed, the influence on the subsequent processing can be reduced, and the residue can be prevented from scattering from the substrate to pollute the surrounding environment. A substrate processing device (1), comprising: a light irradiation unit (2), for comprising a support (10), a substrate (40), and a reaction layer (20) interposed between the support (10) and the substrate (40) The laminate (50) is irradiated with light to modify the reaction layer (20); and the peeling unit (3) peels the substrate (40) from the support (10); and the first cleaning unit (4), The substrate (40) peeled off from the support (10) is cleaned by liquid; and the second cleaning unit (5) is used to clean the substrate (40) peeled off from the support (10) by plasma deal with.

Description

Substrate processing apparatus and substrate processing method

The invention relates to a substrate processing device and a substrate processing method.

In recent years, a so-called fan-out PLP (Fan-out Panel Level Package) technique has been known as an example of a method of manufacturing an electronic device. In the fan-out PLP technology, for example, a support such as a wafer or a glass plate is formed with a reactive layer that is modified by light absorption or heating, 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 after cleaning the substrate, the substrate is cut for each electronic component to obtain an electronic device (for example, refer to Patent Document 1). [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2010-3748

[Problem to be solved by the invention]

In the fan-out PLP technique described above, the substrate is peeled off from the support by applying light or heat to the reaction layer of the laminate, but at this time, residues of the reaction layer may adhere to the substrate. This residue is due to the deterioration of the reaction layer by light or heat, and it may be difficult to remove even by washing with a solvent. If the residues are attached as they are, the residues may affect the subsequent processing. In addition, if the substrate is transported to another place with the residue attached, the residue will scatter from the surface of the substrate, possibly polluting the surrounding environment.

The object of the present invention is to provide a substrate processing apparatus and a substrate processing method, which can reliably remove residues adhering to the substrate, reduce the influence on the subsequent processing, and prevent the residues from flying from the substrate to pollute the surrounding environment. [Technical means to solve the problem]

In a first aspect of the present invention, there is provided a substrate processing apparatus including: a light irradiation unit for irradiating light to a laminate including a support, a substrate, and a reaction layer interposed between the support and the substrate, whereby changing the quality of the reaction layer; and a stripping unit for stripping the substrate from the support; and a first cleaning unit for cleaning the substrate stripped from the support with a liquid; and a second cleaning unit, The said board|substrate peeled off from the said support body is treated with plasma.

In the second aspect of the present invention, there is provided a method for processing a substrate, including: a light irradiation process of irradiating light to a laminate including a support, a substrate, and a reaction layer interposed between the support and the substrate, whereby Deteriorating the aforementioned reaction layer; and stripping process, peeling the aforementioned substrate from the aforementioned support body; and liquid cleaning process, cleaning the aforementioned substrate stripped from the aforementioned support body with liquid; and plasma cleaning process, The said board|substrate peeled off from the said support body was treated with plasma. [compared to the effect of prior art]

According to the present invention, the residue adhering to the substrate is surely removed by the liquid cleaning process done by the first cleaning unit and the plasma cleaning process done by the substrate in the second cleaning unit, thereby reducing the The effect on subsequent processing can also be prevented from scattering residues from the substrate to pollute the surrounding environment.

Embodiments of the present invention will be described below with reference to the drawings. In addition, in the drawings, in order to facilitate the understanding of each structure, some parts are emphasized or some parts are simplified and expressed, which may be different from the actual structure, shape, scale, etc.

＜Substrate processing equipment＞ FIG. 1 is a diagram showing an example of a substrate processing apparatus 1 according to the first embodiment in functional blocks. The substrate processing apparatus 1 shown in FIG. 1 performs various processes on a laminate 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 . In addition, although not shown, the support body 10 separated from the laminated body 50 can be taken out from the substrate processing apparatus 1 as appropriate, and can also be stored in the substrate processing apparatus 1 for a predetermined number of sheets and processed from the substrate collectively. Device 1 is removed. As shown in FIG. 1 , a 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 transfer unit 7 .

The light irradiation unit 2 irradiates the laminated body 50 with light to modify the reaction layer 20 . The light irradiation unit 2 includes, for example, a not-shown mounting table on which the laminate 50 is placed, and a not-shown irradiation device for irradiating light of a wavelength capable of deteriorating the reaction layer 20 . The light from this irradiation device may be irradiated from the support body 10 side of the laminated body 50 or may be irradiated from the substrate 40 side of the laminated body 50 . Details of the light source included in the irradiation device and the light emitted from the light source will be described later. In addition, the light from the irradiation device may be irradiated from both the support body 10 side and the substrate 40 side of the laminated body 50 . In addition, the irradiation of light from the irradiation device may be a method of scanning point-shaped light, or a method of irradiating light on the entire layered body 50, and a part of the layered body 50 is irradiated with light while the irradiated part of the light is irradiated. Any of the methods of gradually stepping and moving.

The light irradiation unit 2 is accommodated in, for example, a dedicated chamber for the light irradiation unit 2 in the substrate processing apparatus 1 . With this chamber, it is possible to prevent light emitted from the irradiation device from leaking out of the chamber inside the substrate processing apparatus 1 .

The peeling unit 3 peels the substrate 40 from the support 10 . The laminate 50 in a state where the reaction layer 20 has been modified by the above-mentioned light irradiation unit 2 is loaded into the peeling unit 3 . The peeling unit 3 has, for example, an unillustrated fixing table for fixing the laminate 50 and an unillustrated adsorption device for adsorbing the support body 10 . The peeling unit 3 fixes the laminated body 50 on the fixing table with the support body 10 as the upper side, and in this state, the suction device is adsorbed to the support body 10 to pull it up, or the fixing table is lowered, thereby holding the support body 10. Peel off from the substrate 40 .

The first cleaning unit 4 cleans the substrate 40 peeled off from the support body 10 with a liquid. The first cleaning unit 4 is a liquid cleaning device. The first cleaning unit 4 includes, for example, an unillustrated stage on which the substrate 40 is placed, an unillustrated liquid supply device that supplies liquid to the substrate 40 placed on the stage, and discharges and cleans the substrate 40. A discharge unit (not shown) for the liquid after that. The first cleaning unit 4 removes the adhesive layer 30 adhering to the substrate 40 peeled off from the support body 10 with a liquid.

The liquid used in the first cleaning unit 4 includes one or more selected from hydrocarbon-based organic solvents, nitrogen-containing organic solvents, ether-based solvents, and ester-based solvents. Examples of hydrocarbon-based organic solvents include linear hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, and tridecane; Branched chain hydrocarbons with carbon numbers from 4 to 15; cyclic hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, tetrahydronaphthalene, etc.; p-menthane, o- Menthane, m-menthane, biphenylmenthane, 1,4-terpene diol, 1,8-terpene diol, camphene, norbornane, pinane, thujane, carane, longifolene, Geraniol, Neroli, Linalool, Citral, Citronellol, Menthol, Isomenthol, Neomenthol, Alpha-Terpineol, Beta-Terpineol, Gamma-Terpineol, Terpineol En-1-ol, Terpinen-4-ol, Terpine Dihydroacetate, 1,4-Cineol, 1,8-Cineol, Camphenol, Carvone, Ionone, Arborvitae Terpene-based solvents such as ketone, camphor, d-limonene, l-limonene, dipentene, etc.; anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, ethyl Aromatic organic solvents such as phenyl ether and butyl phenyl ether. Examples of nitrogen-containing organic solvents include solvents having amide bonds such as N-methylpyrrolidone, N-N-dimethylacetamide, and dimethylformamide. Examples of ether-based solvents include polyvalent alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate and other compounds with ester linkages; cyclic ethers such as dioxane; monomethyl ether, monoethyl ether, monoethyl ether, Derivatives of polyvalent alcohols such as compounds having ether linkages such as monoalkyl ether and monophenyl ether such as monopropyl ether and monobutyl ether. Examples of ester-based solvents include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetic acid, methyl pyruvate, ethyl pyruvate, methoxy Esters such as methyl propionate, ethyl ethoxy propionate, etc. As another readily available solvent, TZNR (registered trademark)-HC thinner manufactured by Tokyo Ohka Kogyo Co., Ltd., etc. can be used.

The first cleaning unit 4 is housed in, for example, a dedicated chamber for the first cleaning unit 4 in the substrate processing apparatus 1 . With this chamber, the liquid supplied from the liquid supply device can be prevented from leaking out of the chamber in the substrate processing apparatus 1 .

The second cleaning unit 5 treats the substrate 40 peeled off from the support body 10 with plasma. The second cleaning unit 5 is a plasma cleaning device. The second cleaning unit 5 includes, for example, a not-shown mounting table on which the substrate 40 is placed, and a not-shown plasma generator for generating plasma. The substrate 40 mounted on the mounting table is touched with the plasma generated by the plasma generator, thereby removing the residue of the reaction layer 20 that has been deteriorated by the above-mentioned light irradiation unit 2 . The second cleaning unit 5 processes the substrate 40 with, for example, oxygen plasma. In addition, the second cleaning unit 5 may be a plasma using gas such as N ₂ , NH ₃ , or CF ₄ instead of oxygen plasma.

The second cleaning unit 5 is accommodated in, for example, a dedicated chamber for the second cleaning unit 5 in the substrate processing apparatus 1 . With this chamber, the plasma generated in the plasma cleaning device can be prevented from leaking out of the chamber in the substrate processing device 1 .

The third cleaning unit 6 cleans the substrate 40 peeled off from the support body 10 with a liquid. The third cleaning unit 6 is a liquid cleaning device. The third cleaning unit 6 includes, for example, an unillustrated stage on which the substrate 40 is placed, an unillustrated liquid supply device that supplies liquid to the substrate 40 placed on the stage, and discharges and cleans the substrate 40. A discharge unit (not shown) for the liquid after that. The third cleaning unit 6 washes away the degenerated part (deteriorated layer 20a described later) attached to the reaction layer 20 of the substrate 40 peeled off from the support 10 by liquid washing. The liquid used in the third cleaning unit 6 includes one or more selected from hydrocarbon-based organic solvents, nitrogen-containing organic solvents, ether-based solvents, and ester-based solvents. The hydrocarbon-based organic solvent, nitrogen-containing organic solvent, ether-based solvent, or ester-based solvent is the same as the liquid used in the first cleaning unit 4 . In addition, the liquid used in the third cleaning unit 6 may be water.

The third cleaning unit 6 is accommodated in, for example, a chamber dedicated to the third cleaning unit 6 in the substrate processing apparatus 1 . With this chamber, the liquid supplied from the liquid supply device can be prevented from leaking out of the chamber in the substrate processing apparatus 1 .

The above-mentioned peeling unit 3, first cleaning unit 4, second cleaning unit 5, and third cleaning unit 6 are arranged in the same space formed by a plurality of wall panels. In this space, the transfer unit 7 for transferring the substrate 40 peeled from the support body 10 or the support body 10 is disposed. The transport unit 7 has a transport device 7a. The conveying device 7 a includes, for example, a not-illustrated holding unit that holds the laminate 50 or the substrate 40 , and a traveling unit that travels along guides and the like laid in the substrate processing apparatus 1 . These holding parts and running parts are driven by a driving device not shown. The transport device 7 a transports the laminate 50 carried into the substrate processing apparatus 1 to the light irradiation unit 2 . Moreover, the conveyance device 7 a conveys the laminated body 50 irradiated with light by the light irradiation unit 2 to the peeling unit 3 . In addition, the transfer device 7 a transfers the substrate 40 from which the support body 10 has been separated by the peeling unit 3 between the first cleaning unit 4 , the second cleaning unit 5 , and the third cleaning unit 6 . In addition, the conveyance device 7 a can also convey the support body 10 separated by the peeling unit 3 .

In addition, the operation of each of the above units will also be described in the substrate processing method described later.

＜Laminated body＞ The laminate 50 processed by the substrate processing apparatus 1 will be described. FIG. 2 shows an example of a laminate to be processed in the substrate processing apparatus 1. FIG. 2(A) is a view of a laminate 50 including an adhesive layer 3, and FIG. 2(B) is a view of a laminate not including an adhesive layer 30. Figure 50A. That is, the laminate 50 shown in FIG. 2(A) includes a support 10 , a reaction layer 20 , an adhesive layer 30 , and a substrate 40 . In addition, a laminate 50A shown in FIG. 2(B) 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 for forming the laminates 50 and 50A, and may be connected to and arranged in this laminate forming unit. The laminate forming unit includes, for example, a reaction layer forming device for forming the reaction layer 20 on the support 10, an adhesive layer forming device for forming the adhesive layer 30 on the reaction layer 20, and an adhesive layer 30 or the reaction layer 20. A substrate forming device that arranges electronic components 41 to form a mold 42 . Elements used in each part of the above-mentioned laminate forming unit will be described below.

(support body) The support body 10 is, for example, a circular or nearly circular semiconductor wafer having a thickness of 50 to 500 μm. The thickness of the semiconductor wafer is arbitrary. In addition, as the support body 10, instead of a semiconductor wafer, for example, a glass plate or the like having a thickness of 500 to 1500 μm may be used. The support body 10 is not limited to a circular shape or a nearly circular shape, and may be other shapes such as a rectangular shape, an elliptical shape, or a polygonal shape, for example.

(reaction layer) The reaction layer 20 is formed of, for example, a material that is modified by absorbing light. In this embodiment, the deterioration of the reaction layer 20 refers to the state that the reaction layer 20 can be destroyed by a slight external force, or the state in which the adhesive force with the layer in contact with the reaction layer 20 is reduced. The reaction layer 20 absorbs light and is denatured, thereby reducing strength or adhesion to the support 10 compared to before denaturation. Therefore, the modified reaction layer 20 will be destroyed or peeled off from the support body 10 by applying a slight external force (for example, lifting the support body 10 , etc.).

The deterioration of the reaction layer 20 may be caused by the energy of absorbed light (heat generation or non-heat generation) decomposition, cross-linking, change in three-dimensional configuration, or dissociation of functional groups (and the hardening of the reaction layer 20 accompanying them, degassing, contraction or expansion), etc. The modification of the reactive layer 20 occurs as a result of light absorption by the material constituting the reactive layer 20 . Therefore, the type of modification of the reaction layer 20 may vary depending on the type of material constituting the reaction layer 20 . In addition, the reaction layer 20 is not limited to a material that is modified by absorbing light. For example, it may be a material that is modified by absorbing heat applied instead of light, or a material that is modified by other solvents or the like.

The thickness of the reaction layer 20 is, for example, more preferably 0.05-50 μm, and still more preferably 0.3-1 μm. If the thickness of the reaction layer 20 converges in the range of 0.05 to 50 μm, the reaction can be achieved by short-time light irradiation and low-energy light irradiation, or short-time heating, and short-time immersion in a solvent. Layer 20 undergoes the desired deterioration. In addition, the thickness of the reaction layer 20 is particularly preferably within a range of 1 μm or less from the viewpoint of productivity.

Hereinafter, the reaction layer 20 that is modified by the energy of absorbed light will be described. The reaction layer 20 is preferably formed only of a material having a light-absorbing structure, but the reaction layer 20 may be formed by adding a material not having a light-absorbing structure within a range that does not impair essential characteristics. In addition, the surface of the reaction layer 20 that faces the adhesive layer 30 is preferably flat (no unevenness is formed), so that the formation of the adhesive layer 30 can be easily performed, and it can be attached uniformly when attaching. attached.

The reaction layer 20 may be modified by absorbing light irradiated from a laser. That is, the light irradiated to the reaction layer 20 (light emitted from the irradiation device of the above-mentioned light irradiation unit 2 ) to modify the reaction layer 20 may be irradiated from a laser. Examples of lasers that emit light irradiated to the reaction layer 20 include solid-state lasers such as YAG lasers, ruby lasers, glass lasers, _YVO4 lasers, LD lasers, fiber lasers, and pigment lasers. Liquid lasers such as _CO2 lasers, excimer lasers, Ar lasers, He-Ne lasers, etc., gas lasers such as semiconductor lasers, free electron lasers, etc., or non-laser light, etc. . The laser that emits light to irradiate the reaction layer 20 can be appropriately selected according to the material constituting the reaction layer 20 , as long as the laser irradiating light with a wavelength that can degrade the material constituting the reaction layer 20 is selected.

(fluorocarbon) The reaction layer 20 can also be composed of fluorocarbons. Since the reaction layer 20 is made of fluorocarbon, it becomes degraded by light absorption, and as a result, it loses the strength and adhesiveness before being irradiated with light. Therefore, by applying a slight external force (such as lifting the support body 10 ), the reaction layer 20 will be destroyed, and the support body 10 and the substrate 40 can be easily separated. The fluorocarbon constituting the reaction layer 20 can be suitably formed into a film by a plasma CVD (Chemical Vapor Deposition) method.

Fluorocarbons, depending on their type, absorb light with an inherent range of wavelengths. By irradiating the reaction layer 20 with light having a wavelength in a range that the fluorocarbon used in the reaction layer 20 absorbs in the light irradiation unit 2 , the fluorocarbon can be suitably denatured. In addition, the light absorption rate in the reaction layer 20 is preferably 80% or more.

As the light irradiated to the reaction layer 20, solid-state lasers such as YAG laser, ruby laser, glass laser, YVO4 laser, LD laser, fiber laser, etc. can be suitably used depending on the wavelength that can be absorbed by fluorocarbons _. liquid lasers such as pigment lasers, gas lasers such as _CO2 lasers, excimer lasers, Ar lasers, He-Ne lasers, etc., laser light such as semiconductor lasers and free electron lasers, or non-laser light. The wavelength at which the fluorocarbon can be denatured is not limited thereto, but, for example, one having a wavelength of 600 nm or less can be used.

(Polymers containing light-absorbing structures in their repeating units) The reaction layer 20 may also contain a polymer having a light-absorbing structure in its repeating unit. This polymer is denatured by being irradiated with light by the light irradiation unit 2 . The deterioration of the polymer occurs because the above-mentioned structure absorbs the irradiated light. The reactive layer 20, as a result of the deterioration of the polymer, loses its strength or adhesiveness before exposure to light. Therefore, by applying a slight external force (such as lifting the support body 10 ), the reaction layer 20 will be destroyed, and the support body 10 and the substrate 40 can be easily separated.

The above-mentioned light-absorbing structure is a chemical structure that absorbs light and denatures a polymer containing the structure as a repeating unit. Such a structure is, for example, an atomic group including a conjugated π-electron system composed of substituted or non-substituted benzene rings, condensed rings, or complex rings. More specifically, the structure may be a CARDO structure, or a benzophenone structure, a diphenylene structure, a diphenylene structure (biphenylene structure), or a diphenylene structure present in the side chain of the above-mentioned polymer. Phenyl structure or diphenylamine structure.

When the above-mentioned structure exists in the side chain of the above-mentioned polymer, the structure can be represented by the following formula.

(In the formula, each R is independently alkyl, aryl, halogen, hydroxyl, keto, arylene, arganyl or N(R ¹ )(R ² ) group (here, R ¹ and R ² are each independently , is a hydrogen atom or an alkyl group with 1 to 5 carbons), Z is absent, or is -CO-, -SO ₂ -, -SO- or -NH-, n is an integer of 0 or 1 to 5). In addition, the above-mentioned polymer includes, for example, a repeating unit represented by any one of (a) to (d) in the following formulae, or represented by (e), or a structure including (f) in its main chain .

(In the formula, l is an integer of 1 or more, m is an integer of 0 or 1 to 2, X is any one of the formulas shown in the above-mentioned chemical formula [Chemical 1] in (a) to (e), and in ( f) is any one of the above formulas represented by [Chem. 1] or does not exist, and Y ₁ and Y ₂ are each independently -CO- or -SO ₂ -. l is preferably an integer of 10 or less).

Examples of the benzene ring, condensed ring, and complex ring represented by the above chemical formula [Chemical 1] include phenyl, substituted phenyl, benzyl, substituted benzyl, naphthalene, substituted naphthalene, anthracene, substituted anthracene, anthracene Quinone, substituted anthraquinone, acridine, substituted acridine, azobenzene, substituted azobenzene, fluorene; fluorene, substituted fluorene; fennel, fluorenone, substituted fluorene, carbazole, substituted carbazole, N-alkylcarb Azole, dibenzofuran, substituted dibenzofuran, phenanthrene, substituted phenanthrene, pyrene and substituted pyrene. When the exemplified substituting group still has a substituting group, the substituting group is, for example, selected from alkyl, aryl, halogen atom, alkoxy, nitro, oxalic, nitrile, amide, dialkylamine, amide , imide, carboxylic acid, carboxylate, sulfonic acid, sulfonate, alkylamine and arylamine.

Among the substituents represented by the above-mentioned chemical formula [Chemical 1], as an example in the case where the fifth substituent having two phenyl groups and Z is -SO ₂ -, bis(2,4- Dihydroxyphenyl) ketone, bis(3,4‐dihydroxyphenyl) ketone, bis(3,5‐dihydroxyphenyl) ketone, bis(3,6‐dihydroxyphenyl) ketone, bis(4‐ Hydroxyphenyl) Phenyl, Bis(3-Hydroxyphenyl) Pyrium, Bis(2-Hydroxyphenyl) Pyrone, and Bis(3,5-Dimethyl-4-Hydroxyphenyl) Pyridine, etc.

Among the substituents represented by the above chemical formula [Chemical 1], as an example of the fifth substituent having two phenyl groups, and Z is -SO-, bis(2,3-di Hydroxyphenyl)one, bis(5-chloro-2,3-dihydroxyphenyl)one, bis(2,4-dihydroxyphenyl)one, bis(2,4-dihydroxy-6 -methylphenyl)phenylene, bis(5-chloro-2,4-dihydroxyphenyl)phenylene, bis(2,5-dihydroxyphenyl)phenylene, bis(3,4-dihydroxyphenyl) Phenyl)phenylene, bis(3,5-dihydroxyphenyl)phenylene, bis(2,3,4-trihydroxyphenyl)phenylene, bis(2,3,4-trihydroxy-6-methyl phenylene)-phenylene, bis(5-chloro-2,3,4-trihydroxyphenyl)phenylene, bis(2,4,6-trihydroxyphenyl)phenylene, bis(5-chloro group-2,4,6-trihydroxyphenyl) phenylene, etc.

Among the substituents represented by the above chemical formula [Chemical 1], as an example of the fifth substituent having two phenyl groups, and Z is -C(=O)-, 2,4 ‐Dihydroxybenzophenone, 2,3,4‐trihydroxybenzophenone, 2,2',4,4'‐tetrahydroxybenzophenone, 2,2',5,6'‐tetrahydroxybenzophenone Benzophenone, 2‐hydroxy‐4‐methoxybenzophenone, 2‐hydroxy‐4‐octyloxybenzophenone, 2‐hydroxy‐4‐dodecyloxybenzophenone, 2 ,2'‐dihydroxy‐4‐methoxybenzophenone, 2,6‐dihydroxy‐4‐methoxybenzophenone, 2,2'‐dihydroxy‐4,4'‐dimethoxy 4-Amine-2'-Hydroxybenzophenone, 4-Dimethylamine-2'-Hydroxybenzophenone, 4-Diethylamine-2'-Hydroxybenzophenone , 4‐dimethylamine‐4'‐methoxy‐2'‐hydroxybenzophenone, 4‐dimethylamine‐2',4'‐dihydroxybenzophenone, and 4‐dimethyl Amine‐3',4'‐dihydroxybenzophenone, etc.

When the above-mentioned structure exists in the side chain of the above-mentioned polymer, the ratio of the repeating unit including the above-mentioned structure to the above-mentioned polymer, the transmittance of light falling on the reaction layer 20 will be 0.001% or more and 10% or less In the range. When the polymer is adjusted so that the ratio falls within such a range, the reaction layer 20 sufficiently absorbs light and can be deteriorated reliably and rapidly. That is, the removal (or separation, peeling) of the support body 10 from the laminated body 50 is easy, and the light irradiation time necessary for this removal can be shortened.

The above-mentioned structure, depending on the selection of its type, can absorb light having a wavelength in a desired range. For example, the wavelength of light that the above structure can absorb is more preferably in the range of not less than 100 nm and not more than 2,000 nm. Within this range, the wavelength of light that the above-mentioned structure can absorb is on the shorter wavelength side, for example, within a range of not less than 100 nm and not more than 500 nm. For example, the above-mentioned structure preferably absorbs ultraviolet light having a wavelength in the range of approximately 300 nm to 370 nm, whereby a polymer including the structure can be denatured.

The above structure can absorb light, for example, from high-pressure mercury lamp (wavelength: above 254nm, below 436nm), KrF excimer laser (wavelength: 248nm), ArF excimer laser (wavelength: 193nm ₎ , F2 excimer laser (wavelength: 157nm), XeCl laser (wavelength: 308nm), XeF laser (wavelength: 351nm) or solid UV laser (wavelength: 355nm), or g-ray (wavelength: 436nm), h-ray (wavelength : 405nm) or i-rays (wavelength: 365nm), etc.

The above-mentioned reaction layer 20 contains the polymer containing the above-mentioned structure as a repeating unit, but the reaction layer 20 may further contain components other than the above-mentioned polymer. As this component, a filler, a plasticizer, and the component which can improve the releasability of the support body 10 etc. are mentioned. These components are appropriately selected from known substances or materials that do not prevent or promote light absorption by the above-mentioned structure and deterioration of the polymer.

(inorganic) The reaction layer 20 can also be composed of inorganic substances. Since the reaction layer 20 is made of an inorganic substance, it becomes degraded by light absorption, and as a result, it loses the strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (such as lifting the support body 10 ), the reaction layer 20 will be destroyed, and the support body 10 and the substrate 40 can be easily separated.

The above-mentioned inorganic substance is only required to be modified by absorbing light, and for example, one or more kinds of inorganic substances selected from the group consisting of metals, metal compounds, and carbon can be suitably used. The so-called metal compounds refer to compounds containing metal atoms, such as metal oxides and metal nitrides. Examples of such inorganic substances are not limited thereto, but examples of such inorganic substances include gold, silver, copper, iron, nickel, aluminum, titanium, chromium, SiO ₂ , SiN, Si ₃ N ₄ , TiN, and carbon. One or more inorganic substances selected from the group. In addition, the so-called carbon is a concept that may also include carbon allotropes, such as diamonds, fullerenes, diamond-like carbon, carbon nanotubes, and the like.

The above-mentioned inorganic substances absorb light having wavelengths within a specific range depending on their types. By irradiating the separation layer with light having a wavelength in a range in which the inorganic substances used in the reaction layer 20 absorb, the above-mentioned inorganic substances can be suitably denatured.

In the light irradiation unit 2, as the light irradiated to the reaction layer 20 composed of inorganic substances, for example, YAG laser, ruby laser, glass laser, YVO ₄ laser, Solid lasers such as LD lasers and fiber lasers, liquid lasers such as pigment lasers, gas lasers such as _CO2 lasers, excimer lasers, Ar lasers, He-Ne lasers, and semiconductor lasers , free electron laser, etc., or non-laser light.

The reaction layer 20 composed of inorganic substances can be formed on the support body 10 by known techniques such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, and spin coating. The thickness of the reaction layer 20 composed of inorganic substances is not particularly limited, as long as it can sufficiently absorb the light used, for example, it is more preferably set to a film thickness in the range of 0.05 μm or more and 10 μm or less. In addition, an adhesive agent may be applied on both sides or one side of the inorganic film (such as a metal film) composed of inorganic substances constituting the reaction layer 20 to be attached to the support body 10 and the substrate 40 .

In addition, when a metal film is used as the reaction layer 20, depending on the film quality of the reaction layer 20, the type of laser light source, laser output and other conditions, reflection of the laser or charging of the film may occur. Therefore, it is preferable to provide an anti-reflection film or an anti-static film on the upper and lower sides of the reaction layer 20 or one of them, so as to achieve these countermeasures.

(Compounds with infrared absorbing structures) The reaction layer 20 may also be formed of a compound having an infrared absorbing structure. This compound is denatured by absorbing infrared rays. The reaction layer 20 loses its strength or adhesiveness before being irradiated with infrared rays as a result of the deterioration of the compound. Therefore, by applying a slight external force (such as lifting the support body, etc.), the reaction layer 20 will be destroyed, and the support body 10 and the substrate 40 can be easily separated.

As a compound having an infrared-absorbing structure or a structure containing an infrared-absorbing structure, for example, an alkane, an alkene (vinyl, trans, cis, vinylidene, three-substituted, four-substituted, conjugated, alkene , cyclic), alkynes (one replacement, two replacements), monocyclic aromatics (benzene, one replacement, two replacements, three replacements), alcohols and phenols (free OH, intramolecular hydrogen bonding, intermolecular hydrogen Bonding, saturated secondary, saturated tertiary, unsaturated secondary, unsaturated tertiary), acetal, ketal, aliphatic ether, aromatic ether, vinyl ether, oxirane ether, Peroxide ethers, ketones, dialkylcarbonyls, aromatic carbonyls, enols of 1,3-diketones, o-hydroxyaryl ketones, dialkyloxanes, aromatic oxones, carboxylic acids (dimers, carboxyl acid anion), formates, acetates, conjugated esters, non-conjugated esters, aromatic esters, lactones (β-, γ-, δ-), aliphatic acid chlorides, aromatic acid chlorides, acid anhydrides (conjugated, non-conjugated, cyclic, non-cyclic), primary amide, secondary amide, lactam, primary amine (aliphatic, aromatic), secondary amine (aliphatic aromatic, aromatic), tertiary amine (aliphatic, aromatic), first-level amine salt, second-level amine salt, third-level amine salt, ammonium ion, aliphatic nitrile, aromatic nitrile, carbodiethylene Amines, aliphatic isonitriles, aromatic isonitriles, isocyanates, thiocyanates, aliphatic isothiocyanates, aromatic isothiocyanates, aliphatic nitro compounds, aromatic nitro compounds, nitroamines, Nitroamines, nitrates, nitrites, nitroso linkages (aliphatic, aromatic, monomers, dimers), sulfur compounds such as thiols, thiophenols, and thiol acids, thiocarbonyl, sub Sulfide, Sulfide, Sulfonyl Chloride, First Level Amide, Second Level Amide, Sulfate, Carbon-Halogen Bond, Si-A ¹ Bond (A ¹ is H, C, O or Halogen), PA ² bonding (A ² is H, C or O), or Ti-O bonding.

Examples of the structure including the carbon-halogen bond include -CH ₂ Cl, -CH ₂ Br, -CH ₂ I, -CF ₂ -, -CF ₃ , -CH=CF ₂ , -CF=CF ₂ , fluorinated aryl, and chlorinated aryl, etc.

Examples of the structure including the aforementioned 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 etc. As a structure including a Si-A ¹ bond, it is particularly preferable to form a siloxane skeleton and a silsesquioxane skeleton.

Examples of the structure including the PA ² linkage include PH, PH ₂ , P-CH ₃ , P-CH ₂ -, PC ₆ H ₅ , A ³ ₃ -PO (A ³ is aliphatic or aromatic), (A ⁴ O) ₃ -PO (A ⁴ is an alkyl group), P-OCH ₃ , P-OCH ₂ CH ₃ , P-OC ₆ H ₅ , POP, P-OH, and O=P-OH, etc.

The above-mentioned structure, depending on the selection of its type, can absorb infrared rays having a wavelength in a desired range. Specifically, the wavelength of infrared rays that the structure can absorb is, for example, in the range of 1 μm to 20 μm, and more suitably absorbs in the range of 2 μm to 15 μm. Also, when the above-mentioned structure is Si—O bonding, Si—C bonding, and Ti—O bonding, it may be within a range of 9 μm or more and 11 μm or less. In addition, the wavelengths of infrared rays that can be absorbed by each structure can be easily understood by those skilled in the art. For example, for the absorption bands in each structure, non-patent literature can be referred to: Silverstein, Bassler, Morrill, "Methods for Identifying Spectra According to Organic Compounds (5th Edition) - Combination of MS, IR, NMR, and UV -" (1992 Year issued) on pages 146 to 151.

The compound having an infrared-absorbing structure used in the formation of the reaction layer 20 is not particularly specific as long as it can be dissolved in a solvent for coating and can be cured to form a solid layer among compounds having the above-mentioned structure. limited. However, in order to effectively change the quality of the compound in the reaction layer 20 and to facilitate the separation of the support 10 and the substrate 40, it is preferable that the absorption of infrared rays in the reaction layer 20 is large, that is to say, the absorption of infrared rays by the light irradiation unit 2 is relatively large. When the reaction layer 20 is irradiated with infrared rays, the transmittance of infrared rays is low. Specifically, preferably, the transmittance of infrared rays in the reaction layer 20 is lower than 90%, and more preferably, the transmittance of infrared rays is lower than 80%.

As an example, as a compound having a siloxane skeleton, for example, a repeating unit represented by the following chemical formula [Chem. 3] and a polymer, that is, a resin, of a repeating unit represented by the following chemical formula [Chem. Or a polymer of the repeating unit represented by the following chemical formula [Chemical 4] and a repeating unit derived from an acrylic compound, that is, a resin.

(In the above chemical formula [Chem. 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 the compound having a siloxane skeleton, it is more preferable to be a polymer of the repeating unit represented by the above chemical formula [Chem. 3] and the repeating unit represented by the following chemical formula [Chem. 5], that is, t-butyl Styrene (TBST)-dimethylsiloxane polymer, more preferably TBST comprising the repeating unit represented by the above chemical formula [Chem. 3] and the repeating unit represented by the following chemical formula [Chem. 5] at a ratio of 1:1 -Dimethicone polymer.

Moreover, as a compound which has a silsesquioxane frame|skeleton, the polymer which is a resin which is the repeating unit represented by the following chemical formula [Chem. 6] and the repeating unit represented by the following chemical formula [Chem. 7] can be used, for example.

(In the above-mentioned chemical formula [Chemical 6], R ⁴ is a hydrogen or an alkyl group with a carbon number of 1 or less and 10 or less, in the above-mentioned chemical formula [Chemical 7], R ⁵ is a carbon number with a carbon number of 1 or more, an alkyl group with 10 or less, or phenyl). As a compound having a silsesquioxane skeleton, in addition, Japanese Patent Application Laid-Open No. 2007-258663 (published on October 4, 2007), Japanese Patent Laid-Open No. 2010-120901 (published on June 2010) can also be suitably used. Various silsesquioxanes disclosed in Japanese Patent Application Publication No. 2009-263316 (published on November 12, 2009) and Japanese Patent Application Publication No. 2009-263596 (published on November 12, 2009) resin.

Among them, the compound having a silsesquioxane skeleton is more preferably a repeating unit represented by the following chemical formula [Chem. 8] and a polymer of repeating units represented by the following chemical formula [Chem. 9]. A polymer comprising a repeating unit represented by the following chemical formula [Chem. 8] and a repeating unit represented by the following chemical formula [Chem. 9] at a ratio of 7:3.

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

In addition, examples of compounds containing Ti-O bonds include (i) tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis(2-ethylhexyloxy)titanium, and Titanium alkoxides such as titanium-i-propoxyoctanediol; (ii) di-i-propoxybis(acetylacetonate)titanium, and propanedioxytitanium bis(ethylacetylacetonate) (iii) iC ₃ H ₇ O-[-Ti(OiC ₃ H ₇ ) ₂ -O-] _n -iC ₃ H ₇ , and nC ₄ H ₉ O-[-Ti(OnC ₄ H ₉ ) ₂ -O-] _n -nC ₄ H ₉ and other titanium polymers; (iv) tri-n-butoxytitanium monostearate, titanium stearate, di-i-propoxytitanium di Isostearic acid, titanium acylation such as (2-n-butoxycarbonylbenzoyloxy) tributoxytitanium; (v) di-n-butoxy bis(triethanol amination ) Water-soluble titanium compounds such as titanium, etc.

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

The above-mentioned reaction layer 20 contains a compound having an infrared-absorbing structure, but the reaction layer 20 may further contain components other than the above-mentioned compounds. As this component, a filler, a plasticizer, and the component which can improve the releasability of the support body 10 etc. are mentioned. These components are appropriately selected from conventionally known substances or materials that do not interfere with or promote infrared absorption by the above-mentioned structure or deterioration of the compound.

(infrared absorbing substance) The reaction layer 20 may also contain an infrared absorbing substance. The reaction layer 20 is constituted by including an infrared absorbing substance, and is deteriorated by light absorption, and as a result, the strength or adhesiveness before being irradiated with light is lost. Therefore, by applying a slight external force (such as lifting the support body 10 ), the reaction layer 20 will be destroyed, and the support body 10 and the substrate 40 can be easily separated.

The infrared-absorbing substance may be modified as long as it absorbs infrared rays, and for example, carbon black, iron particles, or aluminum particles can be suitably used. Infrared-absorbing substances absorb light of wavelengths within a specific range depending on their type. By irradiating the reaction layer 20 in the light irradiation unit 2 with light of a wavelength in a range that the infrared absorbing substance used in the reaction layer 20 absorbs, the infrared absorbing substance can be suitably modified.

The reaction layer 20 is formed by arranging a liquid containing the above materials on one surface (reaction layer forming surface) 110 of the support 10 . For example, the support 10 is placed on a platform such as a coating device, and the liquid is discharged from the slit nozzle to the reaction layer formation surface 110 while moving the slit nozzle for discharging the liquid relative to the support 10 . Thereby, the reaction layer 20 is formed on the entire surface of the reaction layer forming surface 110 of the support body 10 . In addition, the coating method of the reaction layer 20 is not limited to the above-mentioned slit nozzle method, for example, it can also be performed by a coating method such as a spin coating method, a dipping method, a roller knife method, a doctor blade method, or a spray method. .

(next layer) As the resin contained in the adhesive layer 30, as long as it has adhesive properties, for example, hydrocarbon resins, acrylic-styrene resins, maleimide resins, elastomer resins, etc., or a mixture of them combination etc.

The glass transition temperature (Tg) of the adhesive will vary depending on the type or molecular weight of the above-mentioned resin, and the formulation of the plasticizer for the adhesive. The type or molecular weight of the resin contained in the above-mentioned adhesive agent can be appropriately selected according to the types of substrates and supports, but it is preferable that the Tg of the resin used in the adhesive agent is in the range of -60°C or higher and 200°C or lower. good is Above -25°C and below 150°C. The Tg of the resin used for the adhesive agent is in the range of -60°C to 200°C, so that cooling does not require excessive energy, and the adhesive force of the adhesive layer 30 can be appropriately reduced. In addition, the Tg of the adhesive layer 30 can also be adjusted by properly preparing a plasticizer or a resin with a low degree of polymerization. The glass transition temperature (Tg) can be measured using a well-known differential scanning calorimeter (DSC), for example.

(hydrocarbon resin) Hydrocarbon resin, which has a hydrocarbon skeleton, is a resin formed by polymerizing monomer components. Examples of hydrocarbon resins include cycloolefin-based polymers (hereinafter referred to as "resin (A)"), and at least one resin selected from the group consisting of terpene resins, rosin-based resins, and petroleum resins ( Hereinafter, it may be referred to as "resin (B)"), etc., but is not limited thereto.

The resin (A) may be a resin formed by polymerizing a monomer component including a cycloolefin-based monomer. Specifically, a ring-opening (co)polymer of a monomer component including a cycloolefin-based monomer, a resin obtained by additionally (co)polymerizing a monomer component including a cycloolefin-based monomer, and the like are exemplified.

Examples of the cycloolefin-based monomer contained in the monomer components constituting the resin (A) include norbornene, norbornadiene and other bicyclic bodies, dicyclopentadiene, and dihydroxypentadiene. A tricyclic body, a tetracyclic body such as tetracyclododecene, a pentacyclic body such as a trimer of cyclopentadiene, a heptacyclic body such as tetracyclopentadiene, or an alkyl group of these polycyclic bodies (form group, ethyl, propyl, butyl, etc.) substituents, olefin (vinyl, etc.) substituents, alkylene (ethylene, etc.) substituents, aryl (phenyl, tolyl, naphthyl, etc.) substituents body etc. Among them, norbornene, tetracyclododecene, or a norbornene-based monomer selected from the group consisting of these alkyl substituents is particularly preferable.

The monomer component constituting the resin (A) may also contain other monomers that can be copolymerized with the above-mentioned cycloolefin-based monomers, for example, preferably contain olefin monomers. Examples of olefin monomers include ethylene, propylene, 1-butene, isobutylene, 1-hexene, and α-olefins. Olefin monomers may be linear or branched.

In addition, it is preferable to contain a cycloolefin monomer as a monomer component constituting the resin (A) from the viewpoint of high heat resistance (low pyrolysis, thermogravimetric reduction). The ratio of the cycloolefin monomer to the total monomer components constituting the resin (A) is preferably at least 5 mol%, more preferably at least 10 mol%, and still more preferably at least 20 mol%. In addition, although the ratio of the cycloolefin monomer to the entire monomer components constituting the resin (A) is not particularly limited, it is preferably 80 moles from the viewpoint of solubility and stability over time in a solution. mol% or less, more preferably 70 mol% or less.

In addition, as a monomer component constituting the resin (A), a straight-chain or branched-chain olefin monomer may be contained. The ratio of the olefin monomer to the total monomer components constituting the resin (A) is preferably from 10 to 90 mol%, more preferably from 20 to 85 mol%, from the viewpoint of solubility and flexibility , preferably 30-80 mole%.

In addition, the resin (A) is, for example, a resin without a polar group such as a resin obtained by polymerizing a monomer component composed of a cycloolefin monomer and an olefin monomer. better.

There are no particular limitations on the polymerization method, polymerization conditions, and the like when polymerizing the monomer components, and can be appropriately set according to conventional methods.

Commercially available products that can be used as the resin (A) include "TOPAS" manufactured by POLYPLASTIC, "APEL" manufactured by Mitsui Chemicals, "ZEONOR" and "ZEONEX" manufactured by ZEON Japan, JSR Company-made "ARTON", etc.

The glass transition temperature (Tg) of the resin (A) is preferably at least 60°C, particularly preferably at least 70°C. If the glass transition temperature of the resin (A) is 60° C. or higher, softening of the adhesive layer 30 can be further suppressed when the laminate is exposed to a high-temperature environment.

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

The softening point of the resin (B) is not particularly limited, but is preferably 80 to 160°C. When the softening point of resin (B) is 80 degreeC or more, softening can be suppressed when a laminated body is exposed to a high temperature environment, and adhesion failure will not generate|occur|produce. On the other hand, when the softening point of resin (B) is 160 degreeC or less, the peeling rate at the time of peeling a laminated body will become favorable.

The weight average molecular weight of the resin (B) is not particularly limited, but is preferably 300-3,000. When the weight average molecular weight of resin (B) is 300 or more, heat resistance will become sufficient, and the outgassing amount will decrease in a high-temperature environment. On the other hand, when the weight average molecular weight of resin (B) is 3,000 or less, the peeling rate at the time of peeling a laminated body will become favorable. In addition, the weight average molecular weight of resin (B) in this embodiment means the molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC).

Moreover, what mixed resin (A) and resin (B) can also be used as resin. By mixing, heat resistance and peeling speed become favorable. For example, the mixing ratio of resin (A) and resin (B) is (A):(B) =80:20 to 55:45 (mass ratio), the peeling speed, heat resistance at high temperature environment, and softness It is better because of its good nature.

(acrylic-styrene resin) Examples of acrylic-styrene resins include resins obtained by polymerizing styrene or styrene derivatives, and (meth)acrylates as monomers.

Examples of (meth)acrylates include alkyl (meth)acrylates having a chain structure, (meth)acrylates having an aliphatic ring, and (meth)acrylates having an aromatic ring. . Examples of alkyl (meth)acrylates composed of a chain structure include long-chain acrylic acid-based alkyl esters having an alkyl group having 15 to 20 carbons, and acrylic alkanes having an alkyl group having 1 to 14 carbons. base esters etc. Examples of acrylic long-chain alkyl esters include n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-eicosyl. Alkyl esters of acrylic or methacrylic acid. In addition, the alkyl group may be branched.

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

As (meth)acrylates having an aliphatic ring, cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, 1-adamantane (meth)acrylate, norbornyl (meth)acrylate Acrylate, isocamphoryl (meth)acrylate, tricyclodecane (meth)acrylate, tetracyclododecane (meth)acrylate, dicyclopentadiene (meth)acrylate, etc., but Isocamyl methacrylate and dicyclopentadiene (meth)acrylate are more preferable.

The (meth)acrylate having an aromatic ring is not particularly limited, but examples of the aromatic ring include phenyl, benzyl, tolyl, xylyl, biphenyl, naphthyl, anthracenyl, Phenoxymethyl, phenoxyethyl, etc. In addition, the aromatic ring may have a chain or branched alkyl group having 1 to 5 carbon atoms. Specifically, phenoxyethyl acrylate is preferred.

(maleimide resin) Examples of maleimide-based resins include N-methylmaleimide, N-ethylmaleimide, N-n-propylmaleimide, N-isopropyl Maleimide, N-n-butylmaleimide, N-isobutylmaleimide, N-sec-butylmaleimide, N-tert-butylmaleimide , N-n-pentylmaleimide, N-n-hexylmaleimide, N-n-heptylmaleimide, N-n-octylmaleimide, N-dodecylmaleimide Alkyl maleimides such as amine and N-octadecylmaleimide, including N-cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide Aliphatic hydrocarbon-based maleimides such as N-cyclohexylmaleimide, N-cyclohexylmaleimide, N-cyclohexylmaleimide, and N-cyclohexylmaleimide Imines, including N-phenylmaleimide, N-m-methylphenylmaleimide, N-o-methylphenylmaleimide, N-p-methylphenylmaleimide, etc. A resin obtained by polymerizing aromatic maleimides with aromatic groups as monomers.

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

(In the above chemical formula [Chem. 11], n is 0 or an integer of 1 to 3). As such a cycloolefin copolymer, APL 8008T, APL 8009T, and APL 6013T (all are manufactured by Mitsui Chemicals Co., Ltd.) etc. can be used.

(Elastomer) The elastomer preferably includes a styrene unit as a constituent unit of the main chain, and the "styrene unit" may have a substituent. Examples of substituents include alkyl groups having 1 to 5 carbons, alkoxy groups having 1 to 5 carbons, alkoxyalkyl groups having 1 to 5 carbons, acetyloxy groups, carboxyl groups and the like. In addition, the content of the styrene unit is more preferably within a range of not less than 14% by weight and not more than 50% by weight. Also, the elastomer preferably has a weight average molecular weight in the range of not less than 10,000 and not more than 200,000.

When the content of styrene units is in the range of 14% by weight to 50% by weight, and the weight average molecular weight of the elastomer is in the range of 10,000 to 200,000, it is easy to dissolve in the hydrocarbon-based solvents described later, Therefore, the adhesive layer 30 can be removed more easily and quickly. In addition, the content of styrene units and the weight-average molecular weight are within the above-mentioned range, so that when the wafer is supplied to the resist lithography process, the exposed resist solvent (such as PGMEA, PGME, etc.), acid (hydrogen fluoride, etc.) etc.), alkalis (TMAH, etc.) exhibit excellent resistance.

In addition, the above-mentioned (meth)acrylate may be further mixed with the elastomer.

In addition, the content of styrene units is more preferably at least 17% by weight, and more preferably at most 40% by weight.

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

As the elastomer, various elastomers can be used as long as the content of styrene units is in the range of 14% by weight to 50% by weight, and the weight average molecular weight of the elastomer is in the range of 10,000 to 200,000. For example, polystyrene-poly(ethylene/propylene) block copolymers (SEP), styrene-isoprene-styrene block copolymers (SIS), styrene-butadiene-styrene block copolymers, Segment copolymer (SBS), styrene-butadiene-butylene-styrene block copolymer (SBBS), and their hydrogenated products, styrene-ethylene-butylene-styrene block copolymer (SEBS) , styrene-ethylene-propylene-styrene block copolymer (styrene-isoprene-styrene block copolymer) (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer ( SEEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (Septon V9461 (manufactured by KURARAY)) whose styrene block is reactive crosslinkable type, styrene block reactive crosslinkable type Styrene-ethylene-butylene-styrene block copolymers (Septon V9827 (manufactured by Kuraray Co., Ltd.) with reactive polystyrene-based hard blocks), etc., and the content of styrene units and the weight average molecular weight are Those within the above range.

In addition, hydrogenated compounds are more preferred among elastomers. If it is a hydride, the stability with respect to heat will improve, and deterioration, such as decomposition and polymerization, will hardly occur. In addition, it is also more preferable from the viewpoint of solubility in hydrocarbon-based solvents and resistance to resist solvents.

In addition, among the elastomers, block polymers with styrene at both ends are more preferable. This is because higher heat resistance can be exhibited by having high thermal stability styrene blocks at both ends.

More specifically, elastomers, hydrogenated block copolymers of styrene and conjugated diene are more preferred. The thermal stability is improved, and deterioration such as decomposition or polymerization is less likely to occur. In addition, higher heat resistance can be exhibited by adding styrene blocks with high thermal stability to both ends. Also, it is more preferable from the viewpoint of solubility in hydrocarbon-based solvents and resistance to resist solvents.

Examples of commercially available elastomers that can be used as the elastomer contained in the adhesive constituting the adhesive layer 30 include "Septon (trade name)" manufactured by Kuraray Co., Ltd., "Hybrar (trade name)" manufactured by Kuraray Corporation, Asahi Kasei Co., Ltd. "Tuftec (trade name)" manufactured by the company, "DYNARON (trade name)" manufactured by JSR Corporation, etc.

As the content of the elastomer contained in the adhesive constituting the adhesive layer 30, for example, the total amount of the adhesive composition is 100 parts by weight, preferably 50 parts by weight or more and 99 parts by weight or less, more preferably 60 parts by weight. It is in the range of not less than 99 parts by weight, preferably not less than 70 parts by weight and not more than 95 parts by weight. By setting it as these ranges, a wafer and a support body can be bonded suitably, maintaining heat resistance.

In addition, as for the elastomer, a plurality of types may be mixed. That is, the adhesive constituting the adhesive layer 30 may also include plural types of elastic bodies. It is sufficient that at least one of the plurality of types of elastomers contains a styrene unit as a constituent unit of the main chain. In addition, as long as at least one of the plurality of types of elastomers has a styrene unit content in the range of 14% by weight to 50% by weight, or a weight average molecular weight in the range of 10,000 to 200,000, then It is the scope of the present invention. In addition, when the adhesive constituting the adhesive layer 30 contains a plurality of types of elastomers, as a result of mixing, the content of the styrene unit may be adjusted so that the content of the styrene unit falls within the above range. For example, if Septon 4033 of Septon (trade name) manufactured by Kuraray Co., Ltd. with a styrene unit content of 30% by weight and Septon 2063 of Septon (trade name) with a styrene unit content of 13% by weight are compared When mixing 1 to 1, the styrene content will be 21 to 22% by weight with respect to the entire elastomer contained in the adhesive, so it will be 14% by weight or more. In addition, for example, when 10% by weight and 60% by weight of styrene units are mixed at a weight ratio of 1:1, it becomes 35% by weight, which is within the above-mentioned range. This invention can also be such a form. In addition, it is preferable that all of the plurality of types of elastomers included in the adhesive constituting the adhesive layer 30 contain styrene units within the above-mentioned range and have a weight average molecular weight within the above-mentioned range.

Moreover, it is preferable to form the adhesive layer 30 using resin other than photocurable resin (for example, UV curable resin). By using a resin other than the photocurable resin, residues can be prevented from remaining around the fine unevenness of the substrate 40 after peeling or removal of the adhesive layer 30 . In particular, the adhesive constituting the adhesive layer 30 is preferably not dissolved in any solvent but dissolved 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 even from the substrate 40 whose strength has decreased without causing damage or deformation of the substrate 40 .

(dilute solvent) As the diluting solvent used when forming the adhesive layer 30, for example, linear solvents such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, tridecane, etc. Hydrocarbons, branched hydrocarbons with 4 to 15 carbons, such as cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, tetrahydronaphthalene and other cyclic hydrocarbons, p-menth alkanes, o-menthane, m-menthane, biphenylmenthane, 1,4-terpene diol, 1,8-terpene diol, camphane, norbornane, pinane, thujardane, carane, Longifolene, Geraniol, Neroliol, Linalool, Citral, Citronellol, Menthol, Isomenthol, Neomenthol, Alpha-Terpineol, Beta-Terpineol, Gamma-Terpine Alcohol, Terpinen-1-ol, Terpinen-4-ol, Terpineyl Dihydroacetate, 1,4-Cineol, 1,8-Cineol, Camphor, Carvone, Violet Terpene-based solvents such as ketone, thujone, camphor, d-limonene, l-limonene, and dipentene; lactones such as γ-butyrolactone; acetone, butanone, cyclohexanone (CH), formazan Ketones such as n-amyl ketone, methyl isoamyl ketone, and 2-heptanone; polyvalent alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; ethylene glycol monoacetic acid Esters, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate and other compounds with ester linkages, monomethyl ethers of the aforementioned polyvalent alcohols or the aforementioned ester linkage compounds Derivatives of polyvalent alcohols such as monoalkyl ethers such as monoethyl ether, monopropyl ether, monobutyl ether, etc., or compounds with ether linkages such as monophenyl ethers (among them, propylene glycol monomethanol ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) are preferred); cyclic ethers such as dioxane, or methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate esters, methoxybutyl acetic acid, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, etc.; anisole, ethyl benzyl ether, toluene Aromatic organic solvents such as methyl methyl ether, diphenyl ether, dibenzyl ether, ethyl phenyl ether, butyl phenyl ether, etc.

(other ingredients) The adhesive constituting the adhesive layer 30 may further include other substances with miscibility within the scope of not impairing the essential characteristics. For example, various conventional additives such as additional resins, plasticizers, adhesive auxiliary agents, stabilizers, colorants, thermal polymerization inhibitors, and surfactants for improving the performance of adhesives can be used.

The next layer 30 is formed by disposing a liquid containing the above materials on the reaction layer 20 . For example, the support 10 is placed on a platform such as a coating device, and the liquid is discharged from the slit nozzle onto the reaction layer 20 while moving the slit nozzle for discharging the liquid relative to the support 10 . In this way, the adhesive layer 30 is formed on the entire surface of the reaction layer 20 . In addition, the coating method of the adhesive layer 30 is not limited to the above-mentioned slit nozzle method, for example, it can also be performed by a coating method such as a spin coating method, a dipping method, a roller knife method, a doctor blade method, or a spray method. . In addition, after coating the adhesive layer 30 on the reaction layer 20, it may be dried by heating or the like.

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

The mold seal 42 holds the electronic component 41 . In the laminated body 50 shown in FIG. 2(A), 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 addition, in the laminated body 50A shown in FIG. 2(B), the mold 42 is formed so as to cover the entire surface of the substrate formation surface 120 including the reaction layer 20 of the electronic component 41 . By the molding 42 , the electronic component 41 is held in a state of being embedded in the molding 42 . In addition, the mold 42 may be formed so that a part (for example, the upper surface) of the electronic component 41 is exposed. In addition, the molding 42 can also be formed by using, for example, a material that allows light that can degrade the reaction layer 20 to pass through. As such a material, glass, silicon, acrylic resin, etc. are mentioned, for example. In addition, the electronic component 41 may not be arranged on the substrate 40 . When the electronic parts 41 are not arranged, for example, the mold 42 can be simply formed on the adhesive layer 30 , or an electronic circuit formed by rewiring can be formed on the mold 42 . That is to say, the formed substrate 40 may not include the electronic components 41 .

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

In addition, part of the mold 42 is removed by grinding or the like from the state where the electronic component 41 is embedded in the mold 42 , thereby exposing a part (for example, the upper surface) of the electronic component 41 . In addition, the board|substrate 40 is not limited to the single layer in which the electronic component 41 is arrange|positioned. For example, on the mold package 42 where the electronic component 41 is placed, the electronic component 41 may be further arranged to form the mold package 42 . Two or more layers in which the electronic components 41 are arranged in this way may be laminated. In addition, the laminated electronic components 41 may be electrically connected by wiring or the like formed by a patterning method or the like.

＜Retainer＞ FIG. 3 discloses an example of a holder holding the laminated body 50, 50A (or substrate 40) constituted as described above. FIG. 3(A) is a perspective view of the holder holding the laminated body 50, 50A. FIG. 3(B) ) is a cross-sectional view along line A-A of FIG. 3(A). In FIG. 3 , an example of a state in which the holder 60 holds the laminate 50 is shown, and the same applies to the laminate 50A. Furthermore, the holder 60 holds the substrate 40 from which the support body 10 has been peeled off from the laminated bodies 50 and 50A. Moreover, the form of the holder 60 which holds the board|substrate 40 is shown in FIG. 6(B).

The holder 60, for example, holds the laminate 50 in a state of being attached to the substrate 40 side in the peeling unit 3, and holds the support 10 peeled from the laminate 50 by the process in the peeling unit 3. Substrate 40. The holder 60 is used, for example, for handling and transporting the substrate 40 following the peeling unit 3 . The holding (sticking) of the laminate 50 or the substrate 40 of 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 . Moreover, you may provide the dedicated unit for peeling the support body 10 from the laminated body 50. This dedicated unit may also be included in the substrate processing apparatus 1 .

In addition, the laminated body 50 may be conveyed to the substrate processing apparatus 1 in the state held by the holder 60, for example. That is, a dedicated unit for holding the laminate 50 by the holder 60 may be arranged 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 resin. The membrane 61 is, for example, formed in a disk shape so as to match the outer peripheral shape of the ring 62 .

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

The substrate 40 after the support 10 is peeled off from the laminate 50 is thinner than the laminate 50 and loses the rigidity of the support 10, so there is a possibility of cracking or other damage during various handling or transportation. . Therefore, in the peeling unit 3 for peeling the support 10 from the laminate 50, the holder 60 holds the laminate 50 before peeling the support 10, and the support 10 is peeled from the substrate 10 in this state. This makes it possible to hold the substrate 40 by the holder 60 and prevent damage to the substrate 40 or the like. In addition, after peeling the support body 10 from the board|substrate 40 from the laminated body 50, you may stick this board|substrate 40 to the holder 60 again. The substrate 40 is surrounded by the ring 62 of the highly rigid holder 60 and is supported by the elastically deformable film 61, so shocks and vibrations during subsequent handling or transportation are reduced and damage can be avoided. In addition, it is only necessary to hold the holder 60 and the like during various processing and transportation, and it is possible to avoid direct contact of the robot arm and the like with the substrate 40 .

In addition, the substrate 40 (laminated body 50 ) is not limited to being held by the holder 60 as shown in FIG. 3 . For example, the substrate 40 may be directly processed in the first cleaning unit 4, the second cleaning unit 5, or the third cleaning unit 6 without being held by a holder or the like in the substrate processing apparatus 1. The peeling unit 3 is conveyed by the conveyance unit 7 . In addition, when the substrate 40 is carried out from the substrate processing apparatus 1, the substrate 40 may be carried out while being held by the holder 60, for example, stored in a box or the like, or may be carried out while the holder 60 is detached. move out.

<Substrate processing method for laminated body 50> Next, the substrate processing method of this embodiment will be described. Fig. 4 is a schematic flowchart of an example of a substrate processing method according to the embodiment. This substrate processing method is carried out in the substrate processing apparatus 1 . As shown in FIG. 4 , the substrate processing method includes a light irradiation process S10 , a peeling process S20 , and a substrate cleaning process S30 . Each 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 examples, first, a laminate 50 (see FIG. 2(A) ) including the adhesive layer 30 will be described as an example.

(light exposure engineering) In the light irradiation process S10, the laminated body 50 is irradiated with light, whereby the reaction layer 20 is modified. The light irradiation process 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 process S10. FIG. 5(A) is a diagram showing a situation where light is irradiated to the entire layered body 50, and FIG. 5(B) is a situation where light is scanned on a layered body 50. diagram. In addition, the transfer of the laminated body 50 to the light irradiation unit 2 is performed by the transfer unit 7 .

As shown in FIG. 5(A), the light irradiation unit 2, for the laminated body 50 placed on the stage 2a, faces the reaction layer 20 from the side opposite to the substrate 40, that is, from the bottom surface 10b of the support body 10. The light L is irradiated by the irradiation device 2a. The irradiation device 2 a irradiates light L having a wavelength capable of modifying the reaction layer 20 as described above. According to the light irradiation process S10, the reaction layer 20 is modified to form a modified layer (or modified part) 20a (see FIG. 6(A) etc.). The degenerated layer 20a has lower strength or adhesion to the support 10 than the reaction layer 20 . In addition, as shown in FIG. 5(A), the altered layer 20a does not need to be formed across the entire depth direction, but only needs to be formed in at least the region in contact with the support 10 in the reaction layer 20 . FIG. 5(A) shows an example of the case where 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 is provided with an optical element not shown so as to irradiate the entire surface of the laminated body 50 with light L . The irradiation device 2a can be designed so as to be able to irradiate the entire surface of the reaction layer 20 with the light L, but is not limited thereto. For example, the irradiation device 2a may also use a method of irradiating light L not to the entire surface of the laminate 50, but to an area such as a fraction of the entire surface of the laminate 50, so that the light L The irradiation position of L is stepped so that the entire layered body 50 is irradiated with light L. Moreover, as shown in FIG.5(B), for example, the irradiation apparatus 2b which can irradiate the surface of the laminated body 50 with point light as light L can also be used. The irradiation device 2 b moves the light L of point-like light relative to the layered body 50 , so that the light L can be irradiated across the entire surface of the reaction layer 20 by scanning. In FIG. 5(B), the structure which scans the light L by oscillating the irradiation device 2b was given as an example, but it is not limited to this structure. For example, the irradiation device 2b may be configured to scan the light L by sliding it, or may be configured to scan the light L by using an optical element such as a galvanometer mirror.

After the light irradiation process S10 is performed, a transport process of transporting the laminate 50 with the altered layer 20a formed on the reaction layer 20 from the light irradiation unit 2 to the peeling unit 3 by the transport device 7a of the transport unit 7 is performed. In the peeling unit 3, the laminated body 50 conveyed by the conveyance apparatus 7a is hold|maintained by the holder 60 shown in FIG. For example, the laminated body 50 may also be conveyed to the holder 60 arranged in advance on the fixing table 3b of the peeling unit 3 by the conveying device 7a, and placed on the holder 60 by the conveying device 7a, thereby Attached to the film 61.

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

In the peeling process S20, first, the holder 60 is fixed to the fixing table 3b arranged on the peeling unit 3 by vacuum suction or the like. Since the laminated body 50 is attached to the holder 60, the laminated body 50 will be in the state held by the fixing table 3b. After fixing the holder 60, as shown in FIG. 6(A), the bottom surface 10b of the support body 10 opposite to the reaction layer formation surface 110 is vacuum-adsorbed by the adsorption device 3a. In this state, by moving the adsorption device 3a upward, as shown in FIG. 6(B), the support body 10 is lifted from the substrate 40 with the reaction layer 20 as a separation surface. The altered layer 20a in the reaction layer 20 is easily destroyed or the adhesive surface is easily peeled off by the upward movement of the adsorption device 3a due to the reduction in strength or adhesive force by the irradiation of the light L. Thereby, the support body 10 is easily peeled off from the substrate 40 . In the peeling process S20, the support body 10 is peeled from the reaction layer 20 of the laminated body 50.

After the peeling process S20 is performed, the transport process is performed, that is, the substrate 40 from which the support body 10 has been peeled is still held in the holder 60, and is transported from the peeling unit 3 to the first washing machine by the transport device 7a of the transport unit 7. The cleaning unit 4 , the second cleaning unit 5 or the third cleaning unit 6 .

(substrate cleaning process) Substrate cleaning process S30 includes liquid cleaning process and plasma cleaning process. In the liquid cleaning process, the substrate 40 peeled off from the support body 10 is cleaned with a liquid. In the plasma cleaning process, the substrate 40 peeled off from the support body 10 is treated with plasma. In the substrate cleaning process S30, the liquid cleaning process and the plasma cleaning process can be performed in a predetermined order. Specifically, in the substrate cleaning process S30, any process of the following line A to line D can be performed. Production line A is the situation where liquid cleaning process S31 is performed, followed by plasma cleaning process S32. Production line B is for liquid cleaning process S33, followed by plasma cleaning process S34, and then liquid cleaning process S35. Production line C is for plasma cleaning process S36, followed by liquid cleaning process S37. Production line D is for plasma cleaning process S38, followed by liquid cleaning process S39, and then plasma cleaning process S40. Hereinafter, the production line A to the production line D will be described in sequence.

(Production Line A) In production line A, after the liquid cleaning process S31, the plasma cleaning process S32 is performed. When carrying out each process of the production line A, in the transport process after the peeling process S20 is performed, the substrate 40 from which the support body 10 has been peeled is transported from the peeling unit 3 by the transport device 7a of the transport unit 7. to the first cleaning unit 4. After the substrate 40 is transferred to the first cleaning unit 4 , the liquid cleaning step S31 is performed in the first cleaning unit 4 . FIG. 7 discloses an example of the first cleaning unit 4 and the liquid cleaning process S31. FIG. 7(A) is a view of the state where the substrate 40 is being cleaned by liquid, and FIG. 7(B) is the state after the liquid cleaning process S31. Schematic diagram of substrate 40 .

As shown in FIG. 7(A), in the liquid cleaning process S31, first, in the state where the ring 62 is kept at a predetermined height, the substrate 40 is lifted from the bottom of the film 61 by the lifting device 4a to create a relatively In the ring 62, the substrate 40 protrudes upward. In this case, the upper portion of the ring 62 is supported by the support portion 4b, whereby the substrate 40 can easily protrude upward from the ring 62 . The film 61 is elastically deformed and stretched. In addition, the state shown in FIG. 7(A) may be created by pushing the ring 62 downward through the support portion 4b while the substrate 40 is held at a predetermined height. In addition, 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 substrate 40 may be processed without lifting the substrate 40 with respect to the ring 62 .

Next, the cleaning liquid R1 is discharged from the cleaning liquid nozzle 4 c to the reaction layer 20 in a state where the substrate 40 is lifted. As the cleaning solution R1, as described above, for example, one or more selected from hydrocarbon-based organic solvents, nitrogen-containing organic solvents, ether-based solvents, and ester-based solvents that dissolve the reaction layer 20 and the adhesive layer 30 can be used. the solvent. The cleaning liquid R1 discharged from the cleaning liquid nozzle 4 c flows to the membrane 61 side while dissolving the reaction layer 20 and the adhesive layer 30 , and falls from the ring 62 . The washing liquid R1 dropped from the ring 62 is recovered by a recovery unit (not shown).

With the cleaning solution R1, the unmodified part of the reaction layer 20 and the adhesive layer 30 are dissolved and removed. In addition, although the altered layer 20a in the reaction layer 20 will not be dissolved in the cleaning solution R1, most of it will be removed from the substrate 40 by being washed by the cleaning solution R1. In addition, the cleaning liquid R1a for dissolving the reaction layer 20 and the cleaning liquid R1b for dissolving the adhesive layer 30 may be switched and discharged from the cleaning liquid nozzle 4c. In this case, the cleaning solution R1a for dissolving the reaction layer 20 may be discharged first, and then the cleaning solution R1b for dissolving the adhesive layer 30 may be discharged. In addition, the cleaning liquid nozzle 4c may discharge only the cleaning liquid R1b that dissolves the adhesive layer 30 . In this case, the adhesive layer 30 is dissolved by the cleaning solution R1b, whereby the reaction layer 20 on the adhesive layer 30 is also removed from the substrate 40 due to the flow of the cleaning solution R1b.

In the substrate 40 after the liquid cleaning process S31 is performed, for example, as shown in FIG. 7(B) , a part of the altered layer 20a (reaction layer 20 ) may remain without being washed. In view of this, the substrate 40 is transferred to the second cleaning unit 5 in the transfer process after the liquid cleaning step S31 is performed. After the substrate 40 is transferred to the second cleaning unit 5 , the substrate 40 is subjected to a plasma cleaning process S32 in the second cleaning unit 5 . In the plasma cleaning step S32, a part of the altered layer 20a (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 process S32. FIG. 8(A) is a view of the state where the substrate 40 is being cleaned by plasma, and FIG. 8(B) is the plasma cleaning process. A schematic diagram of the substrate 40 after. As shown in FIG. 8(A), in the plasma cleaning process S32, in the state where the holder 60 is placed on the platform 5b, the plasma 5a is injected into the space on the substrate 40 from a plasma generating device not shown. produce. The plasma 5a is, for example, oxygen plasma. With this plasma 5a, a part of the altered layer 20a (reaction layer 20) remaining on the substrate 40 is processed and removed from the substrate 40 as shown in FIG. 8(B). In line A, the substrate 40 is processed in this way.

(Production Line B) In production line B, for the liquid cleaning process S33, after the plasma cleaning process S34 is performed, the liquid cleaning process S35 is performed. When carrying out each process of the production line B, in the transport process after the peeling process S20 is performed, the substrate 40 from which the support body 10 has been peeled is transported from the peeling unit 3 by the transport device 7a of the transport unit 7. to the third cleaning unit 6. The liquid cleaning process S33 is performed in the third cleaning unit 6 . Fig. 9 discloses an example of the third cleaning unit 6 and the liquid cleaning process S33, Fig. 9(A) is a state view of the substrate 40 being cleaned by the liquid, and Fig. 9(B) is the state after the liquid cleaning process S33 Schematic diagram of substrate 40 .

As shown in FIG. 9(A), in the liquid cleaning process S33, like the liquid cleaning process S31 of the production line A, the upper side of the ring 62 is supported at a predetermined height by the support part 6b, and the lifting device 6a lifts it from The lower part of the film 61 lifts up the substrate 40 to create a state in which the substrate 40 protrudes upward with respect to the ring 62 . In addition, the state shown in FIG. 9(A) may be created by pushing the ring 62 downward through the support portion 6b while the substrate 40 is held at a predetermined height. In addition, 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 substrate 40 may be processed without lifting the substrate 40 with respect to the ring 62 .

Next, the cleaning liquid R2 is discharged from the cleaning liquid nozzle 6 c to the reaction layer 20 in a state where the substrate 40 is lifted. The purpose of the cleaning liquid R2 is to wash the deteriorated layer 20 a from the reaction layer 20 away from the reaction layer 20 . As the cleaning liquid R2, for example, water or the like may be used other than the same liquid as the above-mentioned cleaning liquid R1. The cleaning liquid R2 discharged from the cleaning liquid nozzle 6 c flows through the reaction layer 20 and falls to the membrane 61 side. With this cleaning solution R2, as shown in FIG. 9(B), the altered layer 20a in the reaction layer 20 is washed away, and the unaltered portion of the reaction layer 20 remains on the adhesive layer 30.

After the liquid cleaning step S33, in the transfer step, the substrate 40 is transferred from the third cleaning unit 6 to the second cleaning unit 5 by the transfer device 7a. After the substrate 40 is transferred to the second cleaning unit 5 , the plasma cleaning step S34 is performed in the second cleaning unit 5 . Fig. 10 discloses another example of the second cleaning unit 5 and the plasma cleaning process S34. Fig. 10(A) is a view showing the state of cleaning the substrate 40 by the plasma 5a, and Fig. 10(B) is the state of the plasma cleaning process S34. Schematic diagram of substrate 40 after net engineering S34.

As shown in FIG. 10(A), in the plasma cleaning process S34, in the state where the holder 60 is placed on the platform 5b, the space on the bonding layer 30 is filled with plasma from a plasma generating device not shown. 5a produced. The plasma 5a is, for example, oxygen plasma. By this plasma 5a, as shown in FIG. 10(B), the unaltered portion of the reaction layer 20 remaining on the adhesive layer 30 is processed and removed from the substrate 40. In addition, the powder 20 b generated when the reaction layer 20 is treated with the plasma 5 a may also remain on the adhesive layer 30 a little.

After the plasma cleaning step S34 is performed, in the transfer step, the substrate 40 is transferred from the second cleaning unit 5 to the first cleaning unit 4 by the transfer device 7 a. After the substrate 40 is transferred to the first cleaning unit 4 , the liquid cleaning step S35 is performed in the first cleaning unit 4 . FIG. 11 discloses another example of the first cleaning unit 4 and the liquid cleaning process S35. FIG. 11(A) is a state view of the substrate 40 being cleaned by liquid, and FIG. 11(B) is after the liquid cleaning process S35. A schematic diagram of the substrate 40 .

As shown in FIG. 11(A), in the liquid cleaning process S35, as in the above-mentioned liquid cleaning process S33, the upper side of the ring 62 is supported at a predetermined height by the support part 4b, and the film 61 is lifted from the film 61 by the lifting device 4a. The lower part of the ring 62 lifts the substrate 40 to create a state in which the substrate 40 protrudes upward relative to the ring 62 . In addition, the state shown in FIG. 11(A) may be created by pushing the ring 62 downward through the support portion 6b while the substrate 40 is held at a predetermined height. In addition, 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 substrate 40 may be processed without lifting the substrate 40 with respect to the ring 62 .

Next, the cleaning liquid R3 is discharged from the cleaning liquid nozzle 4 c against the adhesive layer 30 in a state where the substrate 40 is lifted. As the cleaning solution R3, as described above, an organic solvent capable of dissolving the adhesive layer 30 or the like can be used. The cleaning liquid R3 discharged from the cleaning liquid nozzle 4 c flows over the adhesive layer 30 and falls to the membrane 61 side. With the cleaning solution R3, as shown in FIG. 11(B), the subsequent layer 30 is dissolved and removed. In addition, the powder 20b of the reaction layer 20 remaining on the adhesive layer 30 is washed away by the cleaning solution R3 along with the removal of the adhesive layer 30 . In line B, the substrate 40 is processed in this way.

(Production Line C) In the production line C, after the plasma cleaning process S36 is performed, the liquid cleaning process S37 is performed. When each process of the production line C is performed, in the transport process after the peeling process S20 is performed, the substrate 40 from which the support body 10 has been peeled is transported from the peeling unit 3 by the transport device 7a of the transport unit 7. to the second cleaning unit 5. After the substrate 40 is transferred to the second cleaning unit 5 , the plasma cleaning step S36 is performed in the second cleaning unit 5 . Fig. 12 discloses another example of the second cleaning unit 5 and the plasma cleaning process S36. Fig. 12(A) is a view of the state of cleaning the substrate 40 by the plasma 5a, and Fig. 12(B) is the state of the plasma cleaning process S36. Schematic diagram of substrate 40 after net engineering S36.

As shown in FIG. 12(A), the plasma cleaning process S36, like the plasma cleaning process S34 in the production line B, is performed on the adhesive layer 30 with the holder 60 placed on the platform 5b. The space generates plasma 5 a from a plasma generating device not shown. The plasma 5a is, for example, oxygen plasma. By this plasma 5a, a part of the reaction layer 20 is processed and removed from the substrate 40 as shown in FIG. 12(B). In addition, the powder 20b of the reaction layer 20 or the degenerated layer 20a may also slightly remain on the adhesive layer 30 .

After the plasma cleaning step S36 is performed, in the transfer step, the substrate 40 is transferred from the second cleaning unit 5 to the first cleaning unit 4 by the transfer device 7 a. After the substrate 40 is transferred to the first cleaning unit 4 , the liquid cleaning process S37 is performed in the first cleaning unit 4 . FIG. 13 discloses another example of the first cleaning unit 4 and the liquid cleaning process S37. FIG. 13(A) is a state view of the substrate 40 being cleaned by liquid, and FIG. 13(B) is after the liquid cleaning process S37. A schematic diagram of the substrate 40 .

As shown in FIG. 13(A), in the liquid cleaning process S37, like the liquid cleaning process S37 mentioned above, the upper part of the ring 62 is supported at a predetermined height by the support part 4b, and the lifting device 4a is lifted from the film 61 The substrate 40 is lifted from below to create a state in which the substrate 40 protrudes upward relative to the ring 62 . In addition, the state shown in FIG. 13(A) may be created by pushing the ring 62 downward by the support portion 6b while holding the substrate 40 at a predetermined height. In addition, in the liquid cleaning process 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 substrate 40 may be processed without lifting the substrate 40 with respect to the ring 62 .

Next, the cleaning liquid R4 is discharged from the cleaning liquid nozzle 4 c against the adhesive layer 30 in a state where the substrate 40 is lifted. As the cleaning solution R4, one or more solvents selected from hydrocarbon-based organic solvents, nitrogen-containing organic solvents, ether-based solvents, and ester-based solvents that can dissolve the adhesive layer 30 can be used as described above. The cleaning liquid R4 discharged from the cleaning liquid nozzle 4 c flows over the adhesive layer 30 and falls to the membrane 61 side. With the cleaning solution R4, as shown in FIG. 13(B), the subsequent layer 30 is dissolved and removed. In addition, the powder 20b of the reaction layer 20 or the deteriorated layer 20a remaining on the adhesive layer 30 will be washed away by the cleaning solution R4 along with the removal of the adhesive layer 30 . In line C, the substrate 40 is processed in this way.

(Production Line D) In the production line B, the plasma cleaning process S38 is performed, and after the liquid cleaning process S39 is performed, the plasma cleaning process S40 is performed. When each process of the production line D is performed, in the transport process after the peeling process S20 is performed, the substrate 40 from which the support body 10 has been peeled is transported from the peeling unit 3 by the transport device 7a of the transport unit 7. to the second cleaning unit 5. After the substrate 40 is transferred to the second cleaning unit 5 , the plasma cleaning step S38 is performed in the second cleaning unit 5 . The plasma cleaning process S38, like the plasma cleaning process S36 in the production line C, is to generate the plasma 5a in the space on the bonding layer 30 with the holder 60 placed on the platform 5b (refer to FIG. 12(A)). By this plasma 5a, a part of the reaction layer 20 is processed and removed from the substrate 40 (see FIG. 12(B)).

After the plasma cleaning step S38 is performed, in the transfer step, the substrate 40 is transferred from the second cleaning unit 5 to the first cleaning unit 4 by the transfer device 7 a. After the substrate 40 is transferred to the first cleaning unit 4 , the liquid cleaning step S39 is performed in the first cleaning unit 4 . In the liquid cleaning process S39, like the liquid cleaning process S37 of the production line C, the upper part of the ring 62 is supported by the support part 4b, and the substrate 40 is lifted from the bottom of the film 61 by the lifting device 4a to create a relatively A state in which the substrate 40 protrudes upward in the ring 62 (see FIG. 13(A)).

Next, with the substrate 40 raised, the same cleaning liquid as the cleaning liquid R4 is discharged from the cleaning liquid nozzle 4 c against the adhesive layer 30 . The cleaning liquid R4 discharged from the cleaning liquid nozzle 4 c flows over the adhesive layer 30 and falls to the membrane 61 side. The following layer 30 is dissolved and removed by the cleaning solution (see FIG. 13(B)). In addition, the powder 20b of the reaction layer 20 or the deteriorated layer 20a remaining on the adhesive layer 30 will be washed away by the cleaning solution R4 along with the removal of the adhesive layer 30 .

14 is a schematic diagram of another example of the substrate 40 after the plasma cleaning process S38 and the liquid cleaning process S39 in the production line D. As shown in FIG. 14 , after the plasma cleaning process S38 and the liquid cleaning process S39 , the powder 20 b of the reaction layer 20 or the degenerated layer 20 a may remain slightly on the substrate 40 . In view of this, 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 transferred to the second cleaning unit 5 , the substrate 40 is subjected to a plasma cleaning process S40 in the second cleaning unit 5 . FIG. 15 discloses another example of the second cleaning unit 5 and the plasma cleaning process S40. FIG. 15(A) is a view showing the state of the substrate 40 being cleaned by plasma, and FIG. 15(B) is the plasma cleaning process. Schematic diagram of the substrate 40 after process S40.

As shown in FIG. 15(A), the plasma cleaning process S40, like the plasma cleaning process S38, is in the state where the holder 60 is placed on the platform 5b, and the space on the bonding layer 30 is never shown. The plasma generating device generates plasma 5a. The plasma 5a is, for example, oxygen plasma. By this plasma 5a, as shown in FIG. 15(B), the powder 20b of the reaction layer 20 or the altered layer 20a remaining on the adhesive layer 30 is processed and removed from the substrate 40. In the production line D, the substrate 40 is formed in this way.

As above, according to the substrate processing apparatus 1 and the substrate processing method of the present embodiment, the liquid cleaning process S31, S33, S35, S37, S39 performed by the first cleaning unit 4, and the second cleaning unit 5 The plasma cleaning processes S32, S34, S36, S38, and S40 are done to reliably remove the reaction layer 20 or metamorphic layer 20a (residue) remaining on the substrate 40, thereby reducing the impact on subsequent processing, In addition, it is possible to prevent residues from flying from the substrate 40 to pollute the surrounding environment.

<Arrangement of units of substrate processing apparatus for processing laminate 50> FIG. 16 is a schematic diagram showing an example of the arrangement of each unit of the substrate processing apparatus 1 . In FIG. 16 , the directions in the figure are described using the XYZ coordinate system. In this XYZ coordinate system, the vertical direction is defined as the Z direction, and the horizontal direction is defined as the X direction and the Y direction. In addition, for each of the X, Y, and Z directions, the direction indicated by the arrow is referred to as the + direction (eg, the +X direction), and the opposite direction is referred to as the - direction (eg, the -X direction). The substrate processing apparatus 1 shown in FIG. 16 processes a laminate 50 including an adhesive layer 30 . The substrate processing apparatus 1 includes the above-mentioned light irradiation unit 2 , peeling unit 3 , first cleaning unit 4 , second cleaning unit 5 , third cleaning unit 6 , and transfer unit 7 . In addition, the substrate processing apparatus 1 has a loading port 8 for loading a container (for example, FOUP, etc.) that accommodates a plurality of laminates 50 or substrates 40 , and a loading port 8 for carrying in or temporarily storing the laminates 50 or substrates 40 . port 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 arranged on the +X side toward the +Y direction. Moreover, in the substrate processing apparatus 1, the 3rd cleaning unit 6 and the 2nd cleaning unit 5 are arrange|positioned toward +Y direction on the -X side. The light irradiation unit 2 is arranged on the +X side in the substrate processing apparatus 1 and is sandwiched by the peeling unit 3 and the first cleaning unit 4 in plan view. The first cleaning unit 4 is sandwiched by the light irradiation unit 2 and the second cleaning unit 5 in plan view on the +X side in the substrate processing apparatus 1 .

In addition, the substrate processing apparatus 1 shown in FIG. 16 is equipped with two second cleaning units 5 . In this case, for example, when the plasma cleaning process takes time, the processing efficiency can be improved by alternately using two second cleaning units 5 . In addition, one of the two second cleaning units 5 may be used as a main machine, and the other may be used as a backup machine for use when the main machine fails or the like.

In the substrate processing apparatus 1, the loading ports 8 and 9 are arranged on the -Y side. The loading ports 8 and 9 are arranged side by side in the X direction on the -Y side of the substrate processing apparatus 1 . The conveyance unit 7 has a conveyance device 7 a for conveying the laminate 50 or the substrate 40 , and a conveyance path 7 b which is a movement path of the conveyance device 7 a. The transport device 7a can move between the units, or between the loading ports 8, 9 and the units by means of rails (not shown) provided on the transport path 7b. The transfer device 7 a has a robot arm (not shown) capable of holding the laminate 50 or the substrate 40 . The transport path 7b 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 transport device 7a transfers the laminate 50 or the substrate 40 between the units, or between the loading ports 8 and 9 and the units by moving on the transport path 7b.

According to the substrate processing apparatus 1 configured in this way, the laminate 50 or the substrate 40 can be efficiently transported to each unit by the transport unit 7, so that the above-mentioned light irradiation process S10, peeling process S20, and Each process of substrate cleaning process S30. In addition, in the substrate cleaning process S30, the liquid cleaning processes S31, S33, S35, S37, S39, and the plasma cleaning processes S32, S34, S36, S38, S40 can be efficiently performed. In addition, in the substrate processing apparatus 1, the area CON is an area for accommodating control substrates and the like.

<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 schematic flowchart of another example of the substrate processing method according to the embodiment. This substrate processing method is performed in the substrate processing apparatus 1 like the laminated body 50 . As shown in FIG. 17 , the substrate processing method for the laminate 50A not including the adhesive layer 30 includes light irradiation step S50 , peeling step S60 , liquid cleaning step S70 , and plasma cleaning step S80 . In addition, after the plasma cleaning process S80, the liquid cleaning process S90 can also be performed.

(light exposure engineering) In the light irradiation process S50, the reaction layer 20 is modified by irradiating the laminated body 50A with light. The light irradiation process 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 process S50. FIG. 18(A) is a diagram showing a situation in which light is irradiated to the entire layered body 50A, and FIG. 18(B) is a situation in which light is scanned on a laminated body 50A. diagram. In addition, the transport of the laminate 50A to the light irradiation unit 2 is performed by the transport unit 7 .

As shown in FIG. 18(A), the light irradiation unit 2, like the above-mentioned light irradiation process S10 for the laminated body 50, for the laminated body 50A placed on the mounting table 2a, from the side opposite to the substrate 40, also That is, the reaction layer 20 is irradiated with light L from the bottom surface 10b of the support body 10 by the irradiation device 2a. For the light L, it is the same as the above-mentioned light irradiation process S10. Through the light irradiation process S50, the reaction layer 20 will be modified to form a modified layer (or modified portion) 20a. As for the degenerated layer 20 a , as in the above-mentioned light irradiation process S10 , its strength or adhesion to the support 10 will be lower than that of the reaction layer 20 . In addition, as shown in FIG. 18(A), the altered layer 20a does not need to be formed across the entire depth direction, but only needs to be formed in a part of the reaction layer 20 in contact with the support body 10 . In FIG. 18(A), an example of the case where the altered layer 20a is formed in a part of the reaction layer 20 in contact with the support 10 is shown.

The composition of the light irradiation unit 2 is the same as above, so the description is simplified, but as shown in FIG. ), the light L that irradiates point-like light is scanned by the irradiation device 2b. After the light irradiation process S50 is performed, a transport process of transporting the laminate 50A having the altered layer 20a formed on the reaction layer 20 from the light irradiation unit 2 to the peeling unit 3 by the transport device 7a of the transport unit 7 is performed. In the peeling unit 3 , the laminate 50A conveyed by the conveyance device 7 a is held by the holder 60 shown in FIG. 3 . For example, the laminated body 50A may be conveyed onto the holder 60 arranged in advance on the fixing table 3b of the peeling unit 3 by the conveying device 7a, and then placed on the holder 60 by the conveying device 7a, thereby Attached to the film 61.

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

In the peeling process S60 , first, the holder 60 is fixed to the fixing table 3 b arranged on the peeling unit 3 by vacuum suction or the like. Since the laminated body 50A is attached to the holder 60, the laminated body 50A will be in the state held by the fixing table 3b. After fixing the holder 60, as shown in FIG. 19(A), the bottom surface 10b of the support body 10 opposite to the reaction layer forming surface 110 is adsorbed by the adsorption device 3a. In this state, by moving the adsorption device 3 a upward, the support body 10 is lifted from the substrate 40 with the reaction layer 20 as a separation surface as shown in FIG. 19(B) . As mentioned above, the degenerated layer 20a in the reaction layer 20 is easily destroyed by the upward movement of the adsorption device 3a, or the adhesive surface is easily damaged by the irradiation of the light L. Peel off. Thereby, the support body 10 is easily peeled off from the substrate 40 . In the peeling process S60, the support body 10 is peeled from the reaction layer 20 of the laminated body 50A.

After the peeling process S50 is performed, the transport process is performed, that is, the substrate 40 from which the support body 10 has been peeled is still held in the holder 60, and is transported from the peeling unit 3 to the third washing machine by the transport device 7a of the transport unit 7. Net unit 6.

(Liquid cleaning project) After the substrate 40 is transferred to the third cleaning unit 6 , the liquid cleaning step S70 is performed in the third cleaning unit 6 . Fig. 20 discloses an example of the third cleaning unit 6 and the liquid cleaning process S70. Fig. 20(A) is a state view of the substrate 40 being cleaned by liquid, and Fig. 20(B) is the state after the liquid cleaning process S70. Schematic diagram of substrate 40 .

As shown in FIG. 20(A), in the liquid cleaning process S70, as in the above-mentioned liquid cleaning process S33 for the laminate 50, the upper side of the ring 62 is supported at a predetermined height by the support portion 6b, and the The lifting device 6 a lifts the substrate 40 from below the film 61 to make the substrate 40 protrude upward relative to the ring 62 . In addition, the state shown in FIG. 20(A) may be created by pushing the ring 62 downward by the support portion 6b while holding the substrate 40 at a predetermined height. In addition, 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 substrate 40 may be processed without lifting the substrate 40 with respect to the ring 62 .

Next, the cleaning liquid R5 is discharged from the cleaning liquid nozzle 6 c to the reaction layer 20 in a state where the substrate 40 is lifted. The purpose of the cleaning solution R5 is to wash the deteriorated layer 20 a from the reaction layer 20 away from the reaction layer 20 . As the cleaning liquid R5, for example, water or the like can be used as in the above-mentioned cleaning liquid R2. The cleaning liquid R5 discharged from the cleaning liquid nozzle 6 c flows through the reaction layer 20 and falls to the membrane 61 side. With this cleaning solution R5, as shown in FIG. 20(B), the altered layer 20a of the reaction layer 20 is washed away, and the unaltered portion of the reaction layer 20 remains on the substrate 40. After the liquid cleaning step S70, in the transfer step, the substrate 40 is transferred from the third cleaning unit 6 to the second cleaning unit 5 by the transfer device 7a.

(plasma cleaning project) After the substrate 40 is transferred to the second cleaning unit 5 , the plasma cleaning step S80 is performed in the second cleaning unit 5 . The plasma cleaning process S80 is performed in the second cleaning unit 5 . FIG. 21 discloses another example of the second cleaning unit 5 and the plasma cleaning process S80. FIG. 21(A) is a view of a state in which the substrate 40 is being cleaned by the plasma 5a, and FIG. 21(B) is a plasma cleaning process. Schematic diagram of substrate 40 after net engineering S80.

As shown in FIG. 21(A), in the plasma cleaning process S80, in the state where the holder 60 is placed on the platform 5b, the space above the reaction layer 20 is filled with plasma from a plasma generating device not shown. 5a produced. The plasma 5a is, for example, oxygen plasma. By this plasma 5a, the unaltered portion of the reaction layer 20 remaining on the substrate 40 is processed and removed from the substrate 40 as shown in FIG. 21(B).

FIG. 22(A) is a schematic diagram of another example of the substrate 40 after the liquid cleaning process S70 and the plasma cleaning process S80 are performed. As shown in FIG. 22(A), after the plasma cleaning process S80, the powder 20b of the reaction layer 20 may remain on the substrate 40 a little. In view of this, after the plasma cleaning process S80 is carried out, in the transport process, the substrate 40 can also be transported from the second cleaning unit 5 to the third cleaning unit 6 by the transport device 7a, and then cleaned in the third cleaning unit 6. The unit 6 performs the liquid cleaning process S90.

(Liquid cleaning project) FIG. 22(B) is a view showing a state where the substrate 40 shown in FIG. 22(A) is being cleaned by liquid. As shown in FIG. 22(B), in the liquid cleaning process S90, like the above-mentioned liquid cleaning process S70, the upper side of the ring 62 is supported at a predetermined height by the support part 6b, and the film 61 is lifted from the film 61 by the lifting device 6a. The lower part of the ring 62 lifts the substrate 40 to create a state in which the substrate 40 protrudes upward relative to the ring 62 . In addition, the state shown in FIG. 22(B) may be created by pushing the ring 62 downward by the support portion 6b while holding the substrate 40 at a predetermined height. In addition, 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 substrate 40 may be processed without lifting the substrate 40 with respect to the ring 62 .

Next, the cleaning liquid R6 is discharged from the cleaning liquid nozzle 6 c against the adhesive layer 30 in a state where the substrate 40 is lifted. The cleaning solution R5 is used for rinsing the powder 20 b remaining on the substrate 40 from the substrate 40 . As the cleaning liquid R6, water or the like can also be used as in the above-mentioned cleaning liquid R5. The cleaning liquid R6 discharged from the cleaning liquid nozzle 6 c flows over the substrate 40 and falls to the film 61 side. The powder 20b remaining on the substrate 40 is washed away by the cleaning solution R6. In this way, the substrate 40 is formed. In addition, it is optional whether to perform the liquid cleaning process S90, or not to perform the liquid cleaning process S90.

As above, according to the substrate processing apparatus 1 and the substrate processing method of the present embodiment, the liquid cleaning processes S70 and S90 performed by the third cleaning unit 6 and the plasma cleaning performed by the second cleaning unit 5 Cleaning process S80, to reliably remove the reaction layer 20 or altered layer 20a (residue) remaining on the substrate 40, thereby reducing the impact on subsequent processing, and preventing the residue from flying from the substrate 40 to pollute the surrounding environment .

<Arrangement of units of substrate processing apparatus for processing laminate 50A> FIG. 23 is a schematic diagram showing an example of the arrangement of each unit of the substrate processing apparatus 1A. In FIG. 23 , the directions in the figure are described using the XYZ coordinate system as in FIG. 16 . When processing a laminated body 50A that does not include the adhesive layer 30, although the substrate processing apparatus 1 shown in FIG. The first cleaning unit 4. Therefore, when processing the laminated body 50A, the substrate processing apparatus 1A shown in FIG. 23 can also be used. The substrate processing apparatus 1A shown in FIG. 23 processes a laminate 50A not including the adhesive layer 30 . The substrate processing apparatus 1A includes the above-mentioned light irradiation unit 2 , peeling unit 3 , second cleaning unit 5 , third cleaning unit 6 , and transfer unit 7 . In addition, the substrate processing apparatus 1 has a loading port 8 for loading a container for accommodating a plurality of laminates 50 or substrates 40 , and a loading port 9 for carrying in or temporarily storing the laminates 50 or substrates 40 .

The substrate processing apparatus 1A has a rectangular shape 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 toward the +Y direction. In addition, in the substrate processing apparatus 1A, the third cleaning unit 6 is disposed on the -X side. The light irradiation unit 2 is sandwiched by the peeling unit 3 and the second cleaning unit 5 in plan view.

In the substrate processing apparatus 1A, the loading ports 8 and 9 are similar to the substrate processing apparatus 1 shown in FIG. 16 , and description thereof will be omitted. The conveyance unit 7 has a conveyance device 7 a for conveying the laminate 50A or the substrate 40 , and a conveyance path 7 b which is a movement path of the conveyance device 7 a. The transport device 7a can move between the units, or between the loading ports 8, 9 and the units by means of rails (not shown) provided on the transport path 7b. The transfer device 7 a has a robot arm (not shown) capable of holding the laminate 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 transport device 7a transfers the laminate 50 or the substrate 40 between the units, or between the loading ports 8 and 9 and the units by moving on the transport path 7b.

According to the substrate processing apparatus 1A configured in this way, the laminate 50A or the substrate 40 can be efficiently transferred to each unit by the transfer unit 7, so that the above-mentioned light irradiation process S50, peeling process S60, liquid Cleaning process S70, plasma cleaning process S80, and liquid cleaning process S90. In addition, in the substrate processing apparatus 1A, the region CON is a region for accommodating control substrates and the like.

As mentioned above, although embodiment and an Example were described, this invention is not limited to the said description, Various changes are possible in the range which does not deviate from the summary of this invention. For example, the substrate 40 is cut according to each electronic component 41, and such a cutting unit can also be included in the above-mentioned substrate processing apparatus 1, 1A, and the cutting unit can also be connected and configured in the substrate processing apparatus 1, 1A .

R1, R2, R3, R4, R5, R6‧‧‧Cleaning solution 1. 1A‧‧‧substrate processing equipment 2‧‧‧light irradiation unit 2a, 2b‧‧‧Irradiation device 3‧‧‧Peel off unit 3a‧‧‧Adsorption device 4‧‧‧1st cleaning unit 5‧‧‧The second cleaning unit 6‧‧‧The third cleaning unit 7‧‧‧Conveyor unit 7a‧‧‧Conveyor 8, 9‧‧‧load port 10‧‧‧Support 20‧‧‧reaction layer 20a‧‧‧metamorphic layer 30‧‧‧adhesion layer 40‧‧‧substrate 50, 50A‧‧‧laminated body 60‧‧‧Retainer

[FIG. 1] A diagram showing an example of a substrate processing apparatus according to the first embodiment in functional blocks. [Fig. 2] An example of a laminate processed in a substrate processing apparatus is shown, (A) is a view of a laminate including an adhesive layer, and (B) is a view of a laminate not including an adhesive layer. [ Fig. 3 ] Showing an example of a holder holding a laminate, (A) is a perspective view of the holder holding a laminate, and (B) is a cross-sectional view along line A-A of (A). [FIG. 4] A schematic flowchart of an example of the substrate processing method related to the embodiment. [ Fig. 5 ] Showing an example of a light irradiation unit and a light irradiation process, (A) is a diagram showing how light is irradiated to the entire surface of the laminate, and (B) is a diagram showing how light has been scanned across the laminate. [ Fig. 6 ] An example of a peeling unit and a peeling process is shown, (A) is a diagram before the support is peeled off, and (B) is a diagram after the support is peeled off. [Fig. 7] An example of the first cleaning unit and liquid cleaning process is shown, (A) is a view of the substrate being cleaned by liquid, and (B) is a schematic diagram of the substrate after the liquid cleaning process. [Fig. 8] Continuing from Fig. 7, an example of the second cleaning unit and the plasma cleaning process is disclosed, (A) is the state of the substrate being cleaned by the plasma, and (B) is after the plasma cleaning process The schematic diagram of the substrate. [ Fig. 9 ] An example showing the third cleaning unit and liquid cleaning process, (A) is the state of cleaning the substrate with liquid, (B) is the schematic diagram of the substrate after the liquid cleaning process. [Fig. 10] Continuing from Fig. 9, another example of the second cleaning unit and the plasma cleaning process is disclosed, (A) is the state of the substrate being cleaned by plasma, (B) is the plasma cleaning process Schematic diagram of the substrate after. [Fig. 11] Continuing from Fig. 10, another example of the first cleaning unit and the liquid cleaning process is revealed, (A) is the state of the substrate being cleaned by the liquid, and (B) is the substrate after the liquid cleaning process schematic diagram. [Fig. 12] Another example showing the second cleaning unit and the plasma cleaning process, (A) is the state of the substrate being cleaned by the plasma, (B) is the schematic diagram of the substrate after the plasma cleaning process . [Fig. 13] Continuing from Fig. 12, another example of the first cleaning unit and the liquid cleaning process is disclosed, (A) is the state of the substrate being cleaned by the liquid, and (B) is the substrate after the liquid cleaning process schematic diagram. [Fig. 14] Another schematic diagram of the substrate after the liquid cleaning process and the plasma cleaning process. [Fig. 15] Continuing from Fig. 14, another example of the second cleaning unit and the plasma cleaning process is revealed, (A) is the state of the substrate being cleaned by plasma, (B) is the plasma cleaning process Schematic diagram of the substrate after. [ Fig. 16 ] A schematic diagram showing an example of the arrangement of each unit of the substrate processing apparatus. [FIG. 17] A schematic flowchart of another example of the substrate processing method of the embodiment. [ Fig. 18 ] Showing another example of the light irradiation unit and the light irradiation process, (A) is a diagram showing how light is irradiated to the entire surface of the laminate, and (B) is a diagram showing how light is scanned across the laminate. [ Fig. 19 ] Shows another example of the peeling unit and the peeling process, (A) is the figure before peeling the support body, (B) is the figure after peeling the support body. [Fig. 20] Another example showing the third cleaning unit and the liquid cleaning process, (A) is the state of the substrate being cleaned by the liquid, and (B) is the schematic diagram of the substrate after the liquid cleaning process. [Fig. 21] Continuing from Fig. 20, another example of the second cleaning unit and the plasma cleaning process is disclosed, (A) is the state of the substrate being cleaned by plasma, (B) is the plasma cleaning process Schematic diagram of the substrate after. [Fig. 22] (A) is another schematic diagram of the substrate after the liquid cleaning process and the plasma cleaning process, and (B) is a continuation of (A) and a state diagram of the substrate being cleaned by the liquid. [ Fig. 23 ] A schematic diagram showing another example of the arrangement of each unit of the substrate processing apparatus.

1‧‧‧Substrate processing equipment

2‧‧‧light irradiation unit

3‧‧‧Peel off unit

4‧‧‧1st cleaning unit

5‧‧‧The second cleaning unit

6‧‧‧The third cleaning unit

7‧‧‧Conveyor unit

7a‧‧‧Conveyor

10‧‧‧Support

20‧‧‧reaction layer

30‧‧‧adhesion layer

40‧‧‧substrate

41‧‧‧Electronic Parts

42‧‧‧Mold sealing

50‧‧‧laminated body

Claims (15)

A substrate processing apparatus comprising: a light irradiation unit for irradiating light to a laminate including a support, a substrate, and a reaction layer interposed between the support and the substrate, thereby deteriorating the reaction layer; and a peeling unit, The substrate is peeled from the support; and the first cleaning unit cleans the substrate peeled off the support with a liquid; and the second cleaning unit cleans the substrate peeled off from the support. The substrate is treated with plasma; and a holder holding the laminate; the holder having: a film elastically deformable and attached to the substrate among the laminates; and a ring to surround the laminate The above-mentioned first cleaning unit is attached to the above-mentioned film in such a way that the above-mentioned substrate protrudes above the above-mentioned ring by deforming the above-mentioned film during cleaning. The substrate processing device as described in claim 1 of the patent claims, wherein the laminate further has an adhesive layer between the reaction layer and the substrate, and the first cleaning unit is attached to the substrate from the support The aforementioned adhesive layer of the aforementioned substrate that has been peeled off is removed with a liquid. The substrate processing apparatus described in claim 1 or claim 2, wherein the liquid used in the first cleaning unit is selected from hydrocarbon-based organic solvents, nitrogen-containing organic solvents, and ether-based solvents. 1 or more selected from ester-based solvents. The substrate processing apparatus according to claim 1 or claim 2, wherein the second cleaning unit processes the substrate with oxygen plasma. The substrate processing apparatus described in claim 1 or claim 2, wherein the first cleaning unit, the second cleaning unit, and the stripping unit are arranged in a structure formed by a plurality of wall panels in the same space. The substrate processing apparatus according to claim 5, wherein a transfer device for transferring the substrate from the support or the substrate peeled off from the support is provided in the space. A method for treating a substrate, comprising: a light irradiation process of irradiating light to a laminate including a support, a substrate, and a reaction layer interposed between the support and the substrate, thereby deteriorating the reaction layer; and a peeling process, peeling the aforementioned substrate from the aforementioned support body; and a liquid cleaning process of cleaning the aforementioned substrate peeled from the aforementioned support body with a liquid; and a plasma cleaning process of removing the aforementioned substrate peeled from the aforementioned support body By plasma treatment; the aforementioned laminated body is held in a holder having: a film elastically deformable and attached to the aforementioned substrate in the aforementioned laminated body; and a ring in such a manner as to surround the aforementioned laminated body Attached to the film; the liquid cleaning process is performed in a state in which the substrate protrudes above the ring by deforming the film. The substrate processing method described in item 7 of the scope of the patent application, wherein the aforementioned liquid used in the aforementioned liquid cleaning process includes hydrocarbon-based organic solvents, nitrogen-containing organic solvents, ether-based solvents, and ester-based solvents Choose one or more. The substrate processing method described in claim 7 or claim 8, wherein, in the plasma cleaning process, the substrate is treated with oxygen plasma. The substrate processing method described in claim 7 or claim 8, wherein the plasma cleaning process is performed on the substrate peeled off from the support body after the liquid cleaning process. The substrate processing method described in claim 7 or claim 8, wherein, for the substrate peeled off from the support, the liquid cleaning process is performed after the plasma cleaning process. The substrate processing method described in claim 11 of the patent application, wherein, Different from the aforementioned liquid cleaning process after the aforementioned plasma cleaning process, more than 1 liquid cleaning process is performed before the aforementioned plasma cleaning process. The substrate processing method described in claim 12 of the patent application, wherein the liquid used in the liquid cleaning process before the plasma cleaning process includes hydrocarbon-based organic solvents, nitrogen-containing organic solvents, etc. One or more selected from solvents, ether-based solvents, and ester-based solvents. The substrate processing method described in claim 7 or claim 8, wherein the laminate further has an adhesive layer between the reaction layer and the substrate. The substrate processing method as described in item 7 or 8 of the scope of the patent application, wherein, between the processes of the aforementioned liquid cleaning process, the aforementioned plasma cleaning process, and the aforementioned stripping process, it includes transporting the aforementioned support body or The transfer process of the said board|substrate peeled from the said support body.

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