WO2013172110A1

WO2013172110A1 - Support body separation method and support body separation device

Info

Publication number: WO2013172110A1
Application number: PCT/JP2013/060272
Authority: WO
Inventors: 高瀬　真治; 藤井　恭
Original assignee: 東京応化工業株式会社
Priority date: 2012-05-16
Filing date: 2013-04-04
Publication date: 2013-11-21
Also published as: JP2013239650A; TW201405693A; KR20150013734A

Abstract

Provided is a support body separation method for separating a laminated body (1) formed by laminating the following in this order: a substrate (11); an adhesive layer (14); a separation layer (16) that transforms by absorbing light; and a support plate (12). The method includes a radiation step for radiating pulsed laser light to the separation layer (16). With respect to each pulse of the laser light, the laser light is scanned so that the irradiated regions on the separation layer (16) do not overlap each other.

Description

Support separation method and support separation device

The present invention relates to a support separating method and a support separating apparatus for separating a support from a laminate in which a substrate and a support are laminated.

In recent years, electronic devices such as IC cards and mobile phones have been required to be thinner, smaller, and lighter. In order to satisfy these requirements, a thin semiconductor chip must be used as a semiconductor chip to be incorporated. For this reason, the thickness (film thickness) of the wafer substrate on which the semiconductor chip is based is currently 125 μm to 150 μm, but it is said that it must be 25 μm to 50 μm for the next generation chip. Therefore, in order to obtain a wafer substrate having the above film thickness, a wafer substrate thinning step is indispensable.

Since the strength of the wafer substrate is reduced due to the thinning of the wafer substrate, a circuit on the wafer substrate is automatically transferred while the support plate is bonded to the wafer substrate during the manufacturing process in order to prevent damage to the thinned wafer substrate. Etc. are mounted. Then, after the manufacturing process, the wafer substrate is separated from the support plate. Therefore, it is preferable that the wafer substrate and the support plate are firmly bonded during the manufacturing process, but it is preferable that the wafer substrate can be smoothly separated from the support plate after the manufacturing process.

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

As a semiconductor chip manufacturing method in which a support is bonded to a semiconductor wafer, the semiconductor wafer is processed, and then the support is separated, a method as described in Patent Document 1 is known. In the method described in Patent Document 1, a light-transmitting support and a semiconductor wafer are bonded together via a photothermal conversion layer and an adhesive layer provided on the support, and the semiconductor wafer is processed and then supported. By irradiating radiation energy from the body side, the photothermal conversion layer is decomposed, and the semiconductor wafer is separated from the support.

Japanese Patent Publication “Japanese Patent Laid-Open No. 2005-159155 (released on June 16, 2005)”

However, as described in Patent Document 1, when the support is separated from the semiconductor wafer, irradiation with radiant energy from the support may cause the irradiated laser light to leak from the photothermal conversion layer. Then, the leaked light may reach a substrate such as a semiconductor wafer, or an electric circuit, a display element or the like mounted on the substrate and adversely affect them. As a method for reducing such leakage light, it is conceivable to increase the thickness of the photothermal conversion layer, but it is difficult from the viewpoint of throughput and cost.

The present invention has been made in view of the above-mentioned problems. While realizing strong adhesion between the substrate and the support during the manufacturing process, the substrate and the support can be easily attached by light irradiation after the manufacturing process. The main object of the present invention is to provide a support separating method and a support separating apparatus that are separable and prevent adverse effects of light on the substrate surface.

In order to solve the above-described problems, a support separating method according to the present invention includes a substrate, an adhesive layer, a separation layer that is altered by absorbing light, and a laminate in which the support is stacked in this order. A support separating method for separating a body, comprising an irradiation step of irradiating the separation layer with a pulsed laser beam, wherein the irradiation step is performed on the separation layer in each laser pulse of the laser beam. The laser beam is scanned so that the irradiated areas do not overlap each other.

In addition, the support separating apparatus according to the present invention is a support that separates a laminate formed by laminating a substrate, an adhesive layer, a separation layer that is altered by absorbing light, and a support in this order. The separation apparatus includes an irradiation unit configured to irradiate the separation layer with a pulsed laser beam, and the irradiation unit overlaps the irradiated regions on the separation layer with each other in each laser pulse of the laser beam. In order to avoid this, the laser light is scanned.

According to the present invention, the substrate and the support can be firmly bonded to each other during the manufacturing process, and the substrate and the support can be easily separated by light irradiation after the manufacturing process. There is an effect that the adverse effect of can be prevented.

In the support body separation method which concerns on one Embodiment of this invention, it is a figure which shows the process of irradiating a laser beam, and peeling with a board | substrate and a support plate. In the support body separation method which concerns on one Embodiment of this invention, it is a figure which shows the irradiated area of a laser beam when scanning a laser beam.

[Support Separation Method]
With reference to FIG. 1, the support body separation method which concerns on one Embodiment of this invention is demonstrated. FIG. 1 is a diagram showing a step of irradiating a laser beam and separation of a substrate and a support plate in a support separating method according to an embodiment of the present invention. In the support separating method according to the present embodiment, the substrate 11, the adhesive layer 14, the separation layer 16 that is altered by absorbing light, and the support plate (support) 12 are laminated in this order. The support plate 12 is separated from the laminate 1. The substrate 11 and the support plate 12 are bonded together via an adhesive layer 14 and a separation layer 16.

(substrate)
The substrate 11 is subjected to processes such as thinning and mounting while being supported by the support plate 12. The substrate 11 is not limited to a wafer substrate, and an arbitrary substrate such as a thin film substrate or a flexible substrate can be used. Further, a fine structure of an electronic element such as an electric circuit may be formed on the surface of the substrate 11 on the adhesive layer 14 side.

(Support plate)
The support plate 12 is a support body that supports the substrate 11 and has optical transparency. Therefore, when light is irradiated toward the support plate 12 from outside the stacked body 1, the light passes through the support plate 12 and reaches the separation layer 16. Further, the support plate 12 does not necessarily need to transmit all the light, and it is sufficient if the support plate 12 can transmit the light to be absorbed by the separation layer 16 (having a predetermined wavelength).

The support plate 12 supports the substrate 11 and may have a strength necessary for preventing damage or deformation of the substrate 11 during processes such as thinning, transporting, and mounting of the substrate 11. From the above viewpoint, examples of the support plate 12 include those made of glass, silicon, and acrylic resin.

(Separation layer)
The separation layer 16 is a layer formed of a material that changes in quality by absorbing light irradiated through the support. In the present specification, the “deterioration” of the separation layer 16 means a phenomenon in which the separation layer 16 can be broken by receiving a slight external force, or a state in which the adhesive force with the layer in contact with the separation layer 16 is reduced. means. As a result of the alteration of the separation layer 16 resulting from the absorption of light, the separation layer 16 loses its strength or adhesiveness prior to receiving light irradiation. Therefore, by applying a slight external force (for example, lifting the support plate 12), the separation layer 16 is broken and the support plate 12 and the substrate 11 can be easily separated.

Further, the alteration of the separation layer 16 includes decomposition (exothermic or non-exothermic), cross-linking, configuration change or dissociation of functional groups due to absorbed light energy (and curing of the separation layer and degassing associated therewith). , Contraction or expansion) and the like. The alteration of the separation layer 16 occurs as a result of light absorption by the material constituting the separation layer 16. Therefore, the type of alteration of the separation layer 16 can be changed according to the type of material constituting the separation layer 16.

The separation layer 16 is provided on the surface of the support plate 12 on the side where the substrate 11 is bonded via the adhesive layer 14. That is, the separation layer 16 is provided between the support plate 12 and the adhesive layer 14.

The thickness of the separation layer 16 is more preferably, for example, 0.05 to 50 μm, and further preferably 0.3 to 1 μm. If the thickness of the separation layer 16 is within the range of 0.05 to 50 μm, the separation layer 16 can be altered as desired by short-time light irradiation and low-energy light irradiation. The thickness of the separation layer 16 is particularly preferably within a range of 1 μm or less from the viewpoint of productivity.

In the laminate 1, another layer may be further formed between the separation layer 16 and the support plate 12. In this case, the other layer should just be comprised from the material which permeate | transmits light. Thereby, a layer imparting preferable properties to the stacked body 1 can be appropriately added without hindering the incidence of light on the separation layer 16. The wavelength of light that can be used differs depending on the type of material constituting the separation layer 16. Therefore, the material constituting the other layer does not need to transmit all light, and can be appropriately selected from materials capable of transmitting light having a wavelength that can alter the material constituting the separation layer 16.

The separation layer 16 is preferably formed only from a material having a structure that absorbs light, but the material does not have a structure that absorbs light as long as the essential characteristics of the present invention are not impaired. May be added to form the separation layer 16. Moreover, it is preferable that the surface of the separation layer 16 on the side facing the adhesive layer 14 is flat (unevenness is not formed), so that the separation layer 16 can be easily formed and even when pasted. It becomes possible to paste on.

As the separation layer 16, a material that forms the separation layer 16 as described below may be used by bonding it to the support plate 12 in advance, or the separation layer 16 may be formed on the support plate 12. You may use what applied the material and solidified in the film form. The method of applying the material constituting the separation layer 16 on the support plate 12 is appropriately selected from conventionally known methods such as chemical vapor deposition (CVD) deposition according to the type of material constituting the separation layer 16. can do.

The separation layer 16 may be altered by absorbing light emitted from the laser. In other words, the light irradiated to the separation layer 16 in order to change the quality of the separation layer 16 may be emitted from a laser. Examples of lasers that emit light for irradiating the separation layer 16 include solid-state lasers such as YAG lasers, Libby lasers, glass lasers, YVO ₄ lasers, LD lasers, and fiber lasers, liquid lasers such as dye lasers, CO ₂ lasers, and excimers. Examples thereof include a gas laser such as a laser, an Ar laser, and a He—Ne laser, a laser beam such as a semiconductor laser and a free electron laser, or a non-laser beam. The laser that emits light to irradiate the separation layer 16 can be appropriately selected according to the material constituting the separation layer 16 and irradiates light having a wavelength that can alter the material constituting the separation layer 16. The laser to be selected may be selected.

<Polymer containing light absorbing structure in its repeating unit>
The separation layer 16 may contain a polymer containing a light-absorbing structure in its repeating unit. The polymer is altered by irradiation with light. The alteration of the polymer occurs when the structure absorbs the irradiated light. The separation layer 16 loses its strength or adhesiveness before being irradiated with light as a result of the alteration of the polymer. Therefore, by applying a slight external force (for example, lifting the support plate 12), the separation layer 16 is broken and the support plate 12 and the substrate 11 can be easily separated.

The above structure having light absorption is a chemical structure that absorbs light and alters a polymer containing the structure as a repeating unit. The structure is an atomic group including a conjugated π electron system composed of, for example, a substituted or unsubstituted benzene ring, condensed ring, or heterocyclic ring. More specifically, the structure may be a cardo structure or a benzophenone structure, diphenyl sulfoxide structure, diphenyl sulfone structure (bisphenyl sulfone structure), diphenyl structure or diphenylamine structure present in the side chain of the polymer.

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

In the formula, each R is independently an alkyl group, aryl group, halogen, hydroxyl group, ketone group, sulfoxide group, sulfone group, or N (R ₁ ) (R ₂ ) (where R ₁ and R ₂ are Each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), Z is absent or is CO—, —SO ₂ —, —SO— or —NH—, and n is 0 or It is an integer from 1 to 5.

In addition, the polymer includes, for example, a repeating unit represented by any one of (a) to (d) among the following formulas, represented by (e), or represented by (f) Contains structure in its main chain.

In the formula, l is an integer of 1 or more, m is 0 or an integer of 1 to 2, and X is any one of the formulas shown in the above “Chemical Formula 1” in (a) to (e). , (F) is any one of the formulas shown in the above “Chemical Formula 1” or does not exist, and Y ₁ and Y ₂ are each independently —CO— or SO ₂ —. l is preferably an integer of 10 or less.

Examples of the benzene ring, condensed ring and heterocyclic ring shown in the above “chemical formula 1” include phenyl, substituted phenyl, benzyl, substituted benzyl, naphthalene, substituted naphthalene, anthracene, substituted anthracene, anthraquinone, substituted anthraquinone, acridine, substituted Examples include acridine, azobenzene, substituted azobenzene, fluoride, substituted fluoride, fluoride, substituted fluoride, carbazole, substituted carbazole, N-alkylcarbazole, dibenzofuran, substituted dibenzofuran, phenanthrene, substituted phenanthrene, pyrene, and substituted pyrene. When the exemplified substituent has a substituent, the substituent is, for example, alkyl, aryl, halogen atom, alkoxy, nitro, aldehyde, cyano, amide, dialkylamino, sulfonamide, imide, carboxylic acid, carboxylic acid Selected from esters, sulfonic acids, sulfonate esters, alkylaminos and arylaminos.

Of the substituents represented by “Chemical Formula 1” above, as an example of the fifth substituent having two phenyl groups and Z is —SO ₂ —, bis (2, 4-dihydroxyphenyl) sulfone, bis (3,4-dihydroxyphenyl) sulfone, bis (3,5-dihydroxyphenyl) sulfone, bis (3,6-dihydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfone, bis (3-hydroxyphenyl) sulfone, bis (2-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone and the like can be mentioned.

Of the substituents represented by “Chemical Formula 1” above, as an example of the fifth substituent having two phenyl groups and Z being —SO—, bis (2,3 -Dihydroxyphenyl) sulfoxide, bis (5-chloro-2,3-dihydroxyphenyl) sulfoxide, bis (2,4-dihydroxyphenyl) sulfoxide, bis (2,4-dihydroxy-6-methylphenyl) sulfoxide, bis (5 -Chloro-2,4-dihydroxyphenyl) sulfoxide, bis (2,5-dihydroxyphenyl) sulfoxide, bis (3,4-dihydroxyphenyl) sulfoxide, bis (3,5-dihydroxyphenyl) sulfoxide, bis (2,3 , 4-Trihydroxyphenyl) sulfoxide, bis (2,3,4-trihydroxy-6-methylphenol) ) -Sulfoxide, bis (5-chloro-2,3,4-trihydroxyphenyl) sulfoxide, bis (2,4,6-trihydroxyphenyl) sulfoxide, bis (5-chloro-2,4,6-tri) Hydroxyphenyl) sulfoxide and the like.

Of the substituents represented by the above “Chemical Formula 1”, the fifth substituent having two phenyl groups and Z is —C (═O) — , 4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2', 5,6'-tetrahydroxybenzophenone, 2-hydroxy-4- Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,6-dihydroxy-4-methoxybenzophenone, 2,2 ' -Dihydroxy-4,4'-dimethoxybenzophenone, 4-amino-2'-hydroxybenzophenone, 4-di Tylamino-2'-hydroxybenzophenone, 4-diethylamino-2'-hydroxybenzophenone, 4-dimethylamino-4'-methoxy-2'-hydroxybenzophenone, 4-dimethylamino-2 ', 4'-dihydroxybenzophenone, and 4 -Dimethylamino-3 ', 4'-dihydroxybenzophenone and the like.

When the structure is present in the side chain of the polymer, the ratio of the repeating unit containing the structure to the polymer is such that the light transmittance of the separation layer 16 is 0.001 to 10%. It is in the range. If the polymer is prepared so that the ratio falls within such a range, the separation layer 16 can sufficiently absorb light and can be reliably and rapidly altered. That is, it is easy to remove the support plate 12 from the laminate 1, and the light irradiation time necessary for the removal can be shortened.

The above structure can absorb light having a wavelength in a desired range by selecting the type. For example, the wavelength of light that can be absorbed by the above structure is more preferably 100 to 2000 nm. Within this range, the wavelength of light that can be absorbed by the structure is on the shorter wavelength side, for example, 100 to 500 nm. For example, the structure can alter the polymer containing the structure by absorbing ultraviolet light, preferably having a wavelength of about 300-370 nm.

The light that can be absorbed by the above structure is, for example, a high-pressure mercury lamp (wavelength: 254 nm to 436 nm), a KrF excimer laser (wavelength: 248 nm), an ArF excimer laser (wavelength: 193 nm), an F ₂ excimer laser (wavelength: 157 nm), Light emitted from XeCl laser (308 nm), XeF laser (wavelength: 351 nm) or solid-state UV laser (wavelength: 355 nm), or g-line (wavelength: 436 nm), h-line (wavelength: 405 nm) or i-line (wavelength: 365 nm) ) Etc.

The separation layer 16 described above contains a polymer containing the above structure as a repeating unit, but the separation layer 16 may further contain components other than the polymer. Examples of the component include a filler, a plasticizer, and a component that can improve the peelability of the support plate 12. These components are appropriately selected from conventionally known substances or materials that do not hinder or promote the absorption of light by the above structure and the alteration of the polymer.

<Inorganic material>
The separation layer 16 may be made of an inorganic material. The separation layer 16 is composed of an inorganic substance, and is thereby altered by absorbing light. As a result, the separation layer 16 loses strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, lifting the support plate 12 or the like), the separation layer 16 is broken and the support plate 12 and the substrate 11 can be easily separated.

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

The above inorganic substance absorbs light having a wavelength in a specific range depending on the type. By irradiating the separation layer with light having a wavelength within a range that is absorbed by the inorganic material used for the separation layer 16, the inorganic material can be suitably altered.

The light applied to the separation layer 16 made of an inorganic material may be, for example, a solid-state laser such as a YAG laser, Libby laser, glass laser, YVO ₄ laser, LD laser, or fiber laser, or a dye laser, depending on the wavelength that the inorganic material can absorb. A liquid laser such as CO ₂ laser, excimer laser, Ar laser, He—Ne laser or other gas laser, semiconductor laser, free electron laser or other laser light, or non-laser light may be used as appropriate.

The separation layer 16 made of an inorganic material can be formed on the support plate 12 by a known technique such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, or spin coating. The thickness of the separation layer 16 made of an inorganic material is not particularly limited as long as it is a film thickness that can sufficiently absorb the light to be used. For example, a film thickness of 0.05 to 10 μm is more preferable. Alternatively, an adhesive may be applied in advance to both surfaces or one surface of an inorganic film (for example, a metal film) made of an inorganic material constituting the separation layer 16 and attached to the support plate 12 and the substrate 11.

When a metal film is used as the separation layer 16, laser reflection or charging of the film may occur depending on conditions such as the film quality of the separation layer 16, the type of laser light source, and laser output. Therefore, it is preferable to take such measures by providing an antireflection film or an antistatic film on the upper and lower sides of the separation layer 16 or one of them.

<Compound having infrared absorbing structure>
The separation layer 16 may be formed of a compound having an infrared absorbing structure. The compound is altered by absorbing infrared rays. The separation layer 16 loses its strength or adhesiveness before being irradiated with infrared rays as a result of the alteration of the compound. Therefore, by applying a slight external force (for example, lifting the support plate), the separation layer 16 is broken and the support plate 12 and the substrate 11 can be easily separated.

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

Examples of the structure containing the carbon-halogen bond include —CH ₂ Cl, —CH ₂ Br, —CH ₂ I, —CF ₂ —, —CF ₃ , —CH═CF ₂ , —CF═CF ₂ , fluorine Aryl chloride, and aryl chloride.

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

Examples of the structure containing the P—A ² bond include PH, PH ₂ , P—CH ₃ , P—CH ₂ —, PC ₆ H ₅ , A ³ ₃ —PO (A ³ is aliphatic or aromatic. Group), (A ⁴ O) ₃ —PO (A ⁴ is alkyl), P—OCH ₃ , P—OCH ₂ CH ₃ , P—OC ₆ H ₅ , P—O—P, P—OH, and O = P—OH and the like.

The above structure can absorb infrared rays having a wavelength in a desired range by selecting the type. Specifically, the wavelength of infrared rays that can be absorbed by the above structure is, for example, in the range of 1 μm to 20 μm, and more preferably in the range of 2 μm to 15 μm. Furthermore, when the structure is a Si—O bond, a Si—C bond, or a Ti—O bond, it can be in the range of 9 μm to 11 μm. In addition, those skilled in the art can easily understand the infrared wavelength that can be absorbed by each structure. For example, as an absorption band in each structure, non-patent literature: SILVERSTEIN / BASSLER / MORRILL, “Identification method by spectrum of organic compound (5th edition) —Combination of MS, IR, NMR and UV” (published in 1992) Reference can be made to the descriptions on pages 146 to 151.

As a compound having an infrared absorbing structure used for forming the separation layer 16, among the compounds having the structure as described above, it can be dissolved in a solvent for coating and solidified to form a solid layer. As long as it is possible, there is no particular limitation. However, in order to effectively alter the compound in the separation layer 16 and facilitate separation of the support plate 12 and the substrate 11, the absorption of infrared rays in the separation layer 16 is large, that is, the separation layer 16 is irradiated with infrared rays. It is preferable that the infrared transmittance is low. Specifically, the infrared transmittance in the separation layer 16 is preferably lower than 90%, and the infrared transmittance is more preferably lower than 80%.

For example, as the compound having a siloxane skeleton, for example, a resin that is a copolymer of a repeating unit represented by the following chemical formula (1) and a repeating unit represented by the following chemical formula (2), or A resin that is a copolymer of a repeating unit represented by the following chemical formula (1) and a repeating unit derived from an acrylic compound can be used.

(In the chemical formula (2), R ₁ is hydrogen, an alkyl group having 10 or less carbon atoms, or an alkoxy group having 10 or less carbon atoms)
Among them, as a compound having a siloxane skeleton, a copolymer of tert-butylstyrene (TBST) -dimethylsiloxane, which is a copolymer of a repeating unit represented by the above chemical formula (1) and a repeating unit represented by the following chemical formula (3). A polymer is more preferable, and a TBST-dimethylsiloxane copolymer containing a repeating unit represented by the above formula (1) and a repeating unit represented by the following chemical formula (3) in a ratio of 1: 1 is further preferable.

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

(In chemical formula (4), R ₂ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and in chemical formula (5), R ₃ is an alkyl group having 1 to 10 carbon atoms, or a phenyl group. Is)
As other compounds having a silsesquioxane skeleton, Patent Document 3: JP 2007-258663 A (published October 4, 2007), Patent Document 4: JP 2010-120901 A (2010). (Published on June 3, 2009), Patent Document 5: JP 2009-263316 A (published on November 12, 2009), and Patent Document 6: JP 2009-263596 (published on November 12, 2009) Each disclosed silsesquioxane resin can be suitably used.

Among them, the compound having a silsesquioxane skeleton is more preferably a repeating unit represented by the following chemical formula (6) and a copolymer of a repeating unit represented by the following chemical chemical formula (7). A copolymer containing a repeating unit represented by formula (7) and a repeating unit represented by the following chemical formula (7) in a ratio of 7: 3 is more preferable.

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

Examples of the compound containing a Ti—O bond include (i) tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, and titanium-i-propoxyoctylene glycolate. (Ii) chelating titanium such as (ii) di-i-propoxy bis (acetylacetonato) titanium and propanedioxytitanium bis (ethylacetoacetate), (iii) iC ₃ H ₇ O — [— Ti (O—i—C ₃ H ₇ ) ₂ —O—] n —i—C ₃ H ₇ , and nC ₄ H ₉ O — [— Ti (On—C ₄ H ₉ ) ₂ —O -] Titanium polymers such as _n- n-C ₄ H ₉ , (iv) tri-n-butoxy titanium monostearate, titanium stearate, di-i-propoxy titanium diiso Stearate, and acylate titanium such as (2-n-butoxycarbonylbenzoyloxy) tributoxytitanium, and (v) water-soluble titanium compounds such as di-n-butoxy-bis (triethanolaminato) titanium. .

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

Although the separation layer 16 described above contains a compound having an infrared absorbing structure, the separation layer 16 may further contain components other than the above-described compound. Examples of the component include a filler, a plasticizer, and a component that can improve the peelability of the support plate 12. These components are appropriately selected from conventionally known substances or materials that do not interfere with or promote infrared absorption by the above structure and alteration of the compound.

<Fluorocarbon>
The separation layer 16 may be made of a fluorocarbon. Since the separation layer 16 is composed of fluorocarbon, the separation layer 16 is altered by absorbing light. As a result, the separation layer 16 loses strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, lifting the support plate 12), the separation layer 16 is broken and the support plate 12 and the substrate 11 can be easily separated.

From one viewpoint, the fluorocarbon constituting the separation layer 16 can be suitably formed by a plasma CVD method. In addition, fluorocarbon includes C _x F _y (perfluorocarbon) and C _x H _y F _z (x, y, and z are integers), but is not limited to these, for example, CHF ₃ , CH ₂ F ₂ , C ₂ It can be H ₂ F ₂ , C ₄ F ₈ , C ₂ F ₆ , C ₅ F ₈ or the like. In addition, an inert gas such as nitrogen, helium, or argon, a hydrocarbon such as oxygen, alkane, or alkene, and carbon dioxide or hydrogen are added to the fluorocarbon used to configure the separation layer 16 as necessary. May be. Further, a mixture of these gases may be used (a mixed gas of fluorocarbon, hydrogen, nitrogen, etc.). Further, the separation layer 16 may be composed of a single type of fluorocarbon, or may be composed of two or more types of fluorocarbon.

Fluorocarbon absorbs light having a wavelength in a specific range depending on its type. By irradiating the separation layer with light having a wavelength within a range that is absorbed by the fluorocarbon used in the separation layer 16, the fluorocarbon can be suitably altered. In addition, it is preferable that the light absorption rate in the separation layer 16 is 80% or more.

As light to irradiate the separation layer 16, depending on the wavelength that can be absorbed by the fluorocarbon, for example, YAG laser, Libby laser, glass laser, YVO ₄ laser, LD laser, liquid laser such as fiber laser, liquid laser such as dye laser, etc. A gas laser such as a CO ₂ laser, an excimer laser, an Ar laser, or a He—Ne laser, a laser beam such as a semiconductor laser or a free electron laser, or a non-laser beam may be used as appropriate. The wavelength at which the fluorocarbon can be altered is not limited to this, but for example, a wavelength in the range of 600 nm or less can be used.

<Infrared absorbing material>
The separation layer 16 may contain an infrared absorbing material. The separation layer 16 is configured to contain an infrared absorbing material, so that the separation layer 16 is altered by absorbing light, and as a result, the strength or adhesiveness before receiving the light irradiation is lost. Therefore, by applying a slight external force (for example, lifting the support plate 12 or the like), the separation layer 16 is broken and the support plate 12 and the substrate 11 can be easily separated.

The infrared absorbing material only needs to have a structure that is altered by absorbing infrared rays. For example, carbon black, iron particles, or aluminum particles can be suitably used. The infrared absorbing material absorbs light having a wavelength in a specific range depending on the type. By irradiating the separation layer 16 with light having a wavelength in a range that is absorbed by the infrared absorbing material used for the separation layer 16, the infrared absorbing material can be suitably altered.

(Adhesive layer)
The adhesive layer 14 is configured to adhere and fix the substrate 11 to the support plate 12 and at the same time to cover and protect the surface of the substrate 11. Therefore, the adhesive layer needs to have adhesiveness and strength for maintaining the fixing of the substrate 11 to the support plate 12 and the covering of the surface to be protected of the substrate 11 when the substrate 11 is processed or transported. . On the other hand, when it becomes unnecessary to fix the substrate 11 to the support plate 12, it needs to be easily peeled or removed from the substrate 11.

Therefore, the adhesive layer 14 usually has strong adhesiveness, and the adhesive layer 14 is composed of an adhesive whose adhesiveness is reduced by some treatment or has solubility in a specific solvent. For example, the thickness of the adhesive layer 14 is more preferably 1 to 200 μm, and further preferably 10 to 150 μm. The adhesive layer 14 can be formed by applying an adhesive material as described below onto the substrate 11 by a conventionally known method such as spin coating.

As the adhesive, for example, various adhesives known in the art such as acrylic, novolak, naphthoxan, hydrocarbon, and polyimide can be used as the adhesive constituting the adhesive layer 14 according to the present invention. is there. Below, the composition of resin which the contact bonding layer 14 in this Embodiment contains is demonstrated.

The resin contained in the adhesive layer 14 is not particularly limited as long as it has adhesiveness, and examples thereof include hydrocarbon resins, acrylic-styrene resins, maleimide resins, and combinations thereof.

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

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

Examples of the cycloolefin monomer contained in the monomer component constituting the resin (A) include bicyclic compounds such as norbornene and norbornadiene, tricyclic compounds such as dicyclopentadiene and dihydroxypentadiene, and tetracyclododecene. Tetracycles, pentacycles such as cyclopentadiene trimer, heptacycles such as tetracyclopentadiene, or polycyclic alkyl (methyl, ethyl, propyl, butyl, etc.) substituted alkenyls (vinyl, etc.) Examples include substituted, alkylidene (such as ethylidene) substituted, and aryl (phenyl, tolyl, naphthyl, etc.) substituted. Among these, norbornene-based monomers selected from the group consisting of norbornene, tetracyclododecene, and alkyl-substituted products thereof are particularly preferable.

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

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

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

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

The polymerization method and polymerization conditions for polymerizing the monomer component are not particularly limited and may be appropriately set according to a conventional method.

Examples of commercially available products that can be used as the resin (A) include “TOPAS” manufactured by Polyplastics, “APEL” manufactured by Mitsui Chemicals, “ZEONOR” and “ZEONEX” manufactured by Nippon Zeon, and JSR “ARTON” made by the manufacturer can be mentioned.

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

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

The softening point of the resin (B) is not particularly limited, but is preferably 80 to 160 ° C. When the softening point of the resin (B) is 80 ° C. or higher, the adhesive laminate can be suppressed from being softened when exposed to a high temperature environment, and adhesion failure does not occur. On the other hand, when the softening point of the resin (B) is 160 ° C. or lower, the peeling rate when peeling the adhesive laminate is good.

The molecular weight of the resin (B) is not particularly limited, but is preferably 300 to 3000. When the molecular weight of the resin (B) is 300 or more, the heat resistance is sufficient, and the degassing amount is reduced under a high temperature environment. On the other hand, when the molecular weight of the resin (B) is 3000 or less, the peeling rate when peeling the adhesive laminate is good. In addition, the molecular weight of resin (B) in this embodiment means the molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC).

In addition, you may use what mixed resin (A) and resin (B) as resin. By mixing, heat resistance and peeling speed are improved. For example, the mixing ratio of the resin (A) and the resin (B) is (A) :( B) = 80: 20 to 55:45 (mass ratio). Since it is excellent in tolerance and flexibility, it is preferable.

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

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

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

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

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

<Maleimide resin>
Examples of maleimide resins include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, N-sec as monomers. -Butylmaleimide, N-tert-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide, N-laurylmaleimide, N-stearylmaleimide, etc. Males having an aliphatic hydrocarbon group such as maleimide having an alkyl group, N-cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, N-cyclooctylmaleimide Resins obtained by polymerizing aromatic maleimides having an aryl group such as imide, N-phenylmaleimide, Nm-methylphenylmaleimide, No-methylphenylmaleimide, and Np-methylphenylmaleimide It is done.

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

(In the chemical formula (9), n is 0 or an integer of 1 to 3.)
As such cycloolefin copolymer, APL 8008T, APL 8009T, APL 6013T (all manufactured by Mitsui Chemicals, Inc.) and the like can be used.

In addition, it is preferable to form the adhesive layer 14 using a resin other than a photocurable resin (for example, a UV curable resin). This is because the photocurable resin may remain as a residue around the minute irregularities of the substrate 11 after the adhesive layer 14 is peeled or removed. In particular, an adhesive that dissolves in a specific solvent is preferable as a material constituting the adhesive layer 14. This is because the adhesive layer 14 can be removed by dissolving it in a solvent without applying a physical force to the substrate 11. When the adhesive layer 14 is removed, the adhesive layer 14 can be easily removed without damaging or deforming the substrate 11 even from the substrate 11 whose strength has decreased.

As a diluting solvent for forming the separation layer and the adhesive layer described above, for example, hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, tridecane and the like linear hydrocarbons, carbon number 3 to 15 Branched hydrocarbons of the following: p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpine, 1,8-terpine, bornane, norbornane, pinane, tsujang, karan, longifolene, geraniol, nerol, Linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, dihydroterpinyl acetate, 1,4-cineole, 1,8-cineole, Borne Terpene solvents such as alcohol, carvone, ionone, thuyon, camphor, d-limonene, l-limonene, dipentene; lactones such as γ-butyrolactone; acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, Ketones such as methyl isopentyl ketone and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate or dipropylene glycol mono Compounds having an ester bond such as acetate, monomethyl ether, monoethyl ether, monopropyl of the polyhydric alcohols or the compound having an ester bond Derivatives of polyhydric alcohols such as monoalkyl ethers such as ether and monobutyl ether or compounds having an ether bond such as monophenyl ether (in these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) Preferred); cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethoxy Esters such as ethyl propionate; aromatic systems such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether Aircraft solvent or the like can be mentioned.

<Other ingredients>
The adhesive material may further contain other miscible substances as long as the essential characteristics of the present invention are not impaired. For example, various conventional additives such as additional resins, plasticizers, adhesion assistants, stabilizers, colorants, antioxidants and surfactants for improving the performance of the adhesive can be further used. .

(Irradiation process)
In the support separating method according to the present embodiment, first, as shown in (1) in FIG. 1, the separation layer 16 is irradiated with a pulsed laser beam via the support plate 12 (irradiation step). At this time, the irradiated laser light passes through the light-transmitting support plate 12 and reaches the separation layer 16. The separation layer 16 is altered as shown in (2) in FIG. 1 by absorbing the laser beam that has reached it. Thereby, the adhesion between the substrate 11 and the support plate 12 is weakened, and the support plate 12 is easily separated from the substrate 11 as shown in FIG.

In order to separate the support plate 12 from the laminate 1, when the separation layer 16 is irradiated with laser light from the support plate 12 side, the laser light may leak from the separation layer 16.

Therefore, the leaked light reaches the substrate 11, and the substrate 11 itself or an electronic element such as an electronic circuit to be protected formed on the substrate 11 may be adversely affected by the leaked light. . Examples of adverse effects of leaked light include disassembly of electronic circuits mounted on the substrate 11, damage to the substrate 11, and the like.

In order to avoid this problem, the present inventors have conducted intensive studies on the damage received by the laser light irradiated to the separation layer 16 on the substrate 11 and the electronic elements formed on the substrate 11, and as a result, It has been found that whether or not the irradiated regions on the separation layer 16 in the laser pulse overlap each other greatly affects the damage to the substrate 11 and the electronic elements formed on the substrate 11.

In the support separating method according to the present embodiment, the substrate 11 and the substrate 11 are scanned by scanning the laser beams so that the irradiated regions on the separation layer 16 in the laser pulses of the laser beams do not overlap each other. The present inventors have found that the damage received by the electronic device formed in the above can be reduced.

That is, when the irradiated regions on the separation layer 16 overlap each other in each laser pulse of the laser beam, the light leaked from the position where the irradiated regions on the separation layer 16 overlap each other is the substrate. 11 and a specific position of the electronic element formed on the substrate 11 are irradiated a plurality of times. For this reason, the intensity of the laser irradiated to a specific position such as the substrate 11 increases, and the substrate 11 or the like is easily damaged.

On the other hand, when each irradiation region on the separation layer 16 in each laser pulse of the laser beam does not overlap with each other, the light leaking from the separation layer 16 is the substrate 11 and a predetermined electronic device formed on the substrate 11. Can be prevented from being irradiated multiple times, and damage to the substrate 11 and the like can be reduced.

Hereinafter, the relationship between each irradiated region and laser beam scanning will be described in detail with reference to FIG. FIG. 2 is a diagram illustrating an example of a region to be irradiated with laser light when the laser light is scanned in the support separating method according to the embodiment of the present invention. The irradiated region is formed on the separation layer 16 by scanning the laser beam and irradiating the separation layer 16 with the laser beam.

First, laser light is scanned to the end of the separation layer 16 along the scanning direction so that the irradiated regions do not overlap each other. Thereafter, the laser beam is scanned in the sub-scanning direction which is a direction perpendicular to the scanning direction. Then, the laser beam is scanned over the region of the separation layer 16 that is not irradiated with the laser beam. When scanning the laser light after scanning the laser light in the sub-scanning direction, the scanning of the laser light is adjusted so that adjacent irradiated regions on the separation layer 16 do not overlap each other. Further, the laser beam may be scanned by moving the irradiation device.

As an example, after scanning the laser beam to the end of the separation layer 16, the laser beam is scanned in the sub-scanning direction to a position where adjacent irradiated regions on the separation layer 16 do not overlap each other, and the scanning direction starts from the position. The laser beam may be irradiated over the entire separation layer 16 by repeating scanning of the laser beam to the opposite end of the separation layer 16. However, the scanning method is not limited to this, and any scanning mode may be used as long as the separation layer 16 can be irradiated with laser light without being biased.

The wavelength of the laser beam is not particularly limited as long as the separation layer 16 can be altered, but is preferably 350 nm or more and 1064 nm or less, and more preferably 495 nm or more and 570 nm or less. A preferable range of the wavelength of the laser light irradiated on the separation layer 16 is a wavelength that can be absorbed by the separation layer 16, and thus varies depending on a material forming the separation layer 16.

The laser intensity of the laser beam necessary for irradiating the separation layer 16 and changing the quality of the separation layer 16 varies depending on the material constituting the separation layer 16, but may be in the range of, for example, 0.1 W or more and 10 W or less. More preferably, the range is 0.5 W or more and 6 W or less.

The laser intensity of the laser beam increases as the laser beam diameter decreases, and decreases as the laser beam diameter increases. The diameter of the laser beam varies depending on the laser intensity required for the alteration of the separation layer 16, but is more preferably in the range of 100 μm or more and 350 μm or less, and further preferably in the range of 120 μm or more and 250 μm or less.

The laser intensity of the laser beam also increases as the pulse width of the laser beam decreases, and decreases as the pulse width of the laser beam increases. The pulse width of the laser light is more preferably in the range of, for example, 20 nanoseconds or more and 150 nanoseconds or less.

Further, the repetition frequency of the laser beam is not particularly limited, but for example, it is more preferably in the range of 20 kHz or more and 100 kHz or less.

Here, in order to prevent the irradiated regions in each laser pulse from overlapping each other, the scanning speed of the laser light may be controlled and the laser light may be scanned so as to satisfy the following formula (1).

r ≦ d (1)
(However, the diameter of the laser beam is r (μm), and the center-to-center distance between irradiated regions in two continuous laser pulses is d (μm).)
Similarly, the scanning of the laser beam is adjusted so that the center-to-center distance (e (μm)) between two irradiated regions continuous in the sub-scanning direction is equal to or smaller than the diameter (r) of the laser beam. Thus, it is possible to prevent the irradiation regions in the laser pulses in the sub-scanning direction from overlapping each other.

For example, when the diameter of the laser beam is 180 μm, the center-to-center distances d (μm) and e (μm) are more preferably in the range of 180 μm to 200 μm. The present invention is not limited to this.

More specifically, it is possible to prevent the irradiated areas from overlapping each other by scanning the laser beam so as to satisfy the following formula (2).

r × f ≦ v (2)
(However, the diameter of the laser beam is r (μm), the repetition frequency of the laser beam is f (kHz), and the scanning speed of the laser beam is v (mm / s).)
By setting the diameter of the laser light, the repetition frequency of the laser light, and the scanning speed of the laser light so as to satisfy the above conditions, the irradiated regions in each laser pulse can be prevented from overlapping each other.

For example, when the laser beam diameter is 180 μm and the repetition frequency is 40 kHz, the laser beam scanning speed v (mm / s) is more preferably in the range of 7200 mm / s to 7500 mm / s. preferable. The present invention is not limited to this.

Particularly preferably, the laser beam is preferably scanned so as to satisfy the following formula (3). When Expression (3) is satisfied, the laser beam can be scanned so that the irradiated areas adjacent in the scanning direction are in contact with each other. Thereby, the damage given to a foundation | substrate can be reduced.

r = d (3)
(However, the diameter of the laser beam is r (μm), and the center-to-center distance between irradiated regions in two continuous laser pulses is d (μm).)
The scanning speed of the laser beam is not limited as long as it satisfies the above formula (2) and can change the entire separation layer 16 to separate the support plate 12 from the laminate 1.

As an irradiation apparatus for irradiating pulsed laser light, a known laser light irradiation apparatus may be used. For example, solid-state laser oscillators such as YAG laser, Libby laser, glass laser, YVO ₄ laser, LD laser, and fiber laser A liquid laser oscillator such as a dye laser, a gas laser oscillator such as a CO ₂ laser, an excimer laser, an Ar laser, or a He—Ne laser, a semiconductor laser oscillator, a free electron laser oscillator, or the like can be used as appropriate.

Note that the scanning direction of the laser light is not limited as shown in FIG. 2, and the laser light can be scanned in an arbitrary direction. In such a case as well, the distance between centers may be set so that the irradiated regions on the separation layer 16 do not overlap each other.

Further, the shape of the laser light irradiation region is not limited to a circular shape, and it is possible to take an arbitrary shape in which the irradiation regions in each laser pulse do not overlap each other. In that case, the diameter refers to the dimension in the scanning direction of each irradiated region.

[Support Separator]
A support separating apparatus according to the present invention is a support separating apparatus that separates a laminated body formed by laminating a substrate, an adhesive layer, a separating layer that is altered by absorbing light, and a support in this order. And an irradiation means for irradiating the separation layer with a pulsed laser beam, wherein the irradiation means prevents the irradiated regions on the separation layer in the laser pulses of the laser light from overlapping each other. Further, the laser beam is scanned.

One embodiment of the irradiation means of the support separating apparatus according to the present invention is an irradiation apparatus that irradiates a laser beam in the irradiation step of the support separating method according to the present invention, and the description of the support separating apparatus according to the present invention is as follows. According to the description of the support separating method according to the present invention.

The support separating method and the support separating apparatus according to the present invention realizes strong adhesion between the substrate and the support during the manufacturing process, and easily separates the substrate and the support by light irradiation after the manufacturing process. It is possible, and there is an effect that an adverse effect on the substrate by light can be prevented.

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

Using a laser irradiation device, the influence of laser light (wavelength 532 nm) on the substrate was examined.

(Create laminate)
A Sn—Ag plate (tin-silver plate, thickness 1 μm) was mounted on a wafer substrate (thickness 700 μm). The Sn-Ag plate was used instead of an element mounted on a wafer substrate, an electric circuit, or the like. Next, TZNR-A3007t (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was baked as an adhesive composition at 100 ° C., 160 ° C. and 220 ° C. for 3 minutes each to form an adhesive layer (thickness 50 μm).

Next, a fluorocarbon film (thickness 1 μm) is supported on a support (glass substrate) by a CVD method using C ₄ F ₈ as a reaction gas under the conditions of a flow rate of 400 sccm, a pressure of 700 mTorr, a high frequency power of 2500 W, and a film formation temperature of 240 ° C. , A thickness of 700 μm), and a separation layer was formed.

Next, the adhesive layer and the separation layer were bonded together to produce a laminate in which the wafer substrate, the Sn-Ag plate, the adhesion layer, the separation layer, and the support plate were laminated in this order. Two laminates were prepared in total.

These laser beams were irradiated from the support plate side under different laser beam irradiation conditions (Examples and Comparative Examples).

〔Example〕
The average output of the laser beam is 3.6 W, the laser beam frequency is 40 kHz, the laser beam diameter is 180 μm, the center-to-center distance between the irradiated regions in the laser pulse is 180 μm, and the scanning speed is Laser light was irradiated under conditions of 7200 mm / s.

In the above laser light irradiation, conditions such as the repetition frequency of the laser light, the diameter of the laser light, the distance between the centers of the irradiated regions, and the scanning speed of the laser light satisfy the expressions (1) and (2). Therefore, the irradiated regions on the separation layer did not overlap each other.

After the laser irradiation, the wafer substrate and the support plate were easily separated by applying a slight force to the laminate.

Next, when the damage received by the Sn-Ag plate was confirmed with a microscope, no damage was found on the Sn-Ag plate.

[Comparative example]
The average output of the laser beam is 3.6 W, the laser beam frequency is 40 kHz, the laser beam diameter is 180 μm, the center-to-center distance between the irradiated regions in the laser pulse is 180 μm, and the scanning speed is Laser light was irradiated under the condition of 5000 mm / s.

In the above laser beam irradiation, the conditions such as the repetition frequency of the laser beam, the diameter of the laser beam, the distance between the centers of the irradiated regions, and the scanning speed of the laser beam did not satisfy the equations (1) and (2). . That is, the irradiated areas on the separation layer partially overlap each other.

Next, when the damage received by the Sn-Ag plate was visually confirmed with a microscope, the Sn-Ag plate was found to be damaged.

From the above examples and comparative examples, when laser light is irradiated so that the laser light irradiated areas overlap each other, damage to the wafer substrate occurs, but the laser light irradiated areas do not overlap each other. It was found that the damage to the substrate can be reduced by irradiating.

The present invention can be suitably used, for example, in a manufacturing process of a miniaturized semiconductor device.

DESCRIPTION OF SYMBOLS 1 Laminated body 2 Irradiation area | region 11 Board | substrate 12 Support plate (support body)
14 Adhesive layer 16 Separation layer

Claims

A substrate separation method for separating a laminate formed by laminating a substrate, an adhesive layer, a separation layer that is altered by absorbing light, and a support in this order,
Including an irradiation step of irradiating the separation layer with pulsed laser light;
In the irradiation step, the laser beam is scanned so that the irradiated regions on the separation layer in the laser pulses of the laser beam do not overlap each other.
In the said irradiation process, the said laser beam is scanned so that following formula (1) may be satisfy | filled, The support body separation method of Claim 1 characterized by the above-mentioned.
r ≦ d (1)
(However, the diameter of the laser beam is r (μm), and the center-to-center distance between the irradiated regions in two consecutive laser pulses is d (μm).)
In the said irradiation process, the said laser beam is scanned so that following formula (2) may be satisfy | filled, The support body separation method of Claim 1 or 2 characterized by the above-mentioned.
r × f ≦ v (2)
(However, the diameter of the laser beam is r (μm), the repetition frequency of the laser beam is f (kHz), and the scanning speed of the laser beam is v (mm / s).)
In the said irradiation process, the said laser beam is scanned so that following formula (3) may be satisfy | filled, The support body separation method of Claim 1 characterized by the above-mentioned.
r = d (3)
(However, the diameter of the laser beam is r (μm), and the center-to-center distance between the irradiated regions in two consecutive laser pulses is d (μm).)
A support separating apparatus for separating a laminate formed by laminating a substrate, an adhesive layer, a separation layer that is altered by absorbing light, and a support in this order,
An irradiation means for irradiating the separation layer with pulsed laser light;
The irradiation means scans the laser beam so that the irradiated areas on the separation layer in each laser pulse of the laser light do not overlap each other. .