JP6114610B2 - Processing method and processing apparatus - Google Patents

Description

  The present invention relates to a processing method and a processing apparatus for processing a laminated body.

  In recent years, there has been an increasing demand for miniaturization, thinning, and high integration of semiconductor chips mounted on electronic devices. For this reason, it is necessary to grind the board | substrate used as the foundation of a semiconductor chip, and to make it thin plate. However, grinding reduces the strength of the substrate. As a result, the substrate is likely to be cracked and warped. Further, since the thinned substrate cannot be automatically transported, it has to be performed manually, and the handling thereof is complicated.

  For this reason, a method has been developed in which the substrate to be ground is bonded to a glass support plate using an adhesive, thereby maintaining the strength of the substrate and preventing the occurrence of cracks and warping of the substrate (patent). (See the description in Document 1).

  In the method described in Patent Document 1, if an adherent such as an organic substance adheres to the support plate, a slight gap is generated between the substrate and the support plate, and the substrate is lost. For this reason, it is necessary to wash | clean a support plate as pre-processing before a board | substrate is stuck.

  In general, the surface area of the support plate is equal to or larger than the surface area of the substrate. For this reason, when wiring is formed on the substrate supported by the support plate, the metal also adheres to the exposed portion of the periphery of the support plate that is not covered by the substrate. Further, the adhesive remains on the support plate after the substrate is peeled off. For this reason, in order to reuse the support plate, it is necessary to completely remove deposits such as metals and organic substances from the support plate after the substrate is peeled off.

  Generally, the metal and organic matter adhering to the support plate can be removed using a chemical solution such as an acid, an alkali, or an organic solvent. For example, the metal can be removed using aqua regia. Organic substances can be removed using an organic solvent or acid.

  In addition, as a glass substrate cleaning method, Patent Document 2 discloses a method of removing a metal or an organic substance attached to a glass substrate by treating the glass substrate with a mixed solution of heated sulfuric acid and hydrogen peroxide solution. Has been.

  Patent Document 3 discloses a method of removing an adhering matter attached to a glass substrate by washing the glass substrate with an acid.

  In addition, as a method for removing a metal film, Patent Document 4 discloses that when a metal film formed on a circuit board is irradiated with laser light to melt and remove the metal film, the circuit board is not thermally damaged by the heat of the laser light. Thus, a method of covering a portion irradiated with laser light with a liquid through which the laser light passes is disclosed.

JP 2005-191550 A (published July 14, 2005) JP 09-227170 A (published September 2, 1997) JP 62-235236 A (released on October 15, 1987) JP-A-63-180393 (released July 25, 1988)

  By the way, for 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 support separated after the separation layer is altered There is a need for a processing method for reuse.

  An object of this invention is to provide the processing method and processing apparatus which remove the residue adhering to the support body after isolation | separation, and enable the reuse of the said support body.

  In order to solve the above problems, the treatment method according to the present invention treats a laminated body formed by laminating a substrate, an adhesive layer, a separation layer that is altered by absorbing light, and a support in this order. A separation step of irradiating the separation layer with light to alter the separation layer to separate the support and the substrate, and plasma ashing the surface of the support after separation. And a plasma ashing process for removing residues of the separation layer or the adhesive layer adhering to the surface of the support.

  Further, the processing apparatus according to the present invention alters the separation layer in the laminate formed by laminating the substrate, the adhesive layer, the separation layer that is altered by absorbing light, and the support in this order. A processing apparatus for processing the support after separating the support and the substrate, wherein the separation layer is attached to the surface of the support by plasma ashing the surface of the support Alternatively, plasma generating means for removing the residue of the adhesive layer and cleaning means for cleaning the plasma-ashed surface of the support with a solvent are provided.

  The processing apparatus according to the present invention has an effect of removing the residue adhering to the support after separation, and enabling reuse of the support.

It is a figure which shows the process of the processing method which processes the laminated body which concerns on this embodiment. It is a figure which shows the processing apparatus which concerns on this embodiment.

  Hereinafter, embodiments of the present invention will be described in detail.

[Laminate 10]
First, the laminate 10 that is a processing target of the processing method according to the present embodiment will be described. As shown in FIG. 1 (a), the laminate 10 includes a substrate 1, an adhesive layer 2, a separation layer 3 that is altered by absorbing light, and a support plate (support) 4 in this order. Laminated.

(Substrate 1)
The substrate 1 is subjected to processes such as thinning and mounting while being supported by the support plate 4. The substrate 1 is not limited to a wafer substrate, and an arbitrary substrate such as a thin film substrate or a flexible substrate can be used.

(Support plate 4)
The support plate 4 is a support body that supports the substrate 1 and has optical transparency. Therefore, when light is irradiated from the outside of the laminated body 10 toward the support plate 4, the light passes through the support plate 4 and reaches the separation layer 3. Further, the support plate 4 does not necessarily need to transmit all the light, and it is sufficient if it can transmit the light to be absorbed by the separation layer 3 (having a desired wavelength).

  The support plate 4 supports the substrate 1 and may have a strength necessary for preventing the substrate 1 from being damaged or deformed during processes such as thinning, transporting, and mounting of the substrate 1. From the above viewpoint, examples of the support plate 4 include those made of glass, silicon, and acrylic. When the support plate 4 is a silicon plate, infrared rays having a wavelength of 2 μm or more can be transmitted.

(Separation layer 3)
The separation layer 3 is altered by absorbing light irradiated through the support plate 4. In the present specification, the “deterioration” of the separation layer 3 means a phenomenon in which the separation layer 3 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 3 is reduced. means. Further, the alteration of the separation layer 3 includes decomposition (exothermic or non-exothermic), cross-linking, configuration change or dissociation of functional groups (and curing of the separation layer accompanying these, degassing). , Contraction or expansion) and the like. The alteration of the separation layer 3 occurs as a result of light absorption by the material constituting the separation layer 3. Therefore, the type of alteration of the separation layer 3 can be changed according to the type of material constituting the separation layer 3.

  The separation layer 3 is provided on the surface of the support plate 4 on the side where the substrate 1 is bonded via the adhesive layer 2. That is, the separation layer 3 is provided between the support plate 4 and the adhesive layer 2.

  For example, the thickness of the separation layer 3 is more preferably 0.1 to 50 μm, and further preferably 0.1 to 10 μm. If the thickness of the separation layer 3 is within the range of 0.1 to 50 μm, the separation layer 3 can be altered as desired by irradiation with light for a short time and irradiation with low energy light. The thickness of the separation layer 3 is preferably within a range of 1 μm or less from the viewpoint of productivity.

  In the laminate 10, another layer may be further formed between the separation layer 3 and the support plate 4. In this case, the other layer should just be comprised from the material which permeate | transmits light. Accordingly, a layer imparting preferable properties to the stacked body 10 can be appropriately added without hindering the incidence of light on the separation layer 3. The wavelength of light that can be used differs depending on the type of material constituting the separation layer 3. Therefore, the material constituting the other layer does not need to transmit all light, and can be appropriately selected from materials that can transmit light having a wavelength that can alter the material constituting the separation layer 3.

  The separation layer 3 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 3. Further, it is preferable that the surface of the separation layer 3 on the side facing the adhesive layer 2 is flat (unevenness is not formed), so that the separation layer 3 can be easily formed and is uniform in pasting. It becomes possible to paste on.

  As the separation layer 3, a material that forms the separation layer 3 as described below may be used by bonding it to the support plate 4 in advance, or the separation layer 3 may be formed on the support plate 4. You may use what applied the material and solidified in the film form. The method of applying the material constituting the separation layer 3 on the support plate 4 can be appropriately selected from conventionally known methods according to the type of material constituting the separation layer 3.

The separation layer 3 may be altered by absorbing light irradiated from the laser. That is, the light applied to the separation layer 3 in order to change the quality of the separation layer 3 may be light emitted from a laser. Examples of lasers that emit light irradiated on the separation layer 3 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, and CO ₂ lasers. , Excimer laser, Ar laser, He—Ne laser or other gas laser, semiconductor laser, free electron laser or other laser light, or non-laser light. The laser that emits the light applied to the separation layer 3 can be appropriately selected according to the material constituting the separation layer 3, and light having a wavelength that can alter the material constituting the separation layer 3 is used. What is necessary is just to select the laser to irradiate.

<Polymer containing light absorbing structure in its repeating unit>
The separation layer 3 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 3 has lost 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 4), the separation layer 3 is broken, and the support plate 4 and the substrate 1 can be easily separated.

  The structure having light absorption is a chemical structure that absorbs light and alters the 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 ₄ ) (R ₅ ) (where R ₄ and R ₅ 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 of 1-5.

  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 being —SO ₂ —, bis (2, 4-dihydroxyphenyl) sulfone, bis (3,4-dihydroxyphenyl) sulfone, bis (3,5-dihydroxyphenyl) sulfone, bis (3,6-dihydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfone, bis (3-hydroxyphenyl) sulfone, bis (2-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone and the like can be mentioned.

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

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

  When the structure is present in the side chain of the polymer, the proportion of the repeating unit containing the structure in the polymer is such that the light transmittance of the separation layer 3 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 3 can sufficiently absorb light and can be reliably and rapidly altered. That is, it is easy to remove the support plate 4 from the laminate 10, and the light irradiation time necessary for the removal can be shortened.

  The said structure can absorb the light which has a wavelength of a desired range by selection of the kind. For example, the wavelength of light that can be absorbed by the above structure is more preferably 100 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), KrF excimer laser (wavelength: 248 nm), ArF excimer laser (wavelength: 193 nm), 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.

  Although the separation layer 3 described above contains a polymer containing the above structure as a repeating unit, the separation layer 3 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 4. 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.

<Compound having infrared absorbing structure>
The separation layer 3 may be formed of a compound having an infrared absorbing structure. The compound is altered by absorbing infrared rays. The separation layer 3 has lost its strength or adhesiveness before being irradiated with infrared rays as a result of the alteration of the compound. Therefore, by applying a slight external force (for example, lifting the support plate), the separation layer 3 is broken, and the support plate 4 and the substrate 1 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, enol of 1,3-diketone, 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.

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

Examples of the structure containing the Si—A ¹ bond include SiH, SiH ₂ , SiH ₃ , Si—CH ₃ , Si—CH ₂ —, Si—C ₆ H ₅ , SiO aliphatic, Si—OCH ₃ , Si—OCH. ₂ CH ₃ , Si—OC ₆ H ₅ , Si—O—Si, Si—OH, SiF, SiF ₂ , SiF _{3 and the} like can be mentioned. As a structure including a Si—A1 bond, it is particularly preferable that a siloxane skeleton and a silsesquioxane skeleton are formed.

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

  The said structure can absorb the infrared rays which have the wavelength of a desired range by selection of the kind. For example, the wavelength of infrared rays that can be absorbed by the above-described 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. Further, when the structure is a Si—O bond, a Si—C bond, and 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 Document: SILVERSTEIN / BASSLER / MORRILL, “Identification method by spectrum of organic compound (5th edition) —Combination of MS, IR, NMR and UV” (published in 1992) The description on page 146 to page 151 can be referred to.

  As a compound having an infrared-absorbing structure used for forming the separation layer 3, 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 3 and facilitate separation of the support plate 4 and the substrate 1, the infrared absorption in the separation layer 3 is large, that is, the separation layer 3 is irradiated with infrared rays. It is preferable that the infrared transmittance is low. Specifically, the infrared transmittance in the separation layer 3 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 formula (1) and a repeating unit represented by the following formula (2), or A resin that is a copolymer of a repeating unit represented by the following formula (1) and a repeating unit derived from an acrylic compound can be used.

(In 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 tert-butylstyrene (TBST) -dimethylsiloxane copolymer, which is a copolymer of a repeating unit represented by the above formula (1) and a repeating unit represented by the following formula (3), is used. A polymer is more preferable, and a TBST-dimethylsiloxane copolymer containing a repeating unit represented by the above formula (1) and a repeating unit represented by the following formula (3) at 1: 1 is further preferable.

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

(In Formula (4), R ₂ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and in Formula (5), R ₃ is an alkyl group having 1 to 10 carbon atoms, or a phenyl group. Is)
Other compounds having a silsesquioxane skeleton include Patent Document 3: Japanese Patent Laid-Open No. 2007-258663 (published on October 4, 2007), Patent Document 4: Japanese Patent Laid-Open No. 2010-120901 (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 A (published on November 12, 2009). Each disclosed silsesquioxane resin can be suitably used.

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

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

Examples of the compound containing a Ti-O bond include (i) tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, and titanium-i-propoxyoctylene glycolate. (Ii) chelating titanium such as (ii) di-i-propoxy bis (acetylacetonato) titanium and propanedioxytitanium bis (ethylacetoacetate), (iii) i-C ₃ H ₇ O — [— _{Ti (O-i-C 3} H 7) 2 -O-] n -i-C 3 H 7, and _{n-C 4 H 9 O -} [- Ti (O-n-C 4 H 9) 2 -O - titanium polymers such as _{n -n-C 4 H 9,} (iv) tri -n- butoxy titanium monostearate, titanium stearate, di -i- propoxytitanium diisostearate, and ( Acylate titanium such -n- butoxycarbonyl benzoyloxy) tributoxy titanium, and the like (v) di -n- butoxy bis (triethanolaminato) a water-soluble titanium compound such as 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 3 described above contains a compound having an infrared absorbing structure, the separation layer 3 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 4. 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 3 may be made of a fluorocarbon. Since the separation layer 3 is composed of fluorocarbon, the separation layer 3 is altered by absorbing light. As a result, the separation layer 3 loses strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, lifting the support plate 4), the separation layer 3 is broken, and the support plate 4 and the substrate 1 can be easily separated.

From one point of view, the fluorocarbon constituting the separation layer 3 can be suitably formed by a plasma CVD method. The fluorocarbon includes C _x F _y (perfluorocarbon) and C _x H _y F _z (x, y, and z are natural numbers), but are 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 H ₂ F, C ₂ F ₆ , C ₅ F _8, etc. Further, 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 for constituting the separation layer 3 as necessary. May be. Further, a mixture of these gases may be used (a mixed gas of fluorocarbon, hydrogen, nitrogen, etc.). The separation layer 3 may be composed of a single type of fluorocarbon or may be composed of two or more types of fluorocarbon.

  The fluorocarbon absorbs light having a wavelength in a specific range depending on the type. By irradiating the separation layer with light having a wavelength within a range that is absorbed by the fluorocarbon used in the separation layer 3, the fluorocarbon can be suitably altered. The light absorption rate in the separation layer 3 is preferably 80% or more.

The light applied to the separation layer 3 may be, for example, a solid laser such as a YAG laser, Libby laser, glass laser, YVO ₄ laser, LD laser, or fiber laser, or a dye laser depending on the wavelength that can be absorbed by the fluorocarbon. A liquid laser, a CO ₂ laser, an excimer laser, an Ar laser, a gas laser such as 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.

(Adhesive layer 2)
The adhesive layer 2 is configured to cover and protect the surface of the substrate 1 at the same time as the substrate 1 is bonded and fixed to the support plate 4. Therefore, the adhesive layer 2 needs to have adhesiveness and strength for maintaining the substrate 1 fixed to the support plate 4 and covering the surface to be protected when the substrate 1 is processed or transported. is there. On the other hand, it is necessary that the substrate 1 can be easily separated or removed from the substrate 1 when it is no longer necessary to fix the substrate 1 to the support plate 4 after the manufacturing process.

  Therefore, it is preferable that the adhesive layer 2 includes an adhesive material that usually has strong adhesiveness and whose adhesiveness is lowered by some treatment or has solubility in a specific solvent.

  For example, the thickness of the adhesive layer 2 is more preferably 1 to 150 μm, and still more preferably 10 to 100 μm.

[Adhesive material]
As the adhesive material, for example, various adhesive materials known in the art such as acrylic, novolak, naphthoxan, hydrocarbon, and polyimide are adhesive materials that constitute the adhesive layer 2 according to the present embodiment. It can be used. Below, composition of resin etc. which the adhesive material in this Embodiment contains is demonstrated.

  The adhesive material is not particularly limited as long as it has adhesiveness, and examples thereof include hydrocarbon resins, elastomers, 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.

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

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

  The monomer component constituting the resin (A) may contain another monomer copolymerizable with the above-described cycloolefin monomer, and examples thereof include alkene monomers having 2 to 10 carbon atoms. It is preferable to contain a 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.

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

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

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

  The polymerization method and polymerization conditions for polymerizing the monomer components are not particularly limited and may be 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 more 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 can be further suppressed when the adhesive layer is exposed to a high temperature environment.

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

  Although the softening point of resin (B) is not specifically limited, It is more preferable that it is 80-160 degreeC. When the softening point of the resin (B) is 80 ° C. or higher, the adhesive layer can be prevented 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 speed when peeling the adhesive from the substrate is good.

  Although the molecular weight of resin (B) is not specifically limited, It is more preferable that it is 300-3000. When the molecular weight of the resin (B) is 300 or more, the heat resistance is sufficient, and the degassing amount is reduced under a high temperature environment. On the other hand, when the molecular weight of the resin (B) is 3000 or less, the peeling speed when peeling the adhesive from the substrate 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.

<Elastomer>
The elastomer preferably contains a styrene unit as a constituent unit of the main chain. The elastomer contained in the adhesive composition according to the present invention preferably has a styrene unit content in the range of 14 wt% or more and 50 wt% or less. Furthermore, it is preferable that the elastomer contained in the adhesive composition according to the present invention has a weight average molecular weight in the range of 10,000 to 200,000.

  Examples of the elastomer include polystyrene-poly (ethylene / propylene) block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), and styrene-butadiene-butylene-styrene block. Copolymer (SBBS), ethylene-propylene terpolymer (EPT), and hydrogenated products thereof, styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (styrene-isoprene-styrene) Block copolymer) (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS) and the like.

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

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

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

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

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

<Maleimide resin>
Examples of maleimide resins include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, N-sec as monomers. -Butylmaleimide, N-tert-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide, N-laurylmaleimide, N-stearylmaleimide, etc. Males having an aliphatic hydrocarbon group such as maleimide having an alkyl group, N-cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, N-cyclooctylmaleimide Resin obtained by polymerizing aromatic maleimide having an aryl group such as imide, N-phenylmaleimide, Nm-methylphenylmaleimide, N-o-methylphenylmaleimide, Np-methylphenylmaleimide, etc. It is done.

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

(In formula (9), n is 0 or an integer of 1 to 3)
The adhesive layer 2 is preferably formed using a resin other than a photocurable resin (for example, a UV curable resin). This is because the photocurable resin may remain as a residue around the minute irregularities of the substrate 1 after the separation or removal of the adhesive layer 2. In particular, an adhesive that dissolves in a specific solvent is preferable as a material constituting the adhesive layer 2. This is because the adhesive layer 2 can be removed by dissolving it in a solvent without applying physical force to the substrate 1. When removing the adhesive layer 2, the adhesive layer 2 can be easily removed without damaging or deforming the substrate 1 even from the substrate 1 with reduced strength.

  As a diluting solvent when forming the above-mentioned separation layer and adhesive layer, for example, hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, tridecane, etc., linear hydrocarbons, carbon number 3-15 Branched hydrocarbons of the following: p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpine, 1,8-terpin, bornane, norbornane, pinane, tsujang, kalan, 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, borneo Terpene solvents such as carboxylic, lonone, thoyon, camphor, d-limonene, l-limonene, dipentene; lactones such as γ-butyrolactone; acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl iso Ketones such as pentyl 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 monoacetate A compound having an ester bond, monomethyl ether, monoethyl ether, monopropyl ether of the polyhydric alcohol or the compound having an ester bond. Derivatives of polyhydric alcohols such as compounds having ether bonds such as monoalkyl ethers or monophenyl ethers such as ether and monobutyl 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 organics such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, and butyl phenyl ether Agents, and the like can be mentioned.

(Other ingredients)
The adhesive composition may further contain other miscible materials 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. .

[About processing method]
Next, a method for processing the laminate 10 according to the present embodiment will be described with reference to FIG. FIG. 1 is a diagram showing the steps of a processing method for processing a laminate 10 according to the present embodiment. The processing method of the laminated body 10 according to the present embodiment is a laminated body 10 in which the substrate 1, the adhesive layer 2, the separation layer 3 that is altered by absorbing light, and the support plate 4 are laminated in this order. In which the separation layer 3 is irradiated with light to alter the separation layer 3 and the support plate 4 and the substrate 1 are separated from each other, and the surface of the support plate 4 after the separation is plasma-treated. A plasma ashing step of removing the residue of the separation layer 3 or the adhesive layer 2 adhering to the surface of the support plate 4 by ashing.

(Separation process)
As shown in FIG. 1B, first, the separation layer 3 is irradiated with light to alter the separation layer 3. After the separation layer 3 is altered, the support plate 4 and the substrate 1 are separated by applying a force to the laminate 10 (separation process). By separating the support plate 4 from the laminated body 10, a residue 5 (attachment attached to the surface of the support body of at least one of the adhesive layer and the separation layer) 5 adheres as shown in FIG. The support plate 4 is obtained.

(Plasma ashing process)
Next, as shown in FIG. 1D, the support plate 4 is irradiated with plasma generated from the plasma generator 6, and the surface of the support plate 4 after the separation is plasma ashed (plasma ashing step). Thereby, the residue 5 adhering to the surface of the support plate 4 can be removed.

The plasma ashing process is preferably performed by oxygen ashing. By the oxygen ashing, the residue 5 attached to the surface of the support plate 4 can be burned, and the residue 5 attached to the surface can be suitably removed. In order to perform oxygen ashing on the surface of the support plate 4, oxygen plasma is generated using a known oxygen plasma generator, and the support plate 4 is irradiated with the oxygen plasma. A mixed gas in which at least one selected from nitrogen gas and hydrogen gas is mixed with oxygen gas can also be used. For example, a mixed gas in which oxygen gas contains less than 10% nitrogen gas with respect to the entire mixed gas can be suitably used. Further, for example, when using a mixed gas in which hydrogen is contained in oxygen gas, it is preferable to add hydrogen at a ratio of 5% or more and 20% or less with respect to the entire mixed gas. At this time, a gas in which hydrogen and nitrogen are mixed may be added to the oxygen gas.
As typical methods of the oxygen plasma generator, there are a single wafer type and a batch type, but the present invention is not limited to these.

  Conditions for performing oxygen ashing may be any conditions that can remove the residue 5 attached to the support plate 4. For example, in the case of a batch type, the output of oxygen plasma irradiated to the support plate 4 is usually 500 W or more and 2000 W or less, and preferably 800 W or more and 1500 W or less. In the case of a single wafer type, it is usually 1000 W or more and 3000 W or less, and preferably 1500 W or more and 2800 W or less.

  The pressure of the oxygen plasma irradiated to the support plate 4 is usually 40 Pa or more and 266 Pa or less, and preferably 67 Pa or more and 200 Pa or less.

  In the case of a batch type, the oxygen flow rate of the oxygen plasma irradiated to the support plate 4 is usually 100 to 2000 sccm, and preferably 200 to 1500 sccm. Moreover, the oxygen flow rate of the oxygen plasma irradiated to the support plate 4 is usually 1000 to 5000 sccm, and preferably 2000 to 4000 sccm in the case of a single wafer type. The unit “sccm” is an abbreviation of “standard cc / min” and represents an oxygen flow rate normalized at a constant temperature of 1 atm (atmospheric pressure 1,013 hPa).

  In the case of the batch type, the treatment time of the oxygen plasma irradiated to the support plate 4 is usually 20 to 90 minutes, and preferably 20 to 60 minutes. In the case of the single wafer type, the treatment time of the oxygen plasma applied to the support plate is usually 5 to 30 minutes, and preferably 5 to 20 minutes.

  In one embodiment, the processing conditions when a single wafer type is used as the oxygen plasma generator are, for example, an output of 2800 W, a pressure of 133 Pa (0.5 Torr), an oxygen flow rate of 4000 sccm, a processing time of 5 minutes, and a stage temperature of 200 ° C. .

  In another embodiment, the processing conditions when a batch system is used as the oxygen plasma generator are, for example, an output of 1500 W, a pressure of 133 Pa (0.5 Torr), an oxygen flow rate of 1500 sccm, and a processing time of 20 minutes.

  In the oxygen plasma processing step, the oxygen plasma processing method may be any conditions as long as the residue 5 can be removed. For example, a single wafer type or a batch type may be used. In the oxygen plasma processing step, oxygen plasma may be irradiated on both surfaces of the support plate 4 or only on one surface of the support plate 4 (the surface bonded to the substrate via the adhesive layer 2 and the separation layer 3). Oxygen plasma may be irradiated. When the oxygen plasma treatment process is performed in a single-wafer type and oxygen plasma is irradiated on both surfaces of the support plate 4, it is preferable to pin up the support plate 4.

(Washing process)
Further, as shown in FIG. 1E, it is preferable to clean the surface of the plasma ashed support plate 4 with a solvent using a cleaning brush 7 (cleaning step). Thereby, the residue which could not be removed in the plasma ashing process can be suitably removed.

  The solvent used when cleaning the surface of the support plate 4 is not limited as long as the residue can be removed. The solvent used when cleaning the surface of the support plate 4 is preferably an alkaline solution. The solution showing alkalinity is more preferably an amine compound. As the amine compound, at least one compound selected from the group consisting of primary, secondary, and tertiary aliphatic amines, alicyclic amines, aromatic amines, or heterocyclic amines should be used. Can do.

  Examples of the primary aliphatic amine include monomethanolamine, monoethanolamine (MEA), monoisopropanolamine, ethylenediamine, 2- (2-aminoethoxy) ethanol (DGA), and 2- (2-aminoethylamino) ethanol. Examples of secondary aliphatic amines include 2- (methylamino) ethanol (MMA), diethanolamine, iminobispropylamine, 2-ethylaminoethanol, and the like. Examples of tertiary aliphatic amines include trimethylamine. Examples include ethanolamine, triisopropanolamine, and diethylaminoethanol.

  Examples of alicyclic amines include cyclohexylamine and dicyclohexylamine. Examples of the aromatic amine include benzylamine, dibenzylamine, N-methylbenzylamine and the like. Examples of the heterocyclic amine include N-hydroxyethylpiperidine and 1,8-diazabicyclo [5,4,0] -7-undecene. Among these organic amine compounds, monoethanolamine, 2- (2-aminoethoxy) ethanol, 2-ethylaminoethanol, 2- (methylamino) ethanol (MMA), and other alkanolamines are particularly suitable.

  Further, the stripping solution may be used by mixing with other solvents. Examples of the solvent that may be mixed with the above-described stripping solution include lactones such as γ-butyrolactone, ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone. Examples include organic solvents of polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol, compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate. Further, monomethyl ether, monoethyl ether, monopropyl ether, monobutyl of the polyhydric alcohol or the compound having an ester bond. Derivatives of polyhydric alcohols such as monoalkyl ethers such as ether or compounds having an ether bond such as monophenyl ether, cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, acetic acid Examples include organic solvents such as butyl, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, butyl Aromatic organic solvents such as phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene and the like can be mentioned.

  Moreover, as a solvent that may be mixed with the above-described stripping solution, among these, at least one selected from polyhydric alcohols, compounds having an ester bond, or derivatives of polyhydric alcohols is preferable, diethylene glycol monomethyl ether, Triethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monobutyl ether, propylene glycol monopropyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoisobutyl ether, diethylene glycol dimethyl ether, propylene glycol monoethyl Ether, propylene glycol monomethyl ether (PG E), butyl diglycol, at least one selected from propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monoethyl ether acetate is more preferable.

  The mixing ratio of the alkaline solution and the solvent that may be mixed with the stripping solution is preferably 9: 1 to 1: 9, more preferably 8: 2 to 2: 8, by weight. preferable.

  In the cleaning process, it is preferable to scrub the surface of the support plate 4 as shown in FIG. In this specification, “scrubbing” means using a roll body equipped with a cleaning brush, etc., bringing the cleaning brush into contact with an object to be cleaned and supplying the solvent, water, etc. to the contact portion. It refers to a method of frictionally cleaning an object to be cleaned with a cleaning brush or the like by rotating the body. By scrub cleaning the surface of the support plate 4, the residue 5 adhering to the surface can be more suitably removed.

  In the present embodiment, the surface of the plasma ashed support plate 4 is scrubbed. Therefore, scrub cleaning is performed on the support plate 4 from which most of the residue has been removed by plasma ashing. Thereby, when removing a residue, it can suppress that a washing brush deteriorates or a residue adheres to a washing brush. As described above, after the surface of the support plate 4 is plasma ashed and then scrubbed, a high cleaning effect can be maintained even when a large amount of the support plate 4 is processed using the same cleaning brush. .

  Next, as shown in FIG. 1 (f), the separation layer 3 may be formed on the surface of the cleaned support plate 4. And you may adhere | attach the support plate 4 in which the separation layer 3 was formed, and a board | substrate through the contact bonding layer, and form a laminated body. Thereby, the support plate 4 can be used again for processes such as thinning and mounting while being supported by the substrate.

  In the cleaning step in the processing method according to the present invention, the surface of the support may be paddle cleaned. Paddle cleaning is performed by supplying a chemical solution or the like to the support without rotating the support or rotating at a low speed, and holding the chemical on the support using the surface tension of the chemical. It is.

  In the present invention, most of the residue of the separation layer or adhesive layer adhering to the surface of the support can be removed by the plasma ashing step. And a residue can be removed from a support body more suitably by performing the washing process which wash | cleans the surface of a support body after a plasma ashing process. In the present invention, the cleaning step is not an essential step, and even a configuration not including the cleaning step is included in the scope of the present invention.

  The support from which the residue has been removed by the plasma ashing process and the cleaning process is not easily peeled off when the separation layer and the support are in close contact with each other when the separation layer is formed on the surface of the support. On the other hand, the support from which the residue is not removed easily peels off when the separation layer is formed on the surface of the support because the separation layer and the support do not adhere well. Therefore, a support body can be reused for laminated body formation by the processing method concerning this invention.

[Processing equipment]
Next, the processing apparatus according to the present embodiment will be described with reference to FIG. FIG. 2 is a diagram illustrating the processing apparatus 100 according to the present embodiment. The processing apparatus 100 according to the present embodiment includes a separation layer 10 in a laminate 10 in which a substrate 1, an adhesive layer 2, a separation layer 3 that is altered by absorbing light, and a support plate 4 are laminated in this order. 3 is a processing apparatus 100 for processing the support plate 4 after the support plate 4 and the substrate 1 are separated from each other, and is attached to the surface of the support plate 4 by plasma ashing the surface of the support plate 4. A plasma generating device (plasma generating means) 6 for removing residues of the separating layer 3 or the adhesive layer 2 and a cleaning brush (cleaning means) 7 for cleaning the surface of the plasma-ashed support plate 4 with a solvent. Prepare.

(Plasma generator 6)
The plasma generating device 6 is a device that generates plasma and irradiates the object placed on the mounting table 11 with plasma. Therefore, the support plate 4 with the residue 5 attached on the surface is placed on the mounting table 11 and plasma is generated, whereby the support plate 4 can be irradiated with the plasma. Thereby, the residue 5 adhering on the support plate 4 can be removed. Since the plasma generator 6 conforms to the description of the plasma ashing process described in the processing method according to the present embodiment, detailed description thereof is omitted.

(Cleaning brush 7)
The cleaning brush 7 frictionally cleans the cleaning object by contacting the cleaning object mounted on the mounting table 13. The cleaning brush 7 is connected to the storage tank 12 and cleans the object to be cleaned while supplying solvent, water, etc. from the storage tank 12. Thereby, the support plate 4 after removing the residue 5 by the plasma generator 6 can be washed. The solvent stored in the storage tank 12 is the same as the solvent used in the cleaning process described in the processing method according to this embodiment.

(Separation layer forming means)
Furthermore, the processing apparatus 100 according to this embodiment may further include a separation layer forming unit that forms the separation layer 3 on the surface of the support plate 4 cleaned by the cleaning brush 7. The separation layer forming means is not particularly limited as long as it can generate the separation layer 3 described in the processing method according to this embodiment.

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

[Example 1]
First, the laminated body was produced as follows.

(Production of laminate)
TZNR-3007t (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) as an adhesive composition is spin-coated on a wafer substrate on a 12-inch wafer substrate (thickness: 50 μm), and each is performed at 100 ° C., 160 ° C. and 220 ° C. for 4 minutes. An adhesive layer (thickness 50 μm) was formed by baking. Next, 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 forming temperature of 240 ° C., a fluorocarbon film (thickness 0.7 μm) is supported by a CVD method using C ₄ F ₈ as a reaction gas. A 12-inch glass substrate having a thickness of 670 μm was formed as a separation layer.

  And the wafer substrate and the support body which has a separation layer were bonded together through the contact bonding layer, and the laminated body which laminated | stacked the wafer substrate, the contact bonding layer, the separation layer, and the support body in this order was produced.

(Separation of support)
Next, a YVO ₄ laser having a wavelength of 532 nm was irradiated from the support side of the laminate to the separation layer. The separation layer was altered by laser irradiation, and the support was separated from the laminate. On the separated support, the altered separation layer and adhesive layer remained.

(Oxygen plasma treatment)
Next, an oxygen plasma is generated by a single wafer type oxygen plasma generator (TCA-7222 manufactured by Tokyo Ohka Kogyo Co., Ltd.), and the oxygen plasma is irradiated onto the support, thereby leaving a separation layer remaining on the support. And the adhesive layer was removed. The conditions for generating oxygen plasma (oxygen ashing conditions) were an output of 2800 W, a pressure of 133 Pa (0.5 Torr), an oxygen flow rate of 4000 sccm, a processing time of 5 minutes, and a stage temperature of 200 ° C. As a result, most of the separation layer and the adhesive layer remaining on the support could be removed.

  After removing the separation layer and the adhesive layer remaining on the surface of the support by oxygen ashing, the amount of the residue adhered to the surface was measured using a particle counter (LS6600 manufactured by Hitachi High-Technologies Corporation). . By using this particle counter, it is possible to measure how many particles (residues) are 1 μm to 10 μm on the measurement object. The amount of residue measured with a particle counter was 6977.

[Example 2]
Under the same conditions as in Example 1, a laminate was formed, the support was separated from the laminate, and the support was subjected to oxygen ashing.

  Furthermore, after the separation layer and the adhesive layer remaining on the surface of the support were removed by oxygen ashing, the surface was subjected to paddle cleaning using a solvent. As the solvent, SLR (TZNR (registered trademark) -SL Remover (manufactured by Tokyo Ohka Kogyo Co., Ltd.)), which is an amine solvent showing alkalinity, was used. Thereafter, the amount of residue adhering to the surface was inspected using a particle counter. The amount of residue measured with a particle counter was 4733.

[Discussion based on Examples 1 and 2]
Compared to Example 1 in which only oxygen ashing was performed, Example 2 in which oxygen ashing and solvent cleaning were performed had fewer residues attached to the surface of the support. From this result, it was shown that not only oxygen ashing but also the amount of residue adhering to the surface can be reduced by washing the surface of the support with a solvent.

Example 3
Under the same conditions as in Example 1, a laminate was formed, the support was separated from the laminate, and the support was subjected to oxygen ashing.

Further, the separation layer and the adhesive layer remaining on the surface of the support were removed by oxygen ashing, and then the surface of the support was scrubbed using SLR as a solvent. In scrub cleaning, a PVA brush is used as a cleaning brush, and scrub cleaning conditions are as follows. The following DIW means De-lonized Water;
Scrub cleaning conditions 1st step Cleaning solution: SLR
Rotation speed: 1,000rpm
Brush: Yes
Time: 120 seconds 2nd step Cleaning solution: DIW
Rotation speed: 1,000rpm
Brush: Yes
Time: 120 seconds 3rd step Cleaning solution: DIW
Rotation speed: 1,000rpm
Brush: None
Time: 15 seconds 4th step Number of revolutions: 1,000 rpm
Time: 30 seconds.

  Then, the operation of scrub cleaning the support removed from the laminate formed under the same conditions as in Example 1 after oxygen ashing was repeated. And after processing 70 support bodies in total, the quantity of the residue adhering to the surface of the support body processed last was inspected using the particle counter. The amount of residue adhering to the last treated (70th) support was 42.

[Discussion based on Examples 2 and 3]
By scrub-cleaning the support after oxygen ashing (Example 3), the amount of residue adhering to the surface of the support is less than in the case of paddle-cleaning the support after oxygen ashing (Example 2). Was able to be reduced.

[Comparative Example 1]
After forming the laminate under the same conditions as in Example 1 and removing the support from the laminate, the surface of the support was attached to the surface using a particle counter without oxygen ashing and solvent cleaning. The amount of residue was measured. However, since the amount of the residue adhered to the surface of the support was too much, the amount of the residue could not be measured. Since the maximum number of particles that can be measured in the particle counter is 60000, the amount of residue adhering to the surface of the support is greater than 60000, and even when only oxygen ashing is performed, it adheres to the surface of the support. It was shown that the residue obtained can be removed suitably.

[Comparative Example 2]
Under the same conditions as in Example 1, a laminate was formed, and the support was separated from the laminate. Thereafter, the surface of the support was scrubbed with a cleaning brush using SLR without oxygen ashing. The amount of residue adhering to the surface was measured using a particle counter. The amount of the residue adhering to the support was 64.

  Further, the operation of scrub cleaning the support removed from the laminate formed under the same conditions as in Example 1 with the same cleaning brush without performing oxygen ashing was repeated. And after processing 20 support bodies in total, the quantity of the residue adhering to the surface of the support body processed last was inspected using the particle counter. The amount of residue adhering to the last treated (20th) support was 734.

[Consideration based on Comparative Example 2]
In Comparative Example 2, the number of particles attached to the support treated on the 20th sheet was larger than the number of particles attached to the support treated first. This is because if the support is scrubbed without oxygen ashing, it is necessary to directly remove residues adhering to the surface of the support. Repeat scrub cleaning with the same cleaning brush to It is thought that this is because a residue is attached.

[Consideration Based on Example 3 and Comparative Example 2]
By comparing the results of Example 3 and Comparative Example 2, in the case of Example 3, that is, when scrub cleaning was performed after oxygen ashing, residues were removed from the surface of the support without reducing the cleaning effect of scrub cleaning. Was successfully removed. This is because most of the residue adhering to the surface of the support was removed by oxygen ashing the support, so that when the residue was removed, the cleaning brush deteriorated or the residue adhered to the cleaning brush. It is thought that it was because it was able to suppress doing.

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

1 Substrate 2 Adhesive layer 3 Separation layer 4 Support plate (support)
5 Residue 6 Plasma generator (plasma generator)
7 Cleaning brush (cleaning means)
DESCRIPTION OF SYMBOLS 10 Laminated body 11,13 Mounting stand 12 Storage tank 100 Processing apparatus

Claims (5)

A processing method for processing 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,
A separation step of irradiating the separation layer with light to alter the separation layer and separating the support and the substrate;
A plasma ashing step for removing residues of the separation layer or the adhesive layer adhering to the surface of the support by plasma ashing the surface of the support after the separation ; and
Cleaning the surface of the support subjected to plasma ashing with a solvent ,
The said solvent contains the amine compound which shows alkalinity, The processing method characterized by the above-mentioned . The processing method according to claim 1 , wherein in the cleaning step, the surface of the support is scrubbed. The plasma ashing step, the processing method according to claim 1 or 2 wherein characterized in that it is carried out by oxygen ashing. The support and the substrate were separated by altering the separation layer in the laminate formed by laminating the substrate, the adhesive layer, the separation layer that is altered by absorbing light, and the support in this order. A processing apparatus for processing the support,
Plasma generating means for removing residues of the separation layer or the adhesive layer attached to the surface of the support by plasma ashing the surface of the support;
Cleaning means for cleaning the surface of the support subjected to plasma ashing with a solvent ,
The said solvent contains the amine compound which shows alkalinity, The processing apparatus characterized by the above-mentioned . The processing apparatus according to claim 4 , further comprising a separation layer forming unit that forms a separation layer that is altered by absorbing light on the surface of the washed support.

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