JP2013084950A - Temporary fixing method of substrate, semiconductor device and temporary fixing composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate-processing method capable of forming a temporary fixing material without floatation between a substrate or a support and a temporary fixing material when laminating a substrate and a support in a method for temporary fixing via a temporary fixing material having an adhesive layer and a peeling layer partially formed.SOLUTION: A substrate-temporary fixing method has steps of: (1) forming an adhesive layer and a peeling layer, in this order, on a substrate with a temporary fixing composition having a polymer (A) and a compound (B) substantially immiscible with the polymer (A); (2) temporarily fixing the above substrate and a support via an adhesive layer, except for a part of the above peeling layer; (4) forming the rest of the adhesive layer, the rest of the peeling layer and the support, in this order, on the substrate, except for a part of the above adhesive layer; and (5) peeling the substrate after processing from the support; in this order.

Description

  The present invention relates to a method for temporarily fixing a base material, a semiconductor device, and a raw material composition suitable for forming a temporary fixing material that can be used to temporarily fix the base material on a support when the base material is processed. About.

When processing a substrate such as a semiconductor wafer (eg: dicing, back grinding, photofabrication) or moving (eg: moving a substrate from one device to another), the substrate is displaced from the support and does not move. Thus, it is necessary to temporarily fix the base material and the support using a temporary fixing material or the like. And after a process and / or a movement end, it is necessary to peel a base material from a support body.
For example, in Patent Document 1, the base material and the support are bonded to each other at the peripheral portion of the base material or the support through an adhesive layer, and the other portions are advantageous for peeling the base from the support. A method of temporarily fixing using a temporary fixing material having a layer having a function (for example, a layer formed of a release agent: a release layer) has been proposed.

  As a means for forming such a temporary fixing material, the adhesive layer and the release layer are formed separately, for example, 1) a release layer is formed on a portion other than the peripheral portion of the support, and the substrate A method of forming an adhesive layer on the entire surface of the substrate, and then bonding the support and the substrate so that the release layer and the adhesive layer face each other. 2) Forming the adhesive layer on the substrate, A method in which a release layer is formed on a portion other than the peripheral portion on the adhesive layer, and then the support and the base material are bonded together via the adhesive layer and the release layer. 3) The peripheral portion on the base material A method in which a release layer is formed on a portion other than the substrate, and then an adhesive layer is dispensed on the peripheral portion, and then the support and the substrate are bonded together via the adhesive layer and the release layer. , Was proposed.

Special table 2011-510518 gazette

  By the way, when forming a peeling layer by application | coating, depending on the kind of base material, a coating liquid and a base material repel, and it is difficult to form a peeling layer uniformly on a base material. Further, when the release layer is formed by coating, it is difficult to form the release layer uniformly and thinly on the base material. Therefore, the release layer is formed as a thick film. For this reason, when the base material and the support are bonded together, the release layer is non-uniform or the release layer is a thick film, so that floating occurs between the base material and the support and the temporary fixing material. When processing the base material, there is a problem that the base material falls off from the support due to the floating. In particular, when the base material is large or heavy, the problem that the base material falls off from the support becomes prominent.

  An object of the present invention is to provide a substrate and a support in a method of temporarily fixing via a temporarily fixing material having a partially formed adhesive layer and a release layer, as in the method of temporarily fixing a substrate of Patent Document 1. Providing a temporary fixing method of a base material that can form a temporary fixing material without floating between the base material or the support and the temporary fixing material, and related to the temporary fixing method of the base material The object is to provide a temporary fixing composition and a semiconductor device.

  The present inventors have intensively studied to solve the above problems. As a result, it has been found that the above problems can be solved by a temporary fixing method of a substrate having the following configuration, and the present invention has been completed. That is, the present invention relates to the following [1] to [8], for example.

[1] (1) An adhesive layer and a release layer on a substrate by a temporary fixing composition containing the polymer (A) and the compound (B) substantially immiscible with the polymer (A). Forming the layers in this order;
(2) A step of temporarily fixing the base material and the support through the adhesive layer except for a part of the release layer;
(4) A step of forming a remaining part of the adhesive layer, a remaining part of the release layer, and a support in this order on the substrate, excluding a part of the adhesive layer; and (5) peeling the processed substrate from the support. The step of:
A method for temporarily fixing a base material in this order.
[2] The method for temporarily fixing a base material according to [1], wherein the adhesive layer is an adhesive layer containing a cycloolefin polymer (A1).
[3] In step (4), a part of the adhesive layer is removed by dissolving in a hydrocarbon solvent, and the remaining part of the adhesive layer, the remaining part of the release layer, and the support are formed in this order on the substrate. The method for temporarily fixing a base material according to [2], wherein:
[4] The method for temporarily fixing a substrate according to [1], wherein the release layer has a thickness of 1 to 1000 nm.
[5] A composition for temporary fixing used in the method for temporarily fixing a substrate according to the above [1] to [4], which is substantially immiscible with the polymer (A) and the polymer (A). The composition for temporary fixing containing the compound (B).
[6] The temporarily fixing composition according to [5], wherein the polymer (A) is a cycloolefin polymer (A1).
[7] A composition containing 1 to 30 parts by mass of 100 parts by mass of a cycloolefin polymer (A1) and a polymer (B1) having a repeating unit having a fluorine atom.
[8] A semiconductor device obtained by the method for temporarily fixing a substrate according to [1].

  According to the present invention, when the base material and the support are bonded together, a temporary fixing method of the base material that can form the temporary fixing material without floating between the base material and the support and the temporary fixing material is provided. In addition, a temporary fixing composition and a semiconductor device related to the temporary fixing method of the substrate can be provided.

The schematic diagram of one embodiment of the temporary fixing method of a base material. The schematic diagram of one embodiment of the temporary fixing method of a base material. The schematic diagram of one embodiment of the temporary fixing method of a base material.

Hereinafter, the temporary fixing method of the base material of the present invention, the temporary fixing composition related to the temporary fixing method of the base material, and the semiconductor device obtained by the temporary fixing method of the base material will be described.
In the present invention, the temporary fixing composition is a composition for forming a temporary fixing material. Temporary fixing material refers to processing a substrate such as a semiconductor wafer (eg dicing, back grinding, photofabrication (eg resist pattern formation, metal bump formation by plating, film formation by chemical vapor deposition, RIE) Temporary fixing material used to temporarily fix the base material so that the base material is not displaced and moved from the support when moving the base material from one device to another device) That is.

1. Temporary fixing method of substrate The temporary fixing method of the substrate of the present invention is:
(1) A temporary fixing composition containing the polymer (A) and the compound (B) substantially immiscible with the polymer (A) is used to form an adhesive layer and a release layer on the substrate. Forming in order;
(2) A step of temporarily fixing the base material and the support through the adhesive layer except for a part of the release layer;
(4) A step of forming a remaining part of the adhesive layer, a remaining part of the release layer, and a support in this order on the substrate, excluding a part of the adhesive layer; and (5) peeling the processed substrate from the support. The step of:
In this order. Hereinafter, each said process is also called process (1)-process (5), respectively.

  In the present invention, an adhesive layer and a release layer are formed on a base material from a temporary fixing composition containing a polymer (A) and a compound (B) substantially immiscible with the polymer (A). Therefore, the release layer can be uniformly and thinly formed on the adhesive layer. From this, by removing a part of the release layer, it is possible to form a temporary fixing material having an adhesive part, a remaining part of the release layer, and a remaining part of the adhesive layer. For this reason, a base material and a support body can be bonded together without floating between a base material, a support body, and a temporary fixing material.

1-1. Process (1)
A schematic diagram of the step (1) is shown in FIGS. 1 (a) and 1 (b). In the step (1), a temporary fixing composition containing the polymer (A) and the compound (B) substantially immiscible with the polymer (A) is applied onto the substrate 10. Then, the coating film 20 made of the temporary fixing composition is formed, and then the polymer (A) and the compound (B) are separated from the coating film 20 so as to contain more polymer (A). The layer 21 and the release layer 22 containing more compound (B) are formed on the substrate 10.

  Examples of the base material 10 that is an object to be processed include a semiconductor wafer, a glass substrate, a resin substrate, a metal substrate, and a substrate having a metal foil. A semiconductor wafer is usually formed with bumps, wirings, insulating films, and the like. Examples of the resin coating include a layer containing an organic component as a main component; specifically, a photosensitive resin layer formed from a photosensitive material, an insulating resin layer formed from an insulating material, Examples thereof include a photosensitive insulating resin layer formed from a photosensitive insulating resin material.

  When the coating film 20 is formed on the base material, the surface of the base material can be pretreated in order to form the coating film 20 uniformly in the surface. Examples of the surface treatment method include a method of previously applying a surface treatment agent to the surface of the substrate.

Examples of the surface treatment agent include silicon compounds such as 3-aminopropyltrimethoxysilane and hexamethyldisilazane. These are formed on the substrate by spin coating or in the form of gas.

As a method for applying the temporary fixing composition, a conventionally known coating method such as a spin coating method can be used. In the spin coating method, it is appropriately determined depending on the size of the substrate. For example, in the case of a 12-inch silicon wafer, the rotation speed is usually 300 to 3,500 rpm (preferably 500 to 1,500 rpm) and the acceleration is 500 to 15. , 1,000 rpm / second, and rotation time of 30 to 300 seconds.

After the temporary fixing composition is applied and the coating film 20 is formed, in order to promote the formation of the adhesive layer 21 and the release layer 22 and when the temporary fixing composition contains a solvent, the solvent is added. In order to evaporate, heat treatment can be performed with a hot plate or the like. The temperature of heat processing is 150-275 degreeC normally, Preferably it is 150-260 degreeC, Time is 2 to 15 minutes, More preferably, it is 3 to 10 minutes. The film thickness of the coating film 20 is usually 5 to 500 μm.

As described later, since the compound (B) has a lower surface energy than the polymer (A), the compound (B) is unevenly distributed on the surface of the coating film 20 by layer separation. Due to this uneven distribution, an adhesive layer 21 containing more polymer (A) and a release layer 22 containing more compound (B) are formed. In addition, the peeling layer 22 shows the layer which a compound (B) contains 60weight% or more here, and the contact bonding layer 21 shows layers other than the peeling layer 22 in the layer formed from a coating film.
In addition, content of the compound (B) contained in a peeling layer is the value measured by X-ray electron spectroscopy (ESCA: Electron Spectroscopy for Chemical Analysis).

The film thickness of the adhesive layer 21 is usually 5 to 500 μm. In addition, when there are protrusions such as bumps on the surface of the substrate 10 where the adhesive layer 21 is formed, the protrusions may be covered with the adhesive layer in order to protect the protrusions. From this, the film thickness of the adhesive layer 21 can be determined as appropriate depending on the height of the protrusions. However, when the protrusions are provided, the film thickness of the adhesive layer 21 is usually smaller than the height 1 of the protrusions. It is formed at 1.5 or more.

The thickness of the release layer 22 is usually 1 to 1000 nm, preferably 5 to 900 nm, and more preferably 10 to 800 nm.

1-1-1. Temporary Fixing Composition The temporary fixing composition contains the polymer (A) and a compound (B) that is substantially immiscible with the polymer (A). Moreover, a solvent (C) is contained as needed.

<Polymer (A)>
The polymer (A) may be any polymer such as a thermosetting resin or a thermoplastic resin. Among these, a thermoplastic resin is preferable in order to easily remove a part of the adhesive layer with a solvent in the step (4).

  Thermoplastic resins include cycloolefin resins, polyether resins, polycarbonate resins, polyimide resins, and other high melting temperatures; novolak resins, C5 petroleum resins, C9 petroleum resins, and C5 / C9 mixtures. Petroleum resin, cyclopentadiene resin, polymer of vinyl-substituted aromatic compound, copolymer of olefin and vinyl-substituted aromatic compound, copolymer of cyclopentadiene compound and vinyl-substituted aromatic compound, hydrogenation of these A resin having a low melting temperature such as a product. Two or more thermoplastic resins can be used in combination. For example, the melting temperature of the adhesive layer can be controlled by combining a resin having a high melting temperature and a resin having a low melting temperature. Among these, cycloolefin resin (A1) is preferable.

  Examples of the cycloolefin polymer (A1) include cyclic olefin addition copolymers, cyclic olefin ring-opening metathesis polymers, and polymers obtained by hydrogenating the ring-opening metathesis polymers. Such a polymerization method of the cycloolefin polymer (A1) is conventionally known. The weight average molecular weight (Mw) measured by the gel permeation chromatography (GPC) method of the cycloolefin polymer (A1) is usually 5,000 to 1,000,000, preferably 10,000 in terms of polystyrene. ~ 500,000.

  Examples of the cyclic olefin include norbornene olefin, tetracyclododecene olefin, dicyclopentadiene olefin, and derivatives thereof. Examples of the derivative include an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms) and an alkylidene group (preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms). Alkylidene group), an aralkyl group (preferably an aralkyl group having 7 to 30 carbon atoms, more preferably an aralkyl group having 7 to 18 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms, more preferably 3 to 18 carbon atoms). Cycloalkyl group), a hydroxy group, an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms), an acetyl group, a cyano group, an amide group, an imide group, a silyl group, and an aryl group.

  Examples of commercially available cycloolefin polymers (A1) include “ZEONOR” and “ZEONEX” manufactured by Nippon Zeon Co., Ltd., “ARTON” manufactured by JSR Corporation, Examples include “TOPAS (Topas)” manufactured by TOPAS ADVANCED POLYMERS, “APEL” manufactured by Mitsui Chemicals, Inc., and the like.

<Compound (B)>
The polymer (A) and the substantially immiscible compound (B) are uniformly dissolved or dispersed in the polymer (A) and other components in the temporary fixing composition. The compound which the solubility or dispersibility with a polymer (A) or another component falls when forming a coating film from is shown.

The compound (B) has a lower surface energy than the polymer (A). For this reason, in the coating film containing the polymer (A) and the compound (B), the compound (B) is unevenly distributed on the surface of the coating film to form a release layer. The surface energy is usually 0.01 mN / m or more, preferably 0.1 mN / m or more lower than the surface energy of the polymer (A).

The compound (B) is preferably a polymer (B1) having a repeating unit having a fluorine atom. Specific examples of such repeating units include polymers described in JP 2007-163606 A, JP 2011-095623 A, and JP 2011-170284 A.
As the compound (B), for example, a compound having a silicon atom described in JP-A-2007-163606 can be used.

Among these, the polymer (B1-1) having a repeating unit represented by the following general formula (b1) and / or (b2) can satisfactorily form the adhesive layer 21 and the release layer 22, and the uniform release layer. Therefore, when the base material and the support are bonded, the temporary fixing material can be formed without floating between the base material or the support and the temporary fixing material, which is preferable.

In general formulas (b1) and (b2), R ¹ represents a hydrogen atom, a methyl group, or a trifluoromethyl group. In general formula (b1), Rf ¹ represents a hydrocarbon group having 1 to 30 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. In general formula (b2), R ² represents an (n + 1) -valent linking group. n shows the integer of 1-3. R ³ represents a hydrogen atom or a monovalent organic group. Rf ² independently represents a hydrogen atom or an electron-withdrawing group.

Examples of Rf ^{1 in} the general formula (b1) include linear or branched aliphatic hydrocarbon groups having 1 to 6 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, and at least one hydrogen. There are alicyclic hydrocarbon groups having 4 to 20 carbon atoms in which atoms are substituted with fluorine atoms, or groups derived therefrom.

  Examples of the linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom include a methyl group, an ethyl group, a 1-propyl group, and a 2-propyl group. 1-butyl group, 2-butyl group, 2- (2-methylpropyl) group, 1-pentyl group, 2-pentyl group, 3-pentyl group, 1- (2-methylbutyl) group, 1- (3- Methylbutyl) group, 2- (2-methylbutyl) group, 2- (3-methylbutyl) group, neopentyl group, 1-hexyl group, 2-hexyl group, 3-hexyl group, 1- (2-methylpentyl) group, 1- (3-methylpentyl) group, 1- (4-methylpentyl) group, 2- (2-methylpentyl) group, 2- (3-methylpentyl) group, 2- (4-methylpentyl) group, 3- (2-methylpentyl) group, 3- (3-methyl Rupenchiru) group, or their partially fluorinated or can be exemplified those perfluorinated alkylated group.

  Examples of the alicyclic hydrocarbon group having 4 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom or a group derived therefrom include a cyclopentyl group, a cyclopentylmethyl group, and 1- (1-cyclopentyl). Ethyl) group, 1- (2-cyclopentylethyl) group, cyclohexyl group, cyclohexylmethyl group, 1- (1-cyclohexylethyl) group, 1- (2-cyclohexylethyl group), cycloheptyl group, cycloheptylmethyl group, 1- (1-cycloheptylethyl) group, 1- (2-cycloheptylethyl) group, alicyclic hydrocarbon group such as 2-norbornyl group, or a partially fluorinated or perfluoroalkylated group thereof Etc.

In general formula (b2), R ³ represents a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include a hydrocarbon group which may have a monovalent substituent having 1 to 30 carbon atoms.

  Examples of the monovalent hydrocarbon group having 1 to 30 carbon atoms include a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms and an alicyclic hydrocarbon group having 3 to 30 carbon atoms. A linear or branched alkyl group having 1 to 7 carbon atoms and an alicyclic hydrocarbon group having 3 to 7 carbon atoms are preferable.

  Examples of the linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms include methyl group, ethyl group, 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl group, 2- ( 2-methylpropyl) group, 1-pentyl group, 2-pentyl group, 3-pentyl group, 1- (2-methylbutyl) group, 1- (3-methylbutyl) group, 2- (2-methylbutyl) group, 2 -(3-methylbutyl) group, neopentyl group, 1-hexyl group, 2-hexyl group, 3-hexyl group, 1- (2-methylpentyl) group, 1- (3-methylpentyl) group, 1- (4 -Methylpentyl) group, 2- (2-methylpentyl) group, 2- (3-methylpentyl) group, 2- (4-methylpentyl) group, 3- (2-methylpentyl) group, 3- (3 -Methylpentyl) group and the like. Examples of the alicyclic hydrocarbon group having 3 to 30 carbon atoms include a cyclopentyl group, a cyclopentylmethyl group, a 1- (1-cyclopentylethyl) group, a 1- (2-cyclopentylethyl) group, a cyclohexyl group, and a cyclohexylmethyl group. , Cycloheptyl group, 2-norbornyl group and the like. Moreover, this hydrocarbon group may have a substituent.

In general formula (b2), R ² represents an (n + 1) -valent linking group. Examples of the linking group include a single bond or an (n + 1) -valent hydrocarbon group having 1 to 30 carbon atoms. Further, there are combinations of these hydrocarbon groups with an oxygen atom, a sulfur atom, an imino group, a carbonyl group, a —CO—O— group, or a —CO—NH— group.

In the formula (b2), Rf ² represents a hydrogen atom or an electron-withdrawing group. Examples of the electron withdrawing group include a fluorine atom or a hydrocarbon group having 1 to 30 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, a nitro group, a cyano group, and the like. The at least one hydrocarbon group having 1 to 30 carbon atoms which hydrogen atoms are substituted by fluorine atoms, the same is true with the Rf ^1.

  The polymer (B1-1) having the repeating unit (b1) and / or (b2) is obtained by repeating the repeating unit (b1) in a known method, for example, in a polymerization solvent in the presence of a polymerization initiator or a chain transfer agent. The monomer to be provided and / or the monomer to give the repeating unit (b2) and, if necessary, another monomer (b3) can be synthesized by radical polymerization.

  Examples of the monomer that gives the repeating unit (b1) include trifluoromethyl (meth) acrylic acid ester, 2,2,2-trifluoroethyl (meth) acrylic acid ester, perfluoroethyl (meth) acrylic acid ester, Fluoro n-propyl (meth) acrylate, perfluoro i-propyl (meth) acrylate, perfluoro n-butyl (meth) acrylate, perfluoro i-butyl (meth) acrylate, perfluoro t -Butyl (meth) acrylic acid ester, 2- (1,1,1,3,3,3-hexafluoropropyl) (meth) acrylic acid ester, 1- (2,2,3,3,4,4, 5,5-octafluoropentyl) (meth) acrylic ester, perfluorocyclohexylmethyl (meth) acryl Acid ester, 1- (2,2,3,3,3-pentafluoropropyl) (meth) acrylic acid ester, 1- (3,3,4,4,5,5,6,6,7,7, 8,8,9,9,10,10,10-heptadecafluorodecyl) (meth) acrylic acid ester, 1- (5-trifluoromethyl-3,3,4,4,5,6,6,6 -Octafluorohexyl) (meth) acrylic acid ester and the like. A commercial item can be used for the monomer which gives a repeating unit (b1).

  Examples of the monomer that gives the repeating unit (b2) include monomers represented by the following general formulas (b2-m1) to (b2-m5).

In the formula (b2-m1) ~ (b2 -m5), R 1 and ^{R 3} are the same as ^{R 1} and ^{R 3} in the general formula (b2).

  Examples of the other monomer (b3) include monomers represented by the following general formulas (b3-m1) to (b3-m4), trifluoromethyl (meth) acrylate, 2,2,2-trimethyl Fluoroethyl (meth) acrylic acid ester, perfluoroethyl (meth) acrylic acid ester, perfluoro n-propyl (meth) acrylic acid ester, perfluoro i-propyl (meth) acrylic acid ester, perfluoro n-butyl (meta ) Acrylic acid ester, perfluoro i-butyl (meth) acrylic acid ester, perfluoro t-butyl (meth) acrylic acid ester, 2- (1,1,1,3,3,3-hexafluoropropyl) (meta ) Acrylic acid ester, 1- (2,2,3,3,4,4,5,5-octafluoropentyl) (meth) acrylic acid ester, Fluorocyclohexylmethyl (meth) acrylic acid ester, 1- (2,2,3,3,3-pentafluoropropyl) (meth) acrylic acid ester, 1- (3,3,4,4,5,5,6 , 6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl) (meth) acrylic acid ester, 1- (5-trifluoromethyl-3,3,4,4, 5,6,6,6-octafluorohexyl) (meth) acrylic acid ester, (((trifluoromethyl) sulfonyl) amino) ethyl-1-methacrylate, 2-(((trifluoromethyl) sulfonyl) amino) ethyl Examples thereof include -1-acrylate.

  The content ratio of the repeating structural unit (b1) and the repeating structural unit (b2) contained in the polymer (B1-1) is usually 100 mol% when the total of all repeating structural units in the polymer is 100 mol%. Or less, preferably 50 to 100 mol%, more preferably 60 to 100 mol%.

  The weight average molecular weight (Mw) measured by the gel permeation chromatography (GPC) method of a polymer (B1-1) is 1000-100000 normally in polystyrene conversion, Preferably it is 1000-30000. It is the value measured according to the description of the examples.

Content of a compound (B) is 1-50 mass parts normally with respect to 100 mass parts of polymers (A), Preferably it is 2-30 mass parts. When the content of the compound (B) is in the above range, it is preferable because the temporary fixing material can be formed without floating between the base material or the support and the temporary fixing material.
In addition, when the compound (B) is a polymer (B1) having a repeating unit having a fluorine atom and the polymer (A) is a cycloolefin polymer (A1), the cycloolefin polymer (A1) The polymer (B1) having a repeating unit having a fluorine atom with respect to 100 parts by mass contains 1 to 30 parts by mass, preferably 2 to 20 parts by mass, more preferably 3 to 15 parts by mass. When the content of the polymer (B1) having a repeating unit having a fluorine atom is in the above range, it is preferable that the temporary fixing material can be formed without floating between the base material or the support and the temporary fixing material.

<Solvent (C)>
In order to improve the handling properties of the temporary fixing composition, the temporary fixing composition is uniformly mixed with components contained in the temporary fixing composition such as the polymer (A) and the compound (B). Can be used to

The solvent (C) may be any solvent that can dissolve the polymer (A) and the compound (B). For example, limonene, mesitylene, dipentene, pinene, bicyclohexyl, cyclododecene, 1-tert. -Hydrocarbons such as butyl-3,5-dimethylbenzene, butylcyclohexane, cyclooctane, cycloheptane, cyclohexane, methylcyclohexane, anisole, 4-methyl-2-pentanol, 1-butyl alcohol, 2-butyl alcohol, Isobutyl alcohol, propylene glycol monomethyl ether, dipropylene glycol methyl ether, alcohol / ethers such as diglyme, ethyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl Examples include esters / lactones such as ether acetate and γ-butyrolactone, ketones such as cyclohexanone, amides / lactams such as N-methyl-2-pyrrolidinone, and these may be used alone or in combination of two or more. May be used in combination. Among these, when the cycloolefin polymer (A1) is used as the polymer (A), hydrocarbons are preferable from the viewpoint of the solubility of the cycloolefin polymer (A1).

<Other ingredients>
The temporary fixing composition may further include an adhesion assistant such as γ-glycidoxypropyltrimethoxysilane, if necessary, as described in JP-A No. 2003-191375 for the purpose of improving the elongation of the temporary fixing material. Ultraviolet absorbers such as Lucilin TPO (manufactured by BASF), Irgacure 651 (manufactured by BASF) and carbon black, in order to cause the temporary fixing material to be decomposed by exposure and easily peeled off when the elastomer is peeled after temporary fixing In order to prevent oxidation of the temporary fixing material, an antioxidant such as TINUVIN479 (manufactured by BASF) can be added.

<Preparation of composition for temporary fixation>
The temporary fixing composition is prepared by mixing the above components uniformly. In addition, for the purpose of removing impurities, filtration can be appropriately performed. The content of the polymer (A) contained in the temporary fixing composition is usually 5 to 70% by weight, and the content of the compound (B) is usually 0.01 to 10% by weight.

1-2. Process (2)
A schematic diagram of the step (2) is shown in FIG. 1 (c), FIG. 2 (a), and FIG. 2 (b). In the step (2), a part of the adhesive layer 21 is exposed by removing a part of the release layer 22. Next, by pressing the support 40 from the side having the remaining part 24 of the release layer and the adhesive layer 21, a part of the adhesive layer 21 occupies the part 30 from which the release layer has been removed, so that a part of the adhesive layer 21 Becomes the bonding portion 23. Next, the base material 10 and the support body 40 are temporarily fixed via the bonding portion 23. That is, the base material 10 and the support body 40 are temporarily fixed through the temporary fixing material formed from the adhesive layer 21 and having the adhesive portion 23, the peeling layer remaining portion 24, and the adhesive layer remaining portion 25.

  The release layer 22 is usually removed by bringing the release layer 22 into contact with a soluble solvent. Any solvent may be used as long as the release layer 22 can be dissolved, but usually the polarity mentioned in the above-described temporary fixing composition or the repeating structural unit (b2). When it has a group, water and an aqueous tetramethylammonium hydroxide solution are used. The contact time and temperature between the release layer 22 and the solvent are appropriately selected depending on the type of the solvent and the thickness of the release layer, and are usually 1 to 10000 seconds and 10 to 40 ° C.

  The place where the release layer 22 is removed is preferably a release layer formed above the periphery of the substrate. In the step (4), if the bonding portion 23 is surrounded by other layers or members (base material, support, and other layers or portions), it is very difficult to remove the bonding portion. Since the adhesive part 23 is formed at the place where the release layer 22 is removed, the adhesive part 23 is not surrounded by the base material, the support, and other layers or parts at the place where the release layer 22 is removed. A release layer formed above the periphery of the substrate that can be formed in place is preferred.

In step (3), various process solvents are often used, and the process solvents come into contact with the temporary fixing material. By forming the bonding portion 23 on the peripheral edge portion of the substrate 10, the remaining portion 24 of the peeling layer that is relatively inferior (dissolved) to the process solvent can be protected by the bonding portion 23. Therefore, since the selection of the material of the remaining portion 24 of the release layer can be expanded without being restricted by the process solvent, the release layer formed on the periphery of the base material is preferable as the place where the release layer 22 is removed.

As the support 40, for example, a material such as glass or silicon that is easy to handle and has a hard and flat surface is used.
When the support is pressed, the adhesive layer 21 may be heated (usually at 50 to 350 ° C. for 10 to 300 seconds). By performing the heating while heating the adhesive layer 21, the surface 30 of the exposed adhesive layer 21 and the support 40 can be easily bonded.

1-3. Process (3)
A schematic diagram of the step (3) is shown in FIG. Step (3) is a step of processing the substrate 10, that is, a step of processing the substrate 10 (substrate to be processed) temporarily fixed on the support to obtain the processed substrate 11. The processing of the substrate 10 includes, for example, photofabrication including at least one processing selected from thinning of the substrate (eg, back grinding); etching processing, formation of a sputtered film, plating processing, and plating reflow processing. As well as dicing.

In the step (3), various process solvents are often used, and the process solvents come into contact with the temporary fixing material. In the present invention, by using an adhesive layer containing a cycloolefin polymer (A1) having resistance to the process solvent, the substrate can be treated without being damaged by the process solvent.

  Further, in the photofabrication in the step (3), high temperature processing such as plating reflow processing is often performed, and the temporary fixing material needs to have heat resistance. By using the cycloolefin polymer (A1) excellent in heat resistance as the polymer (A), the temporary fixing material can be treated without being damaged even if the high temperature treatment is performed.

1-4. Step (4)
A schematic diagram of the step (4) is shown in FIG. Step (4) is a step of forming the remaining part 26 of the adhesive layer, the remaining part 27 of the release layer, and the support in this order on the substrate except for a part of the adhesive layer (including the adhesive part 23). The remaining part 27 of the release layer is the remaining part of the release layer after removing the adhesive part 23.

  Examples of a method for removing a part of the adhesive layer including the adhesive portion 23 include a method using a wet process such as a method of dissolving with a solvent; a method using a dry process such as a plasma treatment, an ashing treatment, or an ozone treatment. . Among these, a method using a wet process is preferable because damage to the substrate to be processed can be minimized by selecting the type of solvent.

  Examples of the solvent include hydrocarbons such as limonene, mesitylene, dipentene, pinene, bicyclohexyl, cyclododecene, 1-tert-butyl-3,5-dimethylbenzene, butylcyclohexane, cyclooctane, cycloheptane, cyclohexane, and methylcyclohexane. , Anisole, propylene glycol monomethyl ether, dipropylene glycol methyl ether, diethylene glycol monoethyl ether, diglyme and other alcohols / ethers, ethylene carbonate, ethyl acetate, N-butyl acetate, ethyl lactate, ethyl 3-ethoxypropionate, propylene Glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, esters / lactones such as propylene carbonate and γ-butyrolactone, Ropentanon, cyclohexanone, methyl isobutyl ketone and 2-heptanone, amide / lactam such as N- methyl-2-pyrrolidinone.

Among these, hydrocarbons are preferable in order to suppress damage to the substrate to be processed. Moreover, if the composition for temporary fixing containing a cycloolefin type polymer (A1) is used, since a connection part will contain a cycloolefin type polymer (A1), a cycloolefin type polymer (A1). Hydrocarbons that can be easily dissolved) are preferred.

Examples of the method using a wet process include a method of immersing in a solvent, a method of spraying a solvent, and a method of applying ultrasonic waves while immersing in a solvent. The temperature of the solvent is usually 20 to 80 ° C, preferably 20 to 50 ° C. The immersion time is usually 1 to 180 minutes.

1-5. Process (5)
A schematic diagram of the step (5) is shown in FIG. Step (5) is a step of peeling the processed substrate from the support, and the peeling is usually performed from the remaining portion 27 of the peeling layer. The direction of the force applied at the time of peeling may be any direction as long as the processed substrate 11 is not damaged. For example, the substrate may be peeled from the support by a shearing process (usually 0.1 to 5 N / cm ² ) that shifts the support and the substrate substantially horizontally with respect to the surface of the support, or the support What is necessary is just to peel a base material from a support body by pulling a base material in the direction substantially perpendicular | vertical with respect to the surface of this.

  For example, the base material is slid in the horizontal direction with respect to the surface of the support, and at the same time, the support is fixed, or a force that antagonizes the force applied to the base is added to the support. Is peeled from the support. In the present invention, “shearing” refers to applying a force in a direction substantially parallel to the temporary fixing surface between the support and the substrate.

  In addition, when the release layer lowers the adhesion force by heat or light, the remaining portion 27 of the release layer is peeled after being subjected to heat treatment or exposure treatment, or while being subjected to heat treatment or exposure treatment. May be.

  Since the remaining part of the adhesive layer and the release layer usually remains on the substrate 11 after peeling, it is washed with a solvent (usually, a solvent that can be used when producing the above-described temporary fixing composition), Remove. Examples of the cleaning method include a method of immersing the substrate in the cleaning solution, a method of spraying the cleaning solution on the substrate, and a method of applying ultrasonic waves while immersing the substrate in the cleaning solution. The temperature of the cleaning liquid is not particularly limited, but is preferably 20 to 80 ° C, more preferably 20 to 50 ° C.

The temporary fixing method of the base material of the present invention can form the temporary fixing material without floating between the base material or the support and the temporary fixing material, regardless of the type of the base material. For this reason, it is suitable for various processing required in the scene of modern economic activities (for example, miniaturization processing of various material surfaces, various surface mounting, transportation of semiconductor wafers and semiconductor elements), and the like.

3. Semiconductor device The semiconductor device of the present invention is obtained by the substrate processing method of the present invention. The processing method of the base material of the present invention can form the temporarily fixing material without floating between the base material or the support and the temporarily fixing material, regardless of the type of the base material.
For this reason, in the semiconductor device such as the semiconductor element, the contamination (for example, spots and scorching) due to the temporary fixing material is extremely reduced. In the semiconductor device of the present invention, damage and wear of the base material itself and each member of the base material are extremely reduced.

  Hereinafter, one embodiment of the present invention will be described in detail with reference to examples.

1. Synthesis of Compound (B) [Synthesis Example 1] Synthesis of Compound (B-1) 46.8 g of methacrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-butyl) ester (The following formula (b2-m2-1)) and 4.5 g of 2,2′-azobis- (methyl 2-methylpropionate) were dissolved in 40 g of isopropanol to prepare a monomer solution. 50 g of isopropanol was prepared in a flask substituted with nitrogen, and the monomer solution was added dropwise over 2 hours while heating the inside of the flask to 80 ° C. After dropping, the mixture was further heated at 80 ° C. for 1 hour, and then 10 g of an isopropanol solution containing 3.2 g of vinyl sulfonic acid was dropped over 30 minutes. Then, after heating at 80 degreeC for 1 hour, it cooled and the copolymer liquid was obtained. In the obtained copolymer solution, the solvent was replaced with a 4-methyl-2-pentanol solution to obtain a 4-methyl-2-pentanol solution of the compound (B-1). The weight average molecular weight (Mw) of the compound (B-1) was 10,000. The content ratio of the structural unit derived from the monomer of the following formula (b2-m2-1) by ¹³ CNMR is 98 mol% when the total of all repeating structural units in the compound (B-1) is 100 mol%. there were.

Synthesis Example 2 Synthesis of Compound (B-2) 46.8 g of methacrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-butyl) ester (formula (b2- m2-1)) and 4.5 g of 2,2′-azobis- (methyl 2-methylpropionate) were dissolved in 40 g of isopropanol to prepare a monomer solution in the flask, and the flask was heated at 80 ° C. Heated for 4 hours 30 minutes. Thereafter, the inside of the flask was cooled to 30 ° C. or lower to obtain a copolymer liquid. The obtained copolymer solution was purified with n-hexane and then substituted with a 4-methyl-2-pentanol solution to obtain a 4-methyl-2-pentanol solution of compound (B-2). The weight average molecular weight (Mw) of the compound (B-2) was 10,000.

Mw was measured by GPC under the following conditions.
Apparatus: HLC-8120 (manufactured by Tosoh)
Column: G2000H _XL 2 this, G3000H _XL 1 this, G4000H _XL 1 this (or more, manufactured by Tosoh Corporation)
Elution solvent: Tetrahydrofuran Column temperature: 40 ° C
Flow rate: 1.0 mL / min Standard substance: Monodispersed polystyrene

1. Preparation of Temporary Fixing Composition [Example 1] Preparation of Temporary Fixing Composition 1 100 parts by mass of cycloolefin polymer (trade name “ARTON R5300”, manufactured by JSR Corporation) and 40 parts by mass of hydrogenated In C9 petroleum resin (trade name “Arcon P-140”, manufactured by Arakawa Chemical Industries, Ltd.), 3 parts by weight of product name “TINUVIN 479” (manufactured by BASF), and 7 parts by weight of Synthesis Example 1 A temporary fixing composition 1 was prepared by mixing the obtained compound (B-1), 25 parts by mass of 4-methyl-2-pentanol, and 350 parts by mass of mesitylene.

Example 2 Preparation of Temporary Fixing Composition 2 100 parts by mass of cycloolefin polymer (trade name “ARTON R5300”, manufactured by JSR Corporation) and 40 parts by mass of hydrogenated C9 petroleum resin (trade name) “Alcon P-140” (manufactured by Arakawa Chemical Industries, Ltd.), 3 parts by mass of the trade name “TINUVIN 479” (manufactured by BASF), and 7 parts by mass of the compound obtained in Synthesis Example 2 (B-2) ), 25 parts by mass of 4-methyl-2-pentanol, and 350 parts by mass of mesitylene were prepared to prepare temporary fixing composition 2.

Reference Example 1 Preparation of Composition 1 100 parts by mass of cycloolefin polymer (trade name “ARTON R5300”, manufactured by JSR Corporation) and 40 parts by weight of hydrogenated C9 petroleum resin (trade name “Arcon P” -140 ", manufactured by Arakawa Chemical Industry Co., Ltd.), 3 parts by mass of the trade name" TINUVIN 479 "(manufactured by BASF), and 350 parts by mass of mesitylene were prepared.

[Reference Example 2] Composition 2
Composition 2 was prepared by mixing 100 parts by mass of the compound (B-1) obtained in Synthesis Example 1 and 70 parts by mass of 4-methyl-2-pentanol.

3. Evaluation [Example 3]
The temporary fixing composition 1 prepared in Example 1 was applied on a silicon wafer having a diameter of 8 inches by spin coating, and heated at 160 ° C. for 5 minutes and further at 230 ° C. for 8 minutes using a hot plate, A coating film having a thickness of 40 μm was obtained. The board | substrate which has a coating film was cut | disconnected in the square of 1 cm long and 1 cm wide. Next, a square masking tape having a length of 0.5 cm and a width of 0.5 cm was attached to the center of the surface of the coated film on the cut film of the substrate. The substrate with the masking tape attached was immersed in 4-methyl-2-pentanol (23 ° C.) for 10 seconds, and then the masking tape was peeled off.
Next, the substrate after the masking tape is peeled off and the glass substrate (2 cm long, 2 cm wide, square) are applied with a 5 N force at 180 ° C. for 60 seconds using a die bonder device. Was temporarily fixed via a temporary fixing material. It was confirmed visually that there was no air bubble between the glass substrate and the temporary fixing material. In addition, using a universal bond tester (trade name “Daily 4000”, manufactured by Daisy), a shear force (20 N / cm ² at 23 ° C. at a speed of 500 μm / sec) was applied in a direction parallel to the glass substrate. Since the silicon wafer and the glass substrate were held without displacement, it was confirmed that the silicon wafer and the glass substrate could be temporarily fixed without floating between the base material or the support and the temporary fixing material.
Next, the temporarily fixed base material is immersed in mesitylene (23 ° C.) for 10 minutes, and then the base material after the immersion is used with a universal bond tester (trade name “Daily 4000”, manufactured by Daisy Corporation) When a shear force (5 N / cm ² or less at 23 ° C. at a speed of 500 μm / second) was applied in the parallel direction, the silicon wafer could be peeled from the glass substrate.

[Example 4]
The composition for temporary fixing 2 prepared in Example 2 was applied on a silicon wafer having a diameter of 8 inches by spin coating, and heated at 160 ° C. for 5 minutes and further at 230 ° C. for 8 minutes using a hot plate, A coating film having a thickness of 40 μm was obtained. The board | substrate which has a coating film was cut | disconnected in the square of 1 cm long and 1 cm wide. Next, a square masking tape having a length of 0.5 cm and a width of 0.5 cm was attached to the center of the surface of the coated film on the cut film of the substrate. The substrate with the masking tape attached was immersed in 4-methyl-2-pentanol (23 ° C.) for 10 seconds, and then the masking tape was peeled off.
Next, the substrate after the masking tape is peeled off and the glass substrate (2 cm long, 2 cm wide, square) are applied with a 5 N force at 180 ° C. for 60 seconds using a die bonder device. Was temporarily fixed via a temporary fixing material. It was confirmed visually that there was no air bubble between the glass substrate and the temporary fixing material. In addition, using a universal bond tester (trade name “Daily 4000”, manufactured by Daisy), a shear force (20 N / cm ² at 23 ° C. at a speed of 500 μm / sec) was applied in a direction parallel to the glass substrate. Since the silicon wafer and the glass substrate were held without displacement, it was confirmed that the silicon wafer and the glass substrate could be temporarily fixed without floating between the base material or the support and the temporary fixing material.
Next, the temporarily fixed base material is immersed in mesitylene (23 ° C.) for 10 minutes, and then the base material after the immersion is used with a universal bond tester (trade name “Daily 4000”, manufactured by Daisy Corporation) When a shear force (5 N / cm ² or less at 23 ° C. at a speed of 500 μm / second) was applied in the parallel direction, the silicon wafer could be peeled from the glass substrate.

[Comparative Example 1]
The composition 1 prepared in Reference Example 1 was applied onto a silicon wafer having a diameter of 8 inches by spin coating, heated at 160 ° C. for 5 minutes, and further at 230 ° C. for 8 minutes using a hot plate, and the thickness was 40 μm. The coating film was formed. The obtained substrate was cut into squares having a length of 1 cm and a width of 1 cm to obtain a substrate having a coating film formed from the composition 1.
The composition 2 prepared in Reference Example 2 was applied by spin coating on a glass substrate having a diameter of 0.7 cm and a square masking tape having a width of 0.7 cm and a square mask of 8 inches. The coating was heated for 5 minutes at 5 ° C. to form a 15 μm thick coating film. The masking tape was cut into a square of 2 cm length and 2 cm width so that the masking tape was in the center of the surface of the coating film. After the cut glass substrate is immersed in 4-methyl-2-pentanol (23 ° C.) for 5 minutes, the masking tape is peeled off to have a coating film formed from the composition 2 having a length of 0.7 cm and a width of 0.7 cm. A glass substrate was obtained.
A substrate having a coating film formed from composition 1 and a glass substrate having a coating film formed from composition 2 having a length of 0.7 cm and a width of 0.7 cm are subjected to a force of 5 N at 180 ° C. using a die bonder device. Was added for 60 seconds, and the silicon wafer and the glass substrate were temporarily fixed via a temporary fixing material. Air bubbles were confirmed between the glass substrate and the temporary fixing material.

[Reference Example 3]
The temporary fixing composition 1 prepared in Example 1 was applied on a silicon wafer having a diameter of 8 inches by spin coating, and heated at 160 ° C. for 5 minutes and further at 230 ° C. for 8 minutes using a hot plate, A substrate having a silicon wafer and a coating film having a thickness of 40 μm was obtained. The obtained substrate was cut into squares having a length of 1 cm and a width of 1 cm.
The substrate after cutting and the glass substrate (2 cm long, 2 cm wide, square) are applied with a force of 15 N at 220 ° C. for 120 seconds using a die bonder device, and the silicon wafer and the glass substrate are temporarily fixed composition 1 Was temporarily fixed through a coating film formed from
Next, the temporarily fixed base material was subjected to a force in a direction perpendicular to the glass substrate (14 N / cm ² at 23 ° C. at a speed of 1 mm / second) using an adhesion strength tester (manufactured by Yamamoto Metal Testing Co., Ltd.). As a result, the glass substrate was peeled from the substrate.

[Reference Example 4]
The temporary fixing composition 1 prepared in Example 1 was applied on a silicon wafer having a diameter of 8 inches by spin coating, and heated at 160 ° C. for 5 minutes and further at 230 ° C. for 8 minutes using a hot plate, A substrate having a silicon wafer and a coating film having a thickness of 40 μm was obtained. The obtained substrate was cut into squares having a length of 1 cm and a width of 1 cm. Next, the cut substrate was immersed in 4-methyl-2-pentanol (23 ° C.) for 10 seconds.
A composition 1 for temporarily fixing a silicon wafer and a glass substrate by applying a force of 15 N at 220 ° C. for 120 seconds using a die bonder device on the substrate after immersion and a glass substrate (2 cm long, 2 cm wide, square). Was temporarily fixed through a coating film formed from
Next, the temporarily fixed base material was subjected to force in a direction perpendicular to the glass substrate (20 N / cm ² at 23 ° C. at a speed of 1 mm / sec) using an adhesion strength tester (manufactured by Yamamoto Metal Tester Co., Ltd.). However, it was confirmed that the silicon wafer and the glass substrate were held without displacement.

  From the results of Reference Example 3 and Reference Example 4, it was estimated that the release layer was formed in Example 1 and Example 2, and that the release layer could be removed by 4-methyl-2-pentanol.

Claims (8)

(1) A temporary fixing composition containing the polymer (A) and the compound (B) substantially immiscible with the polymer (A) is used to form an adhesive layer and a release layer on the substrate. Forming in order;
(2) A step of temporarily fixing the base material and the support through the adhesive layer except for a part of the release layer;
(4) A step of forming a remaining part of the adhesive layer, a remaining part of the release layer, and a support in this order on the substrate, excluding a part of the adhesive layer; and (5) peeling the processed substrate from the support. The step of:
A method for temporarily fixing a base material in this order.   The method for temporarily fixing a base material according to claim 1, wherein the polymer (A) is a cycloolefin polymer (A1).   In the step (4), a part of the adhesive layer is removed by dissolving in a hydrocarbon-based solvent, and a remaining part of the adhesive layer, a remaining part of the release layer, and a support are formed in this order on the substrate. The temporary fixing method of the base material according to claim 2. The method for temporarily fixing a substrate according to claim 1, wherein the release layer has a thickness of 1 to 1000 nm. It is a composition for temporary fixation used for the processing method of the base material of Claims 1-4, Comprising: A polymer (A) and the compound (B) substantially immiscible with the said polymer (A) The composition for temporary fixing containing this.   The temporary fixing composition according to claim 5, wherein the polymer (A) is a cycloolefin polymer (A1).   The composition containing 1-30 mass parts of polymers (B1) which have 100 mass parts of cycloolefin type polymers (A1), and the repeating unit which has a fluorine atom.   A semiconductor device obtained by using the method for temporarily fixing a substrate according to claim 1.