JP2011052051A - Adhesive composition, method for processing or moving substrate using the same, and semiconductor element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition that has sufficient adhesion when processing or moving a substrate, enables easy detachment of the substrate from a base after processing or moving, and is easily removed even when adhered to the substrate. <P>SOLUTION: The adhesive composition contains: (A) at least one compound selected from a camphor compound and a crosslinking cyclic hydrocarbon structure analogous to camphor; (B) a compound having two or more groups with a lone electron pair; and (C) a solvent. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an adhesive composition used for fixing a base material to a support when the base material is processed or moved, a base material processing or moving method using the same, and a semiconductor element. More specifically, it has sufficient adhesiveness even at the process temperature in the processing or movement, and the substrate can be easily peeled off from the support after the processing or movement is completed, and even if it adheres to the substrate. The present invention relates to an adhesive composition to be removed, a method of processing or moving a substrate using the same, and a semiconductor device obtained by the processing method.

  When processing a substrate such as a semiconductor wafer (eg, dicing, back grinding) or moving (eg, moving a substrate from one device to another), make sure that the substrate does not move from the support. It is necessary to temporarily fix the base material and the support using a fastening adhesive. And after a process or movement completion | finish, it is necessary to peel a base material from a support body. Conventionally, several temporarily fix | bonded adhesives used for the temporary fixing of a base material are proposed (refer the following patent documents 1-5).

  Patent Document 1: A copolymer of acrylic acid, hydroxyalkyl acrylate, aminoalkyl methacrylate, and alkyl amide of acrylic acid is a main component, and the acid group of the copolymer is neutralized by 80% or more by an inorganic or organic base. Warm water washable liquid adhesive.

  Patent Document 2: A hot water detergency liquid adhesive mainly composed of a block polymer in which a main chain of polyethylene glycol obtained by polymerization of ethylene oxide is a hydrophilic group and partially added and polymerized with propylene oxide as a lipophilic group at both ends thereof.

  Patent Document 3: Adhesive composition containing urethane (meth) acrylate, (meth) acrylic acid derivative monomer, and photopolymerization initiator.

  Patent Document 4: Hot-melt adhesive composition containing a crystalline compound as a main component.

  Patent Document 5: An adhesive containing an ionomer resin in an amount of 40% by weight or less.

  However, in the temporary fixing adhesive of the above-mentioned patent document, it is necessary to wash the base material using a solvent in order to cleanly remove the temporary fixing adhesive from the base material after peeling the base material from the support. For this reason, there are many problems in process management.

JP 7-33212 A JP-A-6-240224 Japanese Patent Laid-Open No. 2006-257312 JP 2005-179654 A Special table 2007-525574

The present invention has sufficient adhesiveness during processing and movement of the substrate, and can be easily peeled off from the support after completion of processing and movement, and easily removed even if attached to the substrate. It is an object of the present invention to provide an adhesive composition. In particular, a conventionally known temporary fixing adhesive has been removed with a solvent or the like after completion of processing or movement of a substrate, but an object is to provide an adhesive composition that does not require cleaning with a solvent. Moreover, this invention makes it a subject to provide the semiconductor element obtained by the processing or moving method of the base material using the said adhesive composition, and the processing method of this base material.

  The present inventors have intensively studied to solve the above problems. As a result, by using a specific compound (A), a compound (B) having two or more groups having a lone electron pair, and a solvent (C), an adhesive composition capable of solving the above problems is provided. The present inventors have found that this can be done and have completed the present invention.

  That is, the present invention and preferred embodiments thereof relate to the following [1] to [14].

  [1] An adhesive composition containing (A) a compound represented by the following formula (1), (B) a compound having two or more groups having a lone pair, and (C) a solvent.

[In Formula (1), a and b represent 0 or 1 each independently, and c and d represent the integer of 0-2 each independently. R ^{1 to} R ²⁰ are each independently a hydrogen atom; a halogen atom; a hydrocarbon group having 1 to 30 carbon atoms; a group represented by —X—R ²¹ (wherein X is an oxygen atom, a sulfur atom, a nitrogen atom, and Represents a linking group having one or more atoms selected from silicon atoms, and R ²¹ represents a hydrocarbon group having 1 to 30 carbon atoms); or represents another polar group. However, at least one selected from R ¹ and R ² , R ³ and R ⁴ , R ¹⁷ and R ¹⁸ , and R ¹⁹ and R ²⁰ may be integrated to form a divalent hydrocarbon group, At least one selected from R ¹ and R ² , R ³ and R ⁴ , R ¹⁷ and R ¹⁸ , and R ¹⁹ and R ²⁰ may be combined to form a ketone group, R ¹ and R ² , At least one selected from R ³ and R ⁴ , R ¹⁷ and R ¹⁸ , and R ¹⁹ and R ²⁰ may be bonded to each other to form a carbocyclic or heterocyclic ring. At least one set selected from R ¹ and R ³ and R ¹⁸ and R ¹⁹ may be directly bonded to each other to form a double bond. ]
[2] The adhesive composition according to [1], wherein the group having a lone electron pair is at least one selected from groups represented by the following formulas (2) to (5).

[In formulas (2) to (5), “-*” and “= *” represent a bond.

However, the bond between a nitrogen atom and a hydrogen atom is excluded. ]
[3] The component (A) is a combination of at least one selected from R ¹ and R ² , R ³ and R ⁴ , R ¹⁷ and R ¹⁸ , and R ¹⁹ and R ²⁰ in the formula (1). The adhesive composition according to [1] or [2], which is a compound having a ketone group formed thereon.

  [4] The adhesive composition according to any one of [1] to [3], wherein the component (A) is a compound in which c and d in the formula (1) are both 0.

  [5] The adhesive composition according to [2], wherein the component (B) is a compound having at least a group represented by the formula (2).

  [6] The adhesive composition according to [2], wherein the component (B) is a compound having two groups represented by the formula (2).

  [7] The adhesive composition according to any one of [1] to [6], wherein the component (A) has a boiling point or sublimation point at 1 atm of 300 ° C. or lower.

  [8] The adhesive composition according to any one of [1] to [7], wherein the component (B) has a boiling point or sublimation point at 1 atm of 300 ° C. or lower.

  [9] The adhesive composition according to any one of [1] to [8], wherein the viscosity of the component (C) at 23 ° C. is 100 to 1,000,000 mPa · s.

  [10] (1) A step of fixing the base material using an adhesive on the support, (2) a step of processing or moving the base material, and (3) a step of peeling the base material from the support. A method of processing or moving a substrate sequentially, wherein the adhesive composition according to any one of [1] to [9] is used as the adhesive, and the adhesive in the step (3) A processing or moving method of a substrate, which removes the substrate from the support by removing the substrate by heat treatment.

  [11] The substrate processing or moving method according to [10], wherein the heat treatment is performed at 40 to 400 ° C. in the step (3).

  [12] In the step (2), the substrate is processed by at least one method selected from thinning of the substrate, etching, formation of a sputtered film, plating treatment, and dicing [10] or [11 ] The processing method of the base material as described in above.

  [13] A semiconductor element obtained using the adhesive composition according to any one of [1] to [9].

  [14] A semiconductor element obtained by the substrate processing method according to any one of [10] to [12].

  According to the present invention, the substrate has sufficient adhesiveness during processing and movement of the substrate, can be easily peeled off from the support after the completion of processing and movement, and even if attached to the substrate. An adhesive composition to be removed is provided. In particular, conventionally known temporary fixing adhesives have been removed with a solvent or the like after completion of processing or movement of the substrate, but an adhesive composition that does not require cleaning with a solvent is provided. Moreover, according to this invention, the semiconductor element obtained by the processing or moving method of the base material using the said adhesive composition, and the processing method of this base material is provided.

  Hereinafter, the adhesive composition of the present invention, a method for processing or moving a substrate using the adhesive composition, and a semiconductor element obtained by the method for processing the substrate will be described in detail.

[Adhesive composition]
The adhesive composition of the present invention contains (A) a compound represented by the formula (1) described later, (B) a compound having two or more groups having a lone pair, and (C) a solvent. . Below, each said component is also called a compound (A), a compound (B), and a solvent (C), respectively.

  The reason why the adhesive composition of the present invention has sufficient adhesiveness during processing and movement of the substrate (working object) is that the compound (B) is a group having a lone electron pair, that is, a group having high nucleophilicity. ”, The compound (A) and the compound (B) interact with each other as in“ Compound (A) -Compound (B) -Compound (A)... -Compound (A) ”. It is presumed that it may function as an adhesive. In particular, when the compound (A) has an electron-withdrawing group such as a ketone group, the electron-withdrawing group and the group having a lone electron pair (group having high nucleophilicity) in the compound (B) are more strongly interacted with each other. Since it acts, the adhesiveness is further improved.

  In addition, the adhesive composition of the present invention is preferably vaporized or sublimated by heat to become a gas. In the case of such an adhesive composition, the substrate can be easily peeled off from the support by low-temperature heat treatment after the processing or movement is completed, and the adhesive composition adhering to the substrate can also be easily removed. There are advantages. In order to obtain an adhesive composition having such characteristics, a low molecular weight compound (A) or compound (B) that can be vaporized or sublimated by heat may be used.

<< Compound (A) >>
The compound (A) is a compound represented by the following formula (1).

[In formula (1), a and b each independently represent 0 or 1, c and d each independently represent an integer of 0 to 2, and c and d are preferably all 0. R ^{1 to} R ²⁰ are each independently a hydrogen atom; a halogen atom; a hydrocarbon group having 1 to 30 carbon atoms; a group represented by —X—R ²¹ (wherein X is an oxygen atom, a sulfur atom, a nitrogen atom, and Represents a linking group having one or more atoms selected from silicon atoms, and R ²¹ represents a hydrocarbon group having 1 to 30 carbon atoms); or represents another polar group. However, at least one selected from R ¹ and R ² , R ³ and R ⁴ , R ¹⁷ and R ¹⁸ , and R ¹⁹ and R ²⁰ may be integrated to form a divalent hydrocarbon group, At least one selected from R ¹ and R ² , R ³ and R ⁴ , R ¹⁷ and R ¹⁸ , and R ¹⁹ and R ²⁰ may be combined to form a ketone group, R ¹ and R ² , At least one selected from R ³ and R ⁴ , R ¹⁷ and R ¹⁸ , and R ¹⁹ and R ²⁰ may be bonded to each other to form a carbocyclic or heterocyclic ring. At least one set selected from R ¹ and R ³ and R ¹⁸ and R ¹⁹ may be directly bonded to each other to form a double bond. ]
Hereinafter, the detail of Formula (1) is demonstrated.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the hydrocarbon group having 1 to 30 carbon atoms include alkyl groups such as methyl group, ethyl group and propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group and allyl group; phenyl group and naphthyl group And aromatic groups such as anthracenyl group. The hydrocarbon group has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

Examples of the linking group include an ether bond (—O—), a carbonyl group (—CO—), a carbonyloxy group (—COO—), a thioether bond (—S—), and a sulfonyl group (—SO ₂ —).
Sulfonyl ester group (—SO ₂ —O—), imino group (—NH—), amide bond (—NHCO—), siloxane bond (—Si (R ²² ) ₂ O—; wherein R ²² is an alkyl group A group having two or more of these; a group in which these groups are bonded to a divalent hydrocarbon group having 1 to 10 carbon atoms (eg, a methylene group or an alkylene group having 2 to 10 carbon atoms), etc. Is mentioned.

As the group represented by the above -XR ²¹ , specifically,
Alkoxy group: methoxy group, ethoxy group, acyl group: acetyl group, propionyl group, alkoxycarbonyl group: methoxycarbonyl group, ethoxycarbonyl group, aryloxycarbonyl group: phenoxycarbonyl group, naphthyloxycarbonyl group, fluorenyloxycarbonyl Group, biphenylyloxycarbonyl group / acyloxy group: alkylcarbonyloxy group such as acetoxy group and propionyloxy group, and arylcarbonyloxy group such as benzoyloxy group.

  Other polar groups include hydroxy group, cyano group, amide group, imide group, carboxyl group, amino group (eg, primary amino group), triorganosiloxy group (eg: trimethylsiloxy group, triethylsiloxy group), Examples include triorganosilyl groups (example: trimethylsilyl group, triethylsilyl group), alkoxysilyl groups (example: trimethoxysilyl group, triethoxysilyl group) and the like.

At least one selected from R ¹ and R ² , R ³ and R ⁴ , R ¹⁷ and R ¹⁸ , and R ¹⁹ and R ²⁰ may be integrated to form a divalent hydrocarbon group. As a bivalent hydrocarbon group, a C1-C20 alkylidene group is mentioned. “Integrate to form a divalent hydrocarbon group” means that, for example, in the case of a combination of R ¹ and R ² , the following structure is formed (only the main part is shown).

Wherein, R 'represents a divalent hydrocarbon group, R ³ to R ⁸ have the same meanings as R ³ to R ⁸ in the formula (1).

It is preferable that at least one selected from R ¹ and R ² , R ³ and R ⁴ , R ¹⁷ and R ¹⁸ , and R ¹⁹ and R ²⁰ are combined to form a ketone group, R ¹ and R ² , More preferably, one set selected from R ³ and R ⁴ , R ¹⁷ and R ¹⁸ , and R ¹⁹ and R ²⁰ is integrated to form a ketone group. “Integrate to form a ketone group” means that, for example, in the case of a pair of R ¹ and R ² , the above structure (here, R ′ is O) is formed. In such a case, R < ¹ > -R < ²⁰ > other than the group which formed the ketone group represents a hydrogen atom or the said C1-C30 hydrocarbon group each independently, for example.

At least one set selected from R ¹ and R ² , R ³ and R ⁴ , R ¹⁷ and R ¹⁸ , and R ¹⁹ and R ²⁰ is bonded to each other to form a carbocyclic or heterocyclic ring (these carbocyclic or heterocyclic rings). May be a monocyclic structure or a polycyclic structure. The carbocycle or heterocycle may be an aromatic ring or a non-aromatic ring.

At least one set selected from R ¹ and R ³ and R ¹⁸ and R ¹⁹ may be directly bonded to each other to form a double bond. “Directly bonding to each other to form a double bond” means that, for example, in the case of a set of R ¹ and R ³ , the following structure is formed (only the main part is shown).

Wherein, R ² and R ⁴ to R ⁸ has the same meaning as R ² and R ⁴ to R ⁸ in the formula (1).

Specific examples of the compound (A) include the following compounds.
Bicyclo [2.2.1] heptane (norbornene)
2-methyl-bicyclo [2.2.1] heptane, 2-ethyl-bicyclo [2.2.1] heptane, 2-propyl-bicyclo [2.2.1] heptane, 2-butyl-bicyclo [2 2.1] heptane, 2-tert-butyl-bicyclo [2.2.1] heptane, 2-isobutyl-bicyclo [2.2.1] heptane, 2-pentyl-bicyclo [2.2.1] heptane 2-hexyl-bicyclo [2.2.1] heptane, 2-heptyl-bicyclo [2.2.1] heptane, 2-octyl-bicyclo [2.2.1] heptane, 2-nonyl-bicyclo [2 2.1] heptane, 2-decyl-bicyclo [2.2.1] heptane, 2-dodecyl-bicyclo [2.2.1] heptane, 2,2-dimethyl-bicyclo [2.2.1] heptane・ 2,3-Dimethyl-Bishi Black [2.2.1] heptane, 2-cyclohexyl-bicyclo [2.2.1] heptane, 2-phenyl-bicyclo [2.2.1] heptane, 2- (4-biphenyl) -bicyclo [2. 2.1] Heptane, 2-methoxycarbonyl-bicyclo [2.2.1] heptane, 2-phenoxycarbonyl-bicyclo [2.2.1] heptane, 2-phenoxyethylcarbonyl-bicyclo [2.2.1] Heptane 2-phenylcarbonyloxy-bicyclo [2.2.1] heptane

2-methyl-2-methoxycarbonyl-bicyclo [2.2.1] heptane, 2-methyl-2-phenoxycarbonyl-bicyclo [2.2.1] heptane, 2-methyl-2-phenoxyethylcarbonyl-bicyclo [2.2.1] Heptane, 2-vinyl-bicyclo [2.2.1] heptane, 2-ethylidene-bicyclo [2.2.1] heptane, 2-trimethoxysilyl-bicyclo [2.2.1] ] Heptane, 2-triethoxysilyl-bicyclo [2.2.1] heptane, 2-fluoro-bicyclo [2.2.1] heptane, 2-chloro-bicyclo [2.2.1] heptane, 2-bromo -Bicyclo [2.2.1] heptane-2,3-difluoro-bicyclo [2.2.1] heptane-2,3-dichloro-bicyclo [2.2.1] heptane-2,3-di Lomo-bicyclo [2.2.1] heptane, 2-hydroxy-bicyclo [2.2.1] heptane, 2-hydroxyethyl-bicyclo [2.2.1] heptane, 2-cyano-bicyclo [2.2 .1] Heptane, 2-amino-bicyclo [2.2.1] heptane, 1,7,7-trimethylbicyclo [2.2.1] heptan-2-one, tricyclo [4.3.0.1 ^{2 , 5} ] decane tricyclo [4.4.0.1 ^2,5 ] undecane 7-methyl-tricyclo [4.3.0.1 ^2,5 ] decane-7-ethyl-tricyclo [4.3.0 .1, ^2,5 ] decane, 7-cyclohexyl-tricyclo [4.3.0.1 ^2,5 ] decane, 7-phenyl-tricyclo [4.3.0.1 ^2,5 ] decane

7- (4-biphenyl) -tricyclo [4.3.0.1 ^2,5 ] decane 7,8-dimethyl-tricyclo [4.3.0.1 ^2,5 ] decane7,8,9 -Trimethyl-tricyclo [4.3.0.1 ^2,5 ] decane, 8-methyl-tricyclo [4.4.0.1 ^2,5 ] undecane, 8-phenyl-tricyclo [4.4.0.1 ^2,5 ] undecane, 7-fluoro-tricyclo [4.3.0.1 ^2,5 ] decane, 7-chloro-tricyclo [4.3.0.1 ^2,5 ] decane, 7-bromo-tricyclo [ 4.3.0.1 ^2,5 ] decane 7,8-dichloro-tricyclo [4.3.0.1 ^2,5 ] decane 7,8,9-trichloro-tricyclo [4.3.0. 1 ^2,5 ] decane-7-chloromethyl-tricyclo [4.3.0.1 ^2,5 ] decane-7-dichloromethyl-tricyclo [4 .3.0.1 ^2,5 ] decane, 7-trichloromethyl-tricyclo [4.3.0.1 ^2,5 ] decane, 7-hydroxy-tricyclo [4.3.0.1 ^2,5 ] decane 7-cyano-tricyclo [4.3.0.1 ^2,5 ] decane 7-amino-tricyclo [4.3.0.1 ^2,5 ] decane tetracyclo [4.4.0.1 ^{2, 5} . 1 ^7,10 ] dodecane pentacyclo [7.4.0.1 ^3,6 . 1 ^10,13 . 0 ^2,7 ] pentadecane hexacyclo [8.4.0.1 ^2,9 . 1 ^4,7 . 1 ^11,14 . 0 ^1,10 ] heptadecane-8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodecane-8-ethyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodecane-8-cyclohexyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodecane-8-phenyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodecane-8- (4-biphenyl) - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodecane-8-methoxycarbonyloxy - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodecane-8-phenoxycarbonyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodecane-8-phenoxyethyl carbonyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] Dodecane

8-phenylcarbonyloxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodecane-8-methyl-8-methoxycarbonyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ]
Dodecane-8-methyl-8-phenoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] Dodecane-8-methyl-8-phenoxyethylcarbonyl-tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10] dodecane-8-vinyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodecane-8-ethylidene - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodecane 8,8-dimethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane 8,9-dimethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane-8-fluoro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodecane-8-chloro - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodecane-8-bromo - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodecane 8,8-dichloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane 8,9-dichloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane 8,8,9,9-tetrachloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane 8-hydroxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane 8-hydroxyethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodecane-8-methyl-8-hydroxyethyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodecane-8-cyano - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodecane-8-amino - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodecane Among these, a compound having an electron-withdrawing group is preferable, and a compound having a ketone group is more preferable in that an adhesive composition excellent in adhesiveness can be obtained.

  The boiling point or sublimation point at 1 atm of the compound (A) is preferably 300 ° C. or less, and more preferably 100 to 300 ° C. When the compound (A) having a boiling point or sublimation point in the above range is used, the compound (A) is easily vaporized or sublimated without damaging the substrate when removing the adhesive composition. Thus, an excellent adhesive composition can be obtained.

  A compound (A) may be used individually by 1 type, and may use 2 or more types together.

  In the adhesive composition of the present invention, the compound (A) is usually contained in the range of 5 to 40% by weight, preferably 10 to 30% by weight. When content of a compound (A) exists in the said range, it is excellent at the point of adhesiveness.

<< Compound (B) >>
The compound (B) is a compound having two or more groups having a lone electron pair (excluding the compound represented by the above formula (1)). The “group having a lone electron pair” is a group having high nucleophilicity and a group that interacts with an electrophile.

  Examples of the compound having a highly nucleophilic group include various carbanions, amines and their conjugate bases (eg, amides), amidines and their derivatives, alcohols and their conjugate bases (eg, alkoxides), and halide ions. It is done.

  The compound (B) is a compound having two or more groups having a lone pair of electrons. However, since the adhesive composition having a higher adhesive property can be obtained by strongly interacting with the compound (A), the lone electrons A compound having 2 to 3 groups having a pair is preferable.

  Since the group having the lone electron pair strongly interacts with the compound (A) to obtain an adhesive composition having more excellent adhesiveness, the group represented by the following formulas (2) to (5) is used. Particularly preferred is at least one selected. That is, the compound (B) is particularly preferably a compound having two or more groups selected from the groups represented by the following formulas (2) to (5). “Having two or more” means that, for example, the compound (B) may have two or more groups represented by the formula (2), or a group represented by the formula (2) and the formula (3 ) Group may be included one by one.

In formulas (2) to (5), “− *” and “= *” represent a bond. However, the bond between a nitrogen atom and a hydrogen atom is excluded. Moreover, the compound represented by the said Formula (1) is remove | excluded among the compounds which have 2 or more types of 1 type or 2 or more types selected from group represented by Formula (2)-(5).

  As the compound (B), 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1,5-diazabicyclo [4.3.0] Non-5-ene (DBN), ethylenediamine and the like.

  The compound (B) is preferably a compound having at least a group represented by the above formula (2), and more preferably a compound having two groups represented by the above formula (2). Examples of the compound having two groups represented by the above formula (2) include 1,4-diazabicyclo [2.2.2] octane.

  The boiling point or sublimation point at 1 atm of the compound (B) is preferably 300 ° C. or less, and more preferably 100 to 300 ° C. The vapor pressure at 1 atm and 23 ° C. of the compound (B) is preferably a low pressure of 1 hPa or less. When the compound (B) having such physical properties is used, the compound (B) is vaporized or sublimated when the adhesive composition is removed, so that an adhesive composition having excellent removability can be obtained.

  A compound (B) may be used individually by 1 type, and may use 2 or more types together.

  In the adhesive composition of the present invention, the compound (B) is usually 100 to 1000 parts by weight, preferably 150 to 500 parts by weight, more preferably 200 to 300 parts by weight with respect to 100 parts by weight of the compound (A). Included in the range. When content of a compound (B) exists in the said range, interaction with a compound (B) and a compound (A) will become strong, and the effect more excellent in the point of adhesiveness will be exhibited.

<< Solvent (C) >>
A conventionally well-known solvent can be used as a solvent (C).

Specific examples of the solvent (C) include alcohols such as methanol, ethanol, isopropanol, butanol, hexanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin and phenol;
n-pentane, cyclopentane, n-hexane, cyclohexane, n-heptane, cycloheptane, n-octane, cyclooctane, n-decane, cyclodecane, dicyclopentadiene hydride, benzene, toluene, xylene, durene, indene, decalin Hydrocarbon solvents such as tetralin, tetrahydronaphthalene, decahydronaphthalene, squalane, ethylbenzene, t-butylbenzene, trimethylbenzene;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone;
Ethers such as ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and dioxane;
Ethyl acetate, butyl acetate, ethyl butyrate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoacetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate , Esters such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate;
Examples include polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, hexamethylphosphomide, dimethyl sulfoxide, γ-butyrolactone, chloroform, and methylene chloride.

  Among these, protic solvents such as alcohols, ketones, and ethers are preferable, and glycerin, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, and tetrahydrofuran are more preferable.

  The viscosity of the solvent (C) at 23 ° C. is usually 100 to 1,000,000 mPa · s. When the solvent (C) having a viscosity in the above range is used, an adhesive composition having better adhesiveness can be obtained.

  A solvent (C) may be used individually by 1 type, and may use 2 or more types together.

  In the adhesive composition of the present invention, the solvent (C) is usually 10 to 300 parts by weight, preferably 20 to 200 parts by weight with respect to 100 parts by weight of the total amount of the compound (A) and the compound (B). More preferably, it is contained in the range of 30 to 100 parts by weight.

"Additive"
The adhesive composition of the present invention may further contain an additive as long as the object of the present invention is not impaired. Examples of the additive include surface tension regulators such as nonionic surfactants; metal oxides such as aluminum oxide, zirconium oxide, titanium oxide, and silicon oxide; polystyrene cross-linked particles.

<< Adhesive composition >>
The adhesive composition of the present invention can be prepared according to a conventionally known method.

The adhesive composition of the present invention has sufficient adhesiveness during processing or movement of the substrate. Specifically, the shear peel strength at 23 ° C. of the adhesive composition of the present invention is usually 1 g / cm ^2.
As mentioned above, Preferably it is 5-10,000 g / cm < ² >. The shear peel strength is measured under the conditions described in the examples described later.

  In addition, since the components are vaporized or sublimated by heat, the base material can be easily peeled off from the support by heating after completion of processing or movement, and the adhesive composition adhering to the base material can be removed. (Ie, no washing with a solvent is required).

  In addition, the adhesive composition of the present invention has the above-mentioned characteristics, fluidity under the bonding conditions of the substrate, heat resistance during the formation of the insulating film and reflow, and solvent resistance against the solvent used during the formation and removal of the resist Property, Cu plating resistance, and vacuum resistance during sputtering. Moreover, the adhesive bond layer which consists of an adhesive composition of this invention is excellent in intensity | strength.

  Because of these characteristics, the adhesive composition of the present invention can be used in various processing processes required in the context of modern economic activities (eg, ultra-thin grinding of semiconductor wafers, miniaturization of various material surfaces). It is suitable as an adhesive for temporarily fixing the base material during processing, transportation of semiconductor wafers and semiconductor elements).

[Processing or moving substrate]
The substrate processing or moving method of the present invention includes (1) a step of fixing the substrate on the support using an adhesive, (2) a step of processing or moving the substrate, and (3) a support. A method of processing or moving a substrate, which sequentially performs a step of peeling the substrate from the substrate, using the above-mentioned adhesive composition as the adhesive, and removing the adhesive by heat treatment in the step (3) By doing so, the substrate is peeled from the support. Hereinafter, the respective steps are also referred to as a step (1), a step (2), and a step (3), respectively.

<< Process (1) >>
In the step (1), the base material is fixed to the support by applying the adhesive composition to the surface of the support or the surface-treated base as necessary, and bonding the base and the support together. Can do. Examples of the base material that is an object to be processed (moved) include a semiconductor wafer, a glass substrate, a resin substrate, a metal substrate, a metal foil, and a polishing pad. In general, wirings, insulating films, and the like are formed on a semiconductor wafer.

  When applying the adhesive composition of the present invention to a base material, it is preferable to hydrophobize the surface of the base material in advance in order to make the adhesive composition spread in the plane.

  Examples of the hydrophobic treatment method include a method of applying a surface treatment agent to the surface of the substrate in advance. Examples of the surface treatment agent include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3- Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxy Silane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triaza Can, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl- 3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) ) -3-Aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, and hexamethyldisilazane.

  As a method for applying the above-mentioned adhesive composition, (a) a method in which the adhesive composition is directly applied to a substrate, (b) a PET (Polyethylene Terephthalate) film that has been subjected to a release treatment. Examples of the method include a method in which a film is formed by applying a constant film thickness thereon and then transferring to a base material by a laminate method.

  The coating amount of the above-mentioned adhesive composition can be arbitrarily selected according to the size of the adhesive surface of the substrate, the degree of adhesion required for processing, etc., but the thickness of the adhesive layer is usually The coating amount may be 0.01 μm to 2 mm, preferably 0.05 μm to 1 mm, more preferably 0.1 μm to 0.5 mm. When the thickness of the adhesive layer is out of the above range, the adhesive force may not be sufficient, and the substrate may peel off from the adhesive surface. In addition, the thickness of an adhesive bond layer can be adjusted with the application amount of an adhesive agent, and the pressure at the time of bonding.

  Examples of the method for bonding the base material and the support include a method of applying the above-described adhesive composition to one or both of the base material and the support and bonding them together. The temperature at this time is usually 23 to 200 ° C. In this way, the substrate and the support are firmly bonded.

<< Step (2) >>
Step (2) is a step of processing or moving the base material fixed to the support as described above. A moving process is a process of moving a base material (example: semiconductor element) with a support body from one apparatus to another apparatus. Further, the processing of the base material fixed to the support as described above is at least one selected from thinning of the base material (such as back surface grinding), etching processing, formation of a sputtered film, plating processing, and dicing. Various methods can be used.

  The processing of the substrate is not particularly limited as long as it is performed at a temperature at which the adhesive composition does not vaporize or sublimate and does not lose adhesiveness, and is usually below the boiling point or sublimation point temperature of the components contained in the composition. Just do it. However, the heating condition of the step (2) may be the same as the heating condition of the step (3), that is, the step (3) may be completed simultaneously with the end of the step (2).

  Hereinafter, as a base material processing process, a processing process performed when three-dimensionally mounting a semiconductor wafer will be described as an example. In the three-dimensional mounting, a through electrode extending in a direction perpendicular to the surface of the semiconductor wafer is formed, and a connection electrode such as a pad electrode or a bump is formed on an end portion or wiring of the through electrode. By connecting the connection electrodes formed in this way, the stacked semiconductor wafers are connected to each other.

  (I) Grinding a base material made of a semiconductor wafer fixed on a support through an adhesive composition in step (1).

  (Ii) A resist is applied on the substrate, and an exposure process and a development process are performed to form a resist layer patterned into a predetermined shape. For example, a plurality of circular resist patterns may be formed on the substrate.

(Iii) Using the resist layer as a mask, a portion of the base material patterned into a predetermined shape is etched to form an opening (hole). Thereafter, the resist layer is stripped by a stripping solution or ashing (eg, O ₂ ashing). As the etching, dry etching or wet etching can be used, but it is preferable to use dry etching. Examples of dry etching include reactive ion etching (RIE).

(Iv) An insulating layer made of SiO ₂ or the like is formed on the surface of the substrate where the opening is formed.

  (V) A barrier layer made of TiW, TiN or the like is formed by sputtering for the purpose of preventing the conductor from diffusing into the insulating layer. Next, a seed layer made of copper or the like is formed by sputtering.

(Vi) A resist is applied on the surface of the base material on which the opening is formed, and an exposure process and a development process are performed to form a resist layer patterned in a shape corresponding to the opening of the base material. Next, a plating process (Sn / Cu plating or the like) is performed to fill the opening in the base material with a conductor to form a through electrode. Thereafter, the resist layer is removed, and the barrier layer and the seed layer are removed by dry etching.

(Vii) A connection electrode such as a pad electrode or a bump is formed on the through electrode of the substrate thus processed. Next, the stacked semiconductor wafers can be connected by connecting the formed connection electrodes.

<< Process 3 >>
After processing or moving the substrate, the substrate is peeled from the support by removing the adhesive by heat treatment. The heat treatment may be performed at the highest boiling point or sublimation point temperature among the components of the adhesive composition, for example, at 40 to 400 ° C. Step (3) may be performed under the heating conditions in step (2), that is, step (3) may be completed simultaneously with the end of step (2).

[Semiconductor element]
The semiconductor element of the present invention is obtained using the above-described adhesive composition, and specifically, obtained by the above-described substrate processing method. Since the above-mentioned adhesive composition is easily removed when the semiconductor element is peeled off, the semiconductor element is greatly reduced in contamination (eg, stains and scorching) due to the adhesive composition.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples at all. In the following examples, unless otherwise specified, “parts” and “%” are used to mean “parts by weight” and “% by weight”, respectively.

Example 1 Preparation of Adhesive Composition (A1) 4 parts of 1,7,7-trimethylbicyclo [2.2.1] heptan-2-one (camphor) and (B1) 1,4-diazabicyclo [2 2.2] 9 parts of octane were dissolved in 7 parts of (C1) glycerin to obtain an adhesive composition.

Boiling point at 1 atm of (A1): 208 ° C.
Boiling point at 1 atm of (B1): 174 ° C.
Viscosity of (C1) at 23 ° C .: 1,500 mPa · s (measured with a rotational viscometer)
[Evaluation of adhesion (1)]
The adhesive composition prepared in Example 1 was applied on a silicon wafer cut to 10 mm × 10 mm at room temperature and normal pressure to form an adhesive layer having a thickness of 20 μm. A silicon wafer cut to 20 mm × 20 mm was stacked on the adhesive layer, and a weight of 500 g was applied to obtain an adhesive substrate.

The shear peel strength of the obtained adhesive substrate was measured using a universal bond tester (manufactured by Daisy). The shear peel strength at 23 ° C. was 15 g / cm ² , and even when the adhesive substrate was tilted at 90 ° and 180 °, no deviation occurred between the two silicon wafers. For this reason, it has confirmed that the adhesive composition prepared in Example 1 had sufficient adhesiveness as a temporary fixative.

[Evaluation of peelability (2)]
The adhesive substrate was placed on a hot plate and heated at 260 ° C. corresponding to the solder melting temperature in a nitrogen atmosphere. As a result, the two silicon wafers could be easily separated. Moreover, when the presence or absence of the adhesive layer on the surface of the silicon wafer after separation was visually evaluated, there were no spots or burns. For this reason, it has also been confirmed that the adhesive composition, which is a temporary fixing agent, can be easily removed by heating without contaminating the silicon wafer.

Claims (14)

(A) a compound represented by the following formula (1);
(B) a compound having two or more groups having a lone pair of electrons;
(C) An adhesive composition containing a solvent.

[In Formula (1), a and b represent 0 or 1 each independently, and c and d represent the integer of 0-2 each independently. R ^{1 to} R ²⁰ are each independently a hydrogen atom; a halogen atom; a hydrocarbon group having 1 to 30 carbon atoms; a group represented by —X—R ²¹ (wherein X is an oxygen atom, a sulfur atom, a nitrogen atom, and Represents a linking group having one or more atoms selected from silicon atoms, and R ²¹ represents a hydrocarbon group having 1 to 30 carbon atoms); or represents another polar group. However, at least one selected from R ¹ and R ² , R ³ and R ⁴ , R ¹⁷ and R ¹⁸ , and R ¹⁹ and R ²⁰ may be integrated to form a divalent hydrocarbon group, At least one selected from R ¹ and R ² , R ³ and R ⁴ , R ¹⁷ and R ¹⁸ , and R ¹⁹ and R ²⁰ may be combined to form a ketone group, R ¹ and R ² , At least one selected from R ³ and R ⁴ , R ¹⁷ and R ¹⁸ , and R ¹⁹ and R ²⁰ may be bonded to each other to form a carbocyclic or heterocyclic ring. At least one set selected from R ¹ and R ³ and R ¹⁸ and R ¹⁹ may be directly bonded to each other to form a double bond. ] The adhesive composition according to claim 1, wherein the group having a lone electron pair is at least one selected from groups represented by the following formulas (2) to (5).

[In formulas (2) to (5), “-*” and “= *” represent a bond.
However, the bond between a nitrogen atom and a hydrogen atom is excluded. ] The component (A) is a ketone group formed by integrating at least one selected from R ¹ and R ² , R ³ and R ⁴ , R ¹⁷ and R ¹⁸ , and R ¹⁹ and R ²⁰ in the formula (1). The adhesive composition according to claim 1, wherein the adhesive composition is a compound that has formed the above.   The adhesive composition according to any one of claims 1 to 3, wherein the component (A) is a compound in which c and d in the formula (1) are both 0.   The adhesive composition according to claim 2, wherein the component (B) is a compound having at least a group represented by the formula (2).   The adhesive composition according to claim 2, wherein the component (B) is a compound having two groups represented by the formula (2).   The adhesive composition according to claim 1, wherein the component (A) has a boiling point or sublimation point at 1 atm of 300 ° C. or less.   The adhesive composition according to any one of claims 1 to 7, wherein the component (B) has a boiling point or sublimation point at 1 atm of 300 ° C or lower.   The adhesive composition according to claim 1, wherein the component (C) has a viscosity at 23 ° C. of 100 to 1,000,000 mPa · s. (1) A step of sequentially performing a step of fixing a base material using an adhesive on a support, (2) a step of processing or moving the base material, and (3) a step of peeling the base material from the support. A method of processing or moving a material,
The adhesive composition according to any one of claims 1 to 9 is used as the adhesive, and the base material is removed from the support by removing the adhesive by heat treatment in the step (3). A method for processing or moving the substrate to be peeled.   The method for processing or moving a substrate according to claim 10, wherein in the step (3), the heat treatment is performed at 40 to 400 ° C.   The substrate according to claim 10 or 11, wherein in the step (2), the substrate is processed by at least one method selected from thinning of the substrate, etching, formation of a sputtered film, plating, and dicing. Processing method.   The semiconductor element obtained using the adhesive composition as described in any one of Claims 1-9.   The semiconductor element obtained by the processing method of the base material as described in any one of Claims 10-12.