JP2017092138A - Method for processing base material, laminate, semiconductor device and manufacturing method thereof, and composition for temporary fixing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for processing a base material, by which a support body and the base material can be readily separated from each other without breaking the base material.SOLUTION: A method for processing a base material comprises the steps of: forming a laminate 1 having a support body 10, a temporarily fixing material 20 and a base material 30, provided that the temporarily fixing material has at least a layer (I)21 which includes at least one component selected from a copolymer of a conjugated diene compound and an aromatic compound including a polymerizable double bond, and a hydrogenated product of the copolymer, and a compound having a polysiloxane structure; processing the base material and/or moving the laminate; and separating the base material from the support body by applying a force to the base material and/or support body in a direction substantially perpendicular to a base surface of the base material.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a substrate processing method, a laminate, a semiconductor device and a manufacturing method thereof, and a temporary fixing composition.

  A method has been proposed in which a base material such as a semiconductor wafer is bonded to a support such as a glass substrate via a temporary fixing material, and processing such as back surface grinding and back surface electrode formation is performed on the base material. The temporary fixing material needs to be able to temporarily fix the base material on the support during the processing, and to easily separate the base material from the support after the processing.

  As a method for treating such a base material, in order to prevent damage to the bumps of the base material, a force is applied in a direction substantially perpendicular to the surface of the support or the base material. A separation method is known (see, for example, Patent Documents 1 to 4). However, in order to prevent the substrate from being damaged, a method of performing the separation with a weaker force at about room temperature is desired.

JP 2013-241568 A JP 2013-048215 A JP2013-110391A JP 2013-179135 A

  The present invention is a method for processing and moving a base material in a state where the base material is temporarily fixed on a support via a temporary fixing material, and easily supports the base and the base material without damaging the base material. It is an object of the present invention to provide a substrate processing method that can be separated.

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 method for treating a substrate having the following constitution, and the present invention has been completed.
That is, the present invention relates to the following [1] to [10], for example.

  [1] (1) A step of forming a laminate having a support, a temporary fixing material and a base material, wherein the temporary fixing material comprises a conjugated diene compound (a1) and a polymerizable double bond-containing aromatic compound ( a layer (I) containing a copolymer of a2) and at least one component (A) selected from hydrogenated products of the copolymer and a compound (B) having a polysiloxane structure (b1) (2) processing the substrate and / or moving the laminate; and (3) the substrate and the substrate in a direction substantially perpendicular to the substrate surface of the substrate. And / or separating the substrate from the support by applying a force to the support.

  [2] The base material according to [1], wherein the component (A) is a hydrogenated product of a copolymer of a conjugated diene compound (a1) and a polymerizable double bond-containing aromatic compound (a2). Processing method.

  [3] The above [1] or [2], wherein the compound (B) further has at least one structure (b2) selected from a polyoxyalkylene structure, a structure having a phosphate group, and a structure having a sulfo group. ] The processing method of the base material as described in above.

  [4] The method for treating a substrate according to any one of [1] to [3], wherein the temporary fixing material further includes a layer (II) substantially not containing the compound (B).

  [5] The method for treating a substrate according to [4], wherein the laminate has each element in the order of the support, the layer (I), the layer (II), and the substrate as a layer configuration. .

  [6] A laminated body having a support, a layer (I) and a substrate in this order as a layer structure, wherein the layer (I) comprises a conjugated diene compound (a1) and a polymerizable double bond-containing aromatic compound ( It contains at least one component (A) selected from a copolymer of a2), a hydrogenated product of the copolymer, and a compound (B) having a polysiloxane structure (b1). Laminated body.

  [7] A laminate having a support, a layer (I), a layer (II) and a substrate in this order as a layer structure, wherein the layer (I) comprises a conjugated diene compound (a1) and a polymerizable double bond Containing a copolymer of the aromatic compound (a2), at least one component (A) selected from hydrogenated products of the copolymer, and a compound (B) having a polysiloxane structure (b1). The layered product, wherein the layer (II) does not substantially contain the compound (B).

  [8] A method for manufacturing a semiconductor device, wherein the substrate is processed by the substrate processing method according to any one of [1] to [5] to manufacture a semiconductor device.

  [9] A semiconductor device obtained by the manufacturing method according to [8].

  [10] A copolymer of a conjugated diene compound (a1) and a polymerizable double bond-containing aromatic compound (a2), and at least one component (A) selected from a hydrogenated product of the copolymer, A composition for temporary fixing, comprising a compound (B) having a siloxane structure (b1).

  According to the present invention, in a method for processing / moving a base material in a state where the base material is temporarily fixed on a support via a temporary fixing material, the support and the base material are not damaged. A substrate treating method that can be easily separated can be provided.

FIG. 1 is a cross-sectional view of an embodiment according to the laminate of the present invention.

  Hereinafter, after explaining the laminate formed in the present invention and the temporary fixing composition which is a raw material composition of the temporary fixing material constituting the laminate, the substrate processing method, the semiconductor device, and the manufacturing method thereof explain.

  In the present invention, the temporary fixing material refers to a material used for temporarily fixing a base material on a support so that the base material is not displaced and moved when the base material is processed and / or moved. is there.

1. Laminate In the laminate formed according to the present invention, a substrate to be processed or moved is temporarily fixed on a support via a temporary fixing material. In one embodiment, the temporary fixing material is sandwiched between a base material and a support.

  The temporarily fixing material has at least a layer (I) containing a component (A) and a compound (B) having a polysiloxane structure (b1), which will be described later. Component (A) is at least one selected from a copolymer of a conjugated diene compound (a1) and a polymerizable double bond-containing aromatic compound (a2), and a hydrogenated product of the copolymer. Hereinafter, the compound (B) is also referred to as “polysiloxane compound (B)”, and the layer (I) is also referred to as “separation layer (I)”.

Since the separation layer (I) contains the component (A), the separation layer (I) is excellent in heat resistance and stretch physical properties, and has high resistance to a heat load applied to the temporarily fixing material during processing of the substrate.
Since the separation layer (I) contains the polysiloxane compound (B), the adhesive force in the substantially vertical direction of the substrate surface is small. Therefore, when a force is applied to the substrate and / or the support in a direction substantially perpendicular to the substrate surface, peeling or layer (I) at the interface between the layer (I) and another layer (eg, support) ) Mainly due to cohesive failure. For this reason, the base material can be easily removed from the support without damaging the base material by applying a force in a direction substantially perpendicular to the base material surface without particularly performing a high-temperature heat treatment on the temporary fixing material. Can be separated.

  In the processing of the base material, for example, a shearing force in a direction parallel to the substrate surface is applied to the temporarily fixed material in back surface grinding. Usually, the area of the base material is large, and the joint point of the support / temporary fixing material / base material is large. Therefore, the temporary fixing material is not supported on the support against the shearing force applied during the processing of the base material. Sufficient adhesion to hold the material.

  The temporary fixing material may be a temporary fixing material composed of the separation layer (I), but preferably further includes a layer (II) substantially not containing the compound (B). Hereinafter, the layer (II) is also referred to as “adhesive layer (II)”. As described above, the temporary fixing material having two or more layers is a circuit surface protection of the substrate, adhesion between the substrate and the support, separation of the substrate from the support, and heat resistance during processing. It can have functions such as sex in a well-balanced manner.

  The temporary fixing material preferably has a configuration in which at least one layer is the separation layer (I) and at least one layer is the adhesive layer (II). More preferably, it is a two-layer temporary fixing material composed of a separation layer (I) and an adhesive layer (II). For example, the laminate preferably has each element in the order of the support, the separation layer (I), the adhesive layer (II), and the substrate in the lamination direction.

  When the temporary fixing material has two or more layers, the layer in contact with the support is preferably the separation layer (I), and the layer in contact with the substrate is preferably the adhesive layer (II). When the layer in contact with the support is the separation layer (I), it is possible to further prevent the bumps from falling when the base material is separated from the support.

  An example of the laminate is shown in FIG. The laminate 1 includes a support 10, a temporary fixing material 20 formed on the support 10, and a base material 30 temporarily fixed to the support 10 by the temporary fixing material 20. The temporary fixing material 20 includes a separation layer (I) 21 in contact with the support 10 and an adhesive layer (II) 22 formed on the layer (I) 21 and in contact with the substrate 30.

“Substrate surface” refers to a surface 31 perpendicular to the stacking direction of the substrate and the support.
In the example of the laminated body, the temporary fixing material may have any other layer in addition to the separation layer (I) and the adhesive layer (II). For example, an intermediate layer may be provided between the layer (I) and the layer (II), and another layer is provided between the layer (I) and the support and between the layer (II) and the substrate. May be. Preferably, it is a two-layer temporary fixing material composed of the layer (I) and the layer (II).

  The total thickness of the temporary fixing material may be arbitrarily selected according to the size of the temporary fixing surface of the base material, the heat resistance required for processing, and the degree of adhesion between the base material and the support. it can. The total thickness of the temporary fixing material is usually 0.2 to 1000 μm, preferably 2 to 500 μm, more preferably 2 to 300 μm. When the temporary fixing material has the layer (I) and the layer (II), the thickness of each layer of the layer (I) and the layer (II) is usually independently 0.1 to 500 μm, preferably 1 It is -250 micrometers, More preferably, it is 1-150 micrometers. When these thicknesses are within the above ranges, the temporary fixing material has a sufficient holding force for temporarily fixing the base material, and the base material does not fall off from the temporary fixing surface during the processing or moving process. .

  The temporary fixing material is used in various processing processes required in the scene of modern economic activities, such as miniaturization processing of various material surfaces, various surface mounting, transportation of semiconductor wafers and semiconductor chips, etc. It is suitably used as a temporary fixing material.

[Separation layer (I)]
The separation layer (I) can be formed, for example, from the temporary fixing composition of the present invention containing the component (A) and the polysiloxane compound (B).

<Ingredient (A)>
Component (A) is at least one selected from a copolymer of a conjugated diene compound (a1) and a polymerizable double bond-containing aromatic compound (a2), and a hydrogenated product of the copolymer.

  The copolymer is obtained, for example, by polymerizing at least a conjugated diene compound (a1) and a polymerizable double bond-containing aromatic compound (a2), and other polymerizable monomers may be further used as necessary. . The hydrogenated product can be obtained by hydrogenating the copolymer (hereinafter also referred to as “hydrogenation”).

  The copolymer includes a structural unit derived from a conjugated diene compound (a1) (hereinafter also referred to as “structural unit (a1)”) and a structural unit derived from a polymerizable double bond-containing aromatic compound (a2) (hereinafter referred to as “structural unit (a1)”). (Also referred to as “structural unit (a2)”). The copolymer may have two or more types of structural units (a1), and may have two or more types of structural units (a2). The “structural unit derived from a compound” usually means a structural unit based on the reaction of a polymerizable double bond moiety of the compound.

  The structural unit (a1) is, for example, at least one selected from the structural unit represented by the formula (a1-1) and the structural unit represented by the formula (a1-2), and the structural unit (a2) is: For example, it is a structural unit represented by the formula (a2-1).

式（ａ１−１）、（ａ１−２）および（ａ２−１）中、Ｒ¹はそれぞれ独立に水素原子またはアルキル基であり、Ｒ²は水素原子またはアルキル基であり、Ｒ³は直接結合またはアルキレン基であり、Ａｒは置換基を有してもよいアリール基である。アルキル基およびアルキレン基の炭素数は、通常は１〜８、好ましくは１〜４である。アリール基の炭素数は、通常は６〜１８、好ましくは６〜１０であり、例えば、フェニル基、ナフチル基が挙げられる。アリール基における置換基としては、例えば、アルキル基、アルケニル基、アリール基が挙げられる。

In formulas (a1-1), (a1-2) and (a2-1), R ¹ is independently a hydrogen atom or an alkyl group, R ² is a hydrogen atom or an alkyl group, and R ³ is a direct bond Alternatively, it is an alkylene group, and Ar is an aryl group which may have a substituent. Carbon number of an alkyl group and an alkylene group is 1-8 normally, Preferably it is 1-4. Carbon number of an aryl group is 6-18 normally, Preferably it is 6-10, for example, a phenyl group and a naphthyl group are mentioned. Examples of the substituent in the aryl group include an alkyl group, an alkenyl group, and an aryl group.

  Examples of the conjugated diene compound (a1) include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2- Examples include methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 3-butyl-1,3-octadiene, and 4,5-diethyl-1,3-octadiene. Among these, 1,3-butadiene and isoprene are preferable.

  The vinyl bond content in the copolymer is usually 30 to 95 mol%, preferably 50 to 90 mol%. The vinyl bond content is a structural unit of a conjugated diene compound that is incorporated in the copolymer before hydrogenation in a 1,2-bond, 3,4-bond, and 1,4-bond bond mode. It is the total proportion (based on mol%) of structural units incorporated by 1,2-bonds and 3,4-bonds. The vinyl bond content can be determined by an infrared absorption spectrum method (Morero method).

  The compound (a2) is a polymerizable double bond-containing aromatic compound other than the conjugated diene compound (a1). For example, styrene, α-methylstyrene, o, m or p-methylstyrene, t-butylstyrene, Divinylbenzene is mentioned. Among these, styrene and α-methylstyrene are preferable from the viewpoints of availability and ease of polymerization.

  In the copolymer, the content ratio of the structural unit (a1) is preferably 60 to 99% by mass, more preferably 70 to 97% by mass, and still more preferably 80 to 95% by mass; A content rate becomes like this. Preferably it is 1-40 mass%, More preferably, it is 3-30 mass%, More preferably, it is 5-20 mass%. Such an embodiment is preferable in terms of the heat resistance and elongation properties of the copolymer. These content ratios can be measured by NMR.

  The copolymer is preferably a hydrocarbon polymer in terms of excellent resistance to the solvent that can be used in the step (2) of the separation layer (I), and is a structure derived from a monomer having a polymerizable double bond. The unit is preferably a copolymer composed of only the structural unit (a1) and the structural unit (a2).

  The separation layer (I) may be exposed to an environment over a wide temperature range during the processing of the substrate, and it is desirable that the separation layer (I) has a high elongation property in order to prevent deformation such as warpage of the substrate. In the present invention, since the component (A) is used as the substance forming the separation layer (I), such a requirement can be satisfied.

  Used as separation layer (I), heat during bump bonding, heat during gas phase processes such as plasma etching and chemical vapor deposition, solvent used as resist stripper, resist developer during base material processing It is preferable to have high heat resistance and solvent resistance with respect to the alkaline solution used and the hydrofluoric acid used for wet etching. Therefore, the component (A) is preferably a hydrogenated product of the copolymer.

  The hydrogenation rate of the double bond derived from the conjugated diene compound (a1) in the hydrogenated product is preferably 90 mol% or more, and more preferably 95 mol% or more. Such an embodiment is preferable in that high heat resistance and solvent resistance of the separation layer (I) can be obtained.

  The component (A) may be a random copolymer of the above compounds (a1) and (a2) and / or a hydrogenated product thereof, but has a high elongation property, so that it is a block copolymer and / or a hydrogenated product thereof. Preferably, the block copolymer has a polymer block (A1) composed of the structural unit (a1) and a polymer block (A2) composed of the structural unit (a2) and / or a hydrogenated product thereof. Is more preferable, and a hydrogenated product of the block copolymer is more preferable. For example, in the total amount of component (A) of 100% by mass, the content ratio of the block copolymer and the hydrogenated product thereof is preferably 60% by mass or more, more preferably 80% by mass or more.

  In the block copolymer, the content of the polymer block (A1) is preferably 60 to 99% by mass, more preferably 70 to 97% by mass, and still more preferably 80 to 95% by mass; The content ratio of A2) is preferably 1 to 40% by mass, more preferably 3 to 30% by mass, and further preferably 5 to 20% by mass.

As the structure of the block copolymer and its hydrogenated product, the polymer block (A1) and its hydrogenated product are simply expressed as “A1”, the polymer block (A2) is simply expressed as “A2”, and the vinyl bond content The polymer block (A1) having a large size and a hydrogenated product thereof are represented by “A11”, and the polymer block (A1) having a small vinyl bond content and the hydrogenated product thereof are represented by “A12”. Structure is mentioned.
[A1-A2] (1)
[A2-A1-A2] (2)
[A2-A11-A12] (3)
[A12-A11-A12] (4)
[A1-A2] n (5)

  In the above formula, n is an integer of 2 or more. When at least one of A1 and A2 is 2 or more in the block copolymer, each polymer block may be the same or different. Among these, the triblock body of the formula (2) is preferable because it has high elongation properties.

  The block copolymer may be bonded via a residue of the coupling agent. As the coupling agent, a bifunctional or higher functional coupling agent can be used. For example, the coupling agent described in Unexamined-Japanese-Patent No. 2014-095023, Unexamined-Japanese-Patent No. 2010-116570, Unexamined-Japanese-Patent No. 2010-001371, and Unexamined-Japanese-Patent No. 2010-254983 is mentioned. A coupling agent may be used individually by 1 type, and may use 2 or more types together.

  Specific examples of the component (A) include random copolymers such as styrene-butadiene random copolymers and styrene-isoprene random copolymers; polymerizable double bond-containing aromatic compound elastomers such as styrene-butadiene- Styrene block copolymer (SBS), styrene-ethylene / butylene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene / propylene-styrene block copolymer (SEPS) ), Styrene-butadiene block copolymer (SB), styrene-ethylene / butylene block copolymer (SEB), styrene-isoprene block copolymer (SI), styrene-ethylene / propylene block copolymer (SEP), etc. Conjugated diene compounds and polymerizable two Block copolymer of heavy bond-containing aromatic compound and hydrogenated product thereof; Hydrogenated conjugated diene-based elastomer, for example, styrene-ethylene / butylene-olefin crystal block copolymer (SEBC) And olefin crystal block copolymers such as group compound-olefin crystal block copolymer and olefin crystal-ethylene / butylene-olefin crystal block copolymer (CEBC).

  In the above description, for example, a styrene-butadiene-styrene block copolymer means a block copolymer in the form of polystyrene block-polybutadiene block-polystyrene block.

  The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) method of the component (A) is usually 1,000 to 300,000, preferably 2,000 to 250,000, more preferably. 3,000 to 200,000. In the case of a block copolymer and / or a hydrogenated product thereof, the lower limit value of Mw is preferably 10,000, more preferably 20,000, and even more preferably 30,000. Such an embodiment is preferable because it can reduce the adhesive force in the substantially vertical direction of the base material surface and has high stretch properties.

  A well-known method is employable as a manufacturing method of a component (A). For example, a monomer corresponding to each structural unit is subjected to living anion polymerization in an organic solvent using an organic alkali metal compound as a polymerization initiator, and the obtained polymer is hydrogenated as necessary. For example, the methods described in JP 2014-95023 A, JP 2010-254983 A, JP 2010-116570 A, and JP 2010-1371 A may be mentioned.

  The hydrogenation method and reaction conditions for the copolymer are not particularly limited. For example, the copolymerization is performed at 20 to 150 ° C. under hydrogen pressure of 0.1 to 10 MPa in the presence of a hydrogenation catalyst. In this case, the hydrogenation rate can be arbitrarily selected by changing the amount of the hydrogenation catalyst, the hydrogen pressure during the hydrogenation reaction, and the reaction time.

  Examples of the hydrogenation catalyst include JP-A-1-275605, JP-A-5-271326, JP-A-5-271325, JP-A-5-222115, JP-A-11-292924, and JP-A-11-292924. The hydrogenation catalyst described in 2000-37632 gazette and Unexamined-Japanese-Patent No. 7-90017 is mentioned. Only one hydrogenation catalyst may be used, or two or more hydrogenation catalysts may be used in combination.

A component (A) may be used individually by 1 type, and may use 2 or more types together.
In 100% by mass of the solid content excluding the compound (B) of the temporary fixing composition, the content of the component (A) is usually 30% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more. It is. Such an embodiment is preferable in terms of adhesiveness, separability, heat resistance, solvent resistance, and elongation property of the temporary fixing material. Here, “solid content” refers to all components other than the solvent.

<Compound (B)>
The compound (B) has a polysiloxane structure (b1). The compound (B) may further have at least one structure (b2) selected from a polyoxyalkylene structure, a structure having a phosphate group, and a structure having a sulfo group.

  By using a layer containing the component (A) as the coating film forming main component and the polysiloxane compound (B) as the surfactant as the separation layer in the temporary fixing material, the support and the substrate can be used with a weak force. And can be separated. The reason is estimated as follows. When the separation layer contains a surfactant in the entire layer, the adhesive force between the layer and another layer (for example, a support) in a direction substantially perpendicular to the substrate surface is weakened, and the support and the substrate can be separated with a weak force. it is conceivable that. However, in general, surfactants tend to be unevenly distributed on the film surface during the formation of the coating film. For this reason, in order for the surfactant to be present in the entire layer without being unevenly distributed on the film surface, it is necessary to select a coating film-forming main component having high compatibility with the surfactant. In the present invention, the combination of the component (A) and the polysiloxane compound (B) has high compatibility. For this reason, it is considered that the polysiloxane compound (B) can be present in the entire separation layer (I), and therefore the support and the substrate can be separated with a weak force.

<< Polysiloxane structure (b1) >>
The polysiloxane structure (b1) is a structure in which two or more siloxane structures are connected. Examples of the siloxane structure include structures represented by the formula (b1-1) or the formula (b1-2). Since the structure (b1) has a relatively low dipole moment, the compound (B) and the component (A) can be mixed well.

式（ｂ１−１）および（ｂ１−２）中、Ｒ¹は、それぞれ独立に、“アルキル基”または“置換基を有してもよいアリール基”である。アルキル基の炭素数は、好ましくは１〜３０、より好ましくは１〜２０である。アリール基の炭素数は、好ましくは６〜１５、より好ましくは６〜１０である。アリール基における置換基としては、例えば、アルキル基が挙げられる。

In formulas (b1-1) and (b1-2), R ^{1 's} are each independently an “alkyl group” or “aryl group optionally having substituent (s)”. Carbon number of an alkyl group becomes like this. Preferably it is 1-30, More preferably, it is 1-20. Carbon number of an aryl group becomes like this. Preferably it is 6-15, More preferably, it is 6-10. Examples of the substituent in the aryl group include an alkyl group.

In formula (b1-2), R ² represents an “alkylene group” or “an arylene group optionally having a substituent”. Carbon number of an alkylene group becomes like this. Preferably it is 1-30, More preferably, it is 1-20. Carbon number of an arylene group becomes like this. Preferably it is 6-15, More preferably, it is 6-10. Examples of the substituent in the arylene group include an alkyl group. * Is a bond with the structure (b2) such as a polyoxyalkylene structure.

<< Structure (b2) >>
The structure (b2) is at least one structure selected from a polyoxyalkylene structure, a structure having a phosphate group (H ₂ PO ₄ —), and a structure having a sulfo group (—SO ₃ H).
The polyoxyalkylene structure is, for example, a group represented by the formula — (A—O) _n —. In said formula, A is an alkylene group, The carbon number becomes like this. Preferably it is 1-20, More preferably, it is 1-12, n is an integer of 2-50, Preferably it is an integer of 2-40.

<< Specific Example of Compound (B) >>
As the compound (B), the compound having a polyoxyalkylene structure as the structure (b2) is excellent in the effect of reducing the adhesive force of the separation layer (I) in a direction substantially perpendicular to the substrate surface. preferable.

  Specific examples of the compound (B) include, for example, Polyflow KL-245, KL-270, KL-700 (manufactured by Kyoeisha Chemical Co., Ltd.), TEGO WET 270 (manufactured by Evonik Degussa Japan Co., Ltd.), the following formula Examples include polyether-modified polysiloxanes such as the compound represented by (B1).

式（Ｂ１）中、Ｒ¹はそれぞれ独立に炭素数１〜３０のアルキル基または置換基（例：アルキル基）を有してもよい炭素数６〜１５のアリール基であり、Ｒ²は炭素数１〜３０のアルキレン基または置換基（例：アルキル基）を有してもよい炭素数６〜１５のアリーレン基であり、Ａは炭素数１〜２０のアルキレン基であり、Ｒａは水素原子または炭素数１〜５のアルキル基であり、ｎは２〜５０の整数であり、ｘおよびｙは、それぞれ独立に２〜１００の整数である。好ましくは、Ｒ¹はメチル基またはフェニル基であり、Ｒ²はメチレン基であり、Ａはエチレン基であり、ｎは２〜２０の整数であり、ｘおよびｙは、それぞれ独立に２〜１００の整数である。

In formula (B1), each R ¹ is independently an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 15 carbon atoms which may have a substituent (eg, alkyl group), and R ² is carbon. An alkylene group having 1 to 30 carbon atoms or an arylene group having 6 to 15 carbon atoms which may have a substituent (eg, an alkyl group), A is an alkylene group having 1 to 20 carbon atoms, and Ra is a hydrogen atom. Or it is a C1-C5 alkyl group, n is an integer of 2-50, and x and y are integers of 2-100 each independently. Preferably, R ¹ is a methyl group or a phenyl group, R ² is a methylene group, A is an ethylene group, n is an integer of 2 to 20, and x and y are each independently 2 to 100. Is an integer.

  Examples of commercially available compounds represented by the formula (B1) include SH28PA, SH30PA, SH-8400, SH-190, 193, and SF-8428 (manufactured by Toray Dow Corning Co., Ltd.).

In the formula (B1), the —Si (R ¹ ) ₂ O— unit and the —Si (R ¹ ) (R ² — (AO) _n —Ra) O— unit have a block structure or a random structure. Also good.
In 100% by mass of the solid content of the temporary fixing composition, the content of the compound (B) is usually 0.001 to 2% by mass, preferably 0.005 to 1.5% by mass, more preferably 0.008. ˜1% by mass. Similarly, the content of the compound (B) in the separation layer (I) is usually 0.001 to 2% by mass, preferably 0.005 to 1.5% by mass, based on the total mass of the layer (I). %, More preferably 0.008 to 1% by mass. When the content of the compound (B) is equal to or more than the lower limit value, the adhesive force of the temporary fixing material is reduced with respect to the force of pulling up the substrate and / or the support in a direction substantially perpendicular to the substrate surface. On the other hand, the adhesive force of the temporary fixing material can be maintained against the force applied in a substantially horizontal direction with respect to the base material surface.

<Other ingredients>
The temporary fixing composition is selected from thermoplastic resins (excluding component (A)), antioxidants, polymerization inhibitors, adhesion assistants, polystyrene cross-linked particles, and metal oxide particles, if necessary. You may contain 2 or more types. Examples of the metal oxide particles include aluminum oxide, zirconium oxide, titanium oxide, and silicon oxide.

When the composition for temporary fixing contains the thermoplastic resin, the heat resistance of the separation layer (I) can be improved. Examples of the thermoplastic resin include cycloolefin resin, terpene resin, petroleum resin, novolac resin, and polystyrene resin. Polystyrene resins usually have a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC method of 1,000 to 100,000, and the other resins include those in the adhesive layer (II) column. The illustrated resin is mentioned. The said resin may be used individually by 1 type, and may use 2 or more types together. Among these, at least one selected from a novolac resin and a polystyrene-based resin is preferable because of excellent compatibility with the component (A).
In the temporary fixing composition, the content of the thermoplastic resin is usually 100 parts by mass or less, preferably 50 parts by mass or less with respect to 100 parts by mass of the component (A).

[Adhesive layer (II)]
The adhesive layer (II) can be formed using a known adhesive for temporarily fixing the substrate. In the case of a laminate having the respective elements in the order of the support, the separation layer (I), the adhesive layer (II) and the substrate, the adhesive layer (II) temporarily fixes the substrate on the support, In addition, the surface of the base material is covered and protected.

  The adhesive layer (II) preferably does not substantially contain the compound (B) described above. “Substantially free” means that the content of the compound (B) is usually 0.0001% by mass or less, preferably 0.00001% by mass or less, based on 100% by mass of the total solid content of the adhesive. Particularly preferably, it means 0% by mass. Similarly, the content of the compound (B) in the adhesive layer (II) is usually 0.0001% by mass or less, preferably 0.00001% by mass or less, particularly with respect to the total mass of the layer (II). Preferably it is 0 mass%.

  Examples of the adhesive include thermoplastic resin-based, elastomer-based, and thermosetting resin-based adhesives, and may be a mixed system of two or more selected from these. Among these, an elastomeric adhesive is preferable from the viewpoint of elongation properties. The adhesive may be any of a solvent type, an emulsion type, and a hot melt type.

<Thermoplastic resin>
Examples of the thermoplastic resin include cycloolefin resin, terpene resin, petroleum resin, novolac resin, (meth) acrylic resin, phenoxy resin, polyolefin, polyvinyl chloride, and ethylene-vinyl acetate copolymer. Of these, cycloolefin resins are preferred.

  Examples of the cycloolefin resin include an addition copolymer of a cyclic olefin compound and an acyclic olefin compound, a ring-opening metathesis polymer of one or more cyclic olefin compounds, and the ring-opening metathesis polymer. And a polymer obtained by hydrogenation.

  Examples of the cyclic olefin compounds include norbornene olefins, tetracyclododecene olefins, dicyclopentadiene olefins, and derivatives thereof. Examples of the derivatives include alkyl groups, alkylidene groups, aralkyl groups, cycloalkyl groups, hydroxy groups, alkoxy groups, acetyl groups, cyano groups, amide groups, imide groups, silyl groups, aromatic rings, ether bonds, and ester bonds. The substituted derivative which has 1 type, or 2 or more types chosen from is mentioned.

  Examples of the non-cyclic olefin compounds include linear or branched olefins having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably ethylene, propylene, and butene, and particularly preferably ethylene. It is.

  The weight average molecular weight (Mw) in terms of polystyrene measured by the GPC method of the cycloolefin-based resin is usually 10,000 to 100,000, preferably 30,000 to 100,000.

  Examples of the terpene resin include terpene resins, hydrogenated terpene resins, terpene phenol resins, hydrogenated terpene phenol resins, aromatic modified terpene resins, and aromatic modified hydrogenated terpene resins. The weight average molecular weight (Mw) in terms of polystyrene measured by the GPC method of the terpene resin is usually 50,000 or less, preferably 500 to 10,000.

  Examples of petroleum resins include C5 petroleum resins, C9 petroleum resins, C5 / C9 mixed petroleum resins, cyclopentadiene resins, polymers of vinyl-substituted aromatic compounds, and copolymers of olefins and vinyl-substituted aromatic compounds. Examples thereof include a polymer, a copolymer of a cyclopentadiene compound and a vinyl-substituted aromatic compound, a hydrogenated product thereof, and a mixture of two or more selected from these. The weight average molecular weight (Mw) in terms of polystyrene measured by the GPC method of the petroleum resin is usually 20,000 or less, preferably 100 to 20,000.

The novolak resin can be obtained, for example, by addition condensation of a phenol compound and an aldehyde compound in the presence of an acidic catalyst such as oxalic acid. Preferable specific examples of the novolak resin include a phenol / formaldehyde condensed novolak resin, a cresol / formaldehyde condensed novolak resin, and a phenol-naphthol / formaldehyde condensed novolak resin. The weight average molecular weight (Mw) in terms of polystyrene measured by the GPC method of the novolak resin is usually 2,000 or more, preferably 2,000 to 20,000.
A thermoplastic resin may be used individually by 1 type, and may use 2 or more types together.

<Elastomer>
Examples of the elastomer include the component (A) described above, acrylic rubber, nitrile rubber, and urethane rubber. These may be used alone or in combination of two or more.

  The adhesive preferably contains an elastomer from the viewpoint of elongation properties, and the elastomer is preferably the component (A) described above, and the component (A) described above from the viewpoint of heat resistance and solvent resistance. Of these, a hydrogenated product is more preferable.

<Thermosetting resin>
Examples of thermosetting resins include epoxy resins, resol resins, urea resins, melamine resins, unsaturated polyester resins, diallyl phthalate resins, urethane resins, silicone resins, (meth) acryloyl group-containing resins, and thermosetting polyimide resins. Can be mentioned. These may be used alone or in combination of two or more.

<Other ingredients>
The adhesive may contain one or more selected from an antioxidant, a polymerization inhibitor, an adhesion assistant, a surfactant, polystyrene cross-linked particles, and metal oxide particles as necessary. Examples of the metal oxide particles include aluminum oxide, zirconium oxide, titanium oxide, and silicon oxide.

[Production of Temporary Fixing Composition and Adhesive]
The temporary fixing composition and the adhesive are known devices used for processing the resin composition as necessary, for example, a twin screw extruder, a single screw extruder, a continuous kneader, a roll kneader, a pressure kneader, a Banbury mixer. Can be produced by mixing each component. In addition, for the purpose of removing impurities, filtration can be appropriately performed.

In the production of the temporary fixing composition and the adhesive, a solvent may be used in terms of setting these viscosities in a range suitable for coating. Examples of the solvent include toluene, xylene, limonene, mesitylene, dipentene, pinene, bicyclohexyl, cyclododecene, 1-tert-butyl-3,5-dimethylbenzene, butylcyclohexane, cyclooctane, cycloheptane, cyclohexane, methylcyclohexane, and the like. Hydrocarbon solvents: alcohol / ether solvents such as anisole, propylene glycol monomethyl ether, dipropylene glycol methyl ether, diethylene glycol monoethyl ether, diglyme; ethylene carbonate, ethyl acetate, butyl acetate, ethyl lactate, ethyl 3-ethoxypropionate, Esters such as propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene carbonate, γ-butyrolactone Lactone solvents; cyclopentanone, cyclohexanone, methyl isobutyl ketone, ketone solvents such as 2-heptanone; amide / lactam solvents such as N- methyl-2-pyrrolidinone.
A solvent may be used individually by 1 type and may use 2 or more types together.

  When the composition for temporary fixing and the adhesive contain a solvent, it becomes easy to adjust the viscosity thereof, and therefore, it becomes easy to form the temporary fixing material on the substrate or the support. For example, the solvent can be used in such a range that the solid content concentrations of the temporary fixing composition and the adhesive are each independently usually 5 to 70% by mass, more preferably 15 to 50% by mass. Here, the “solid content concentration” is the total concentration of all components other than the solvent.

2. Substrate treatment method The substrate treatment method of the present invention comprises (1) a step of forming the laminate, (2) a step of processing the substrate and / or moving the laminate, 3) separating the substrate from the support by applying a force to the substrate and / or the support in a direction substantially perpendicular to the substrate surface of the substrate; (4) When there is a temporary fixing material remaining on the base material after the separation, a step of removing the temporary fixing material from the base material may be included. Hereinafter, each said process is also called process (1)-process (4), respectively.

<2-1. Step (1)>
In the step (1), for example, (1-1) the temporary fixing material is formed on the surface of the support and / or the base material, and the base material and the support are bonded together via the temporary fixing material. The substrate can be temporarily fixed on the support. Also, (1-2) temporarily fixing the substrate on the support by forming the temporary fixing material on the surface of the support and forming a substrate such as a resin coating film on the temporary fixing material. You can also The base material may be surface-treated as necessary.

  Examples of the method for forming the temporary fixing material described above include (α) a method of directly forming each layer of the temporary fixing material on the support and / or the base material, and (β) a film subjected to a release treatment. An example is a method of forming a film with a fixed film thickness using a temporary fixing composition or an adhesive and then transferring each layer to a support and / or a substrate by a laminating method. From the viewpoint of film thickness uniformity, the method (α) is preferred.

Hereinafter, a method for forming the separation layer (I) using the temporary fixing composition and a method for forming the adhesive layer (II) using the adhesive will be described. The temporary fixing material may have only the separation layer (I), or may have the separation layer (I) and the adhesive layer (II).
Examples of the method for applying the temporary fixing composition and the adhesive that form each layer of the temporary fixing material include a spin coating method and an ink jet method.

  After the temporary fixing composition or adhesive is applied to form a coating film, for example, by heating with a heating device such as a hot plate or oven to evaporate the solvent, the separating layer (I) or adhesive Layer (II) is formed. The heating conditions are appropriately determined according to the boiling point of the solvent. For example, the heating temperature is usually 100 to 350 ° C., and the heating time is usually 1 to 60 minutes.

  In the method (α), as a method of bonding the base material and the support with the temporary fixing material having the separation layer (I) and the adhesive layer (II), for example, the separation layer (I) is formed on the support surface. And forming the adhesive layer (II) on the substrate surface and bonding them so that the layer (I) and the layer (II) are in contact with each other; the layer (II) and the layer (II) on the substrate surface Method 2 in which layer (I) is sequentially formed and a support is bonded onto layer (I); layer (I) and layer (II) are sequentially formed on the support surface, and a substrate is formed on layer (II). The method 3 of bonding is mentioned. The temperature at this time is appropriately selected according to the temporary fixing composition, the components contained in the adhesive, the coating method, and the like. Among these, the method 1 is preferable from the viewpoint of avoiding mixing of the layers (I) and (II) during the formation of each layer.

  The pressure-bonding condition between the substrate and the support is, for example, preferably from room temperature to 400 ° C., more preferably from 150 to 400 ° C. for 0.1 to 20 minutes, and a pressure of 0.01 to 100 MPa is applied in the stacking direction of each layer. To do so. You may heat-process for 10 minutes-3 hours at 150-300 degreeC after crimping | compression-bonding. In this way, the base material is firmly held on the support via the temporary fixing material.

Examples of the base material that is the object to be processed (moved) include a semiconductor wafer, a semiconductor chip, a glass substrate, a resin substrate, a metal substrate, a metal foil, a polishing pad, and a resin coating film. The semiconductor wafer and the semiconductor chip may be formed with at least one selected from bumps, wirings, insulating films, and various elements. Various elements may be formed or mounted on the substrate. 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, A photosensitive insulating resin layer formed from a photosensitive insulating resin material can be used.
Examples of the support include a glass substrate, a quartz substrate, and a transparent resin substrate.

<2-2. Step (2)>
Step (2) is a step of processing the substrate temporarily fixed on the support and / or moving the obtained laminate. The moving process is a process of moving a substrate such as a semiconductor wafer together with a support from one apparatus to another apparatus. Examples of the processing of the substrate temporarily fixed on the support include thinning of the substrate such as dicing and back grinding, photofabrication, stacking of semiconductor chips, and mounting of various elements. The photofabrication includes, for example, one or more processes selected from resist pattern formation, etching processing, sputtered film formation, plating process, and plating reflow process. The etching process and the formation of the sputtered film are performed in a temperature range of about 25 to 300 ° C., for example, and the plating process and the plating reflow process are performed in a temperature range of about 225 to 300 ° C., for example. The processing of the substrate is not particularly limited as long as it is performed at a temperature at which the holding force of the temporarily fixed material is not lost.

  The substrate processing method of the present invention is applicable to semiconductor wafers and semiconductor chips having bumps, particularly semiconductor wafers and semiconductor chips having pillar bumps having poor heat resistance (eg, pillar bumps composed of a copper portion and a solder portion). Can be applied. In particular, when the aspect ratio (height / maximum width) of the bump is 0.8 or more, the effect of preventing the bump from being damaged when the base material is separated from the support is remarkably exhibited as compared with the conventional method.

<2-3. Step (3)>
After the processing and / or movement of the substrate, the substrate is peeled from the support by applying a force to the substrate and / or the support in a direction substantially perpendicular to the substrate surface. To separate them.

  When separating the substrate and the support by applying a force in a direction substantially parallel to the substrate surface, that is, when separating by a shearing force, a shearing force is also applied to the bumps that the substrate has at the time of separation. May fall over. When separation of the base material and the support is performed by applying a force in a direction substantially perpendicular to the base material surface, the shearing force applied to the bumps of the base material at the time of separation is reduced, and the collapse of the bumps can be prevented. In this respect, since bumps having a large aspect ratio (pillar bumps) are used particularly in the mounting process in the manufacture of the laminated chip, the bumps are significantly collapsed. However, the present invention can prevent such collapses.

  For example, there is a method in which one of the substrate and the support is fixed, and the other is separated by lifting the other with a certain angle from the parallel direction with respect to the substrate surface. Specifically, it is preferable to apply a force in a direction substantially perpendicular to the substrate surface to separate the support and the substrate. “Applying a force in a direction substantially perpendicular to the substrate surface” means that the z axis, which is an axis perpendicular to the substrate surface, is usually in the range of 0 ° to 60 °, preferably 0 °. Applying a force in the range of ˜45 °, more preferably in the range of 0 ° to 30 °, even more preferably in the range of 0 ° to 5 °, particularly preferably 0 °, ie perpendicular to the substrate surface. Means.

  The pressure applied in a direction substantially perpendicular to the substrate surface is usually 0.0001 to 100 MPa, preferably 0.001 to 30 MPa, and more preferably 0.005 to 1 MPa. The temperature at the time of separation is usually 5 to 100 ° C, preferably 10 to 45 ° C, and more preferably 15 to 30 ° C. The temperature here means the temperature of the support.

  Separation methods include, for example, a method in which the periphery of the substrate or the support is lifted and peeled in order from the periphery of the substrate or the support toward the center while applying a force in a direction substantially perpendicular to the substrate surface (hook pull). Method). In the present invention, the substrate and the support can be separated by such a method. Further, in order to prevent the base material from being damaged at the time of separation, a reinforcing tape such as a commercially available dicing tape may be attached to the surface of the base material opposite to the temporary fixing surface with the support.

  In the present invention, as described above, the temporary fixing material has the layer (I), and separation of the substrate and the support mainly occurs in the layer (I). When the substrate has bumps, the bumps can be prevented from being damaged during the separation process.

<2-4. Step (4)>
When the temporarily fixing material remains on the substrate after separation from the support, the temporarily fixing material can be removed from the substrate by a simple technique such as peeling and solvent cleaning.
Examples of the peeling treatment include a method of peeling the temporarily fixing material from the base material in a direction substantially perpendicular to the base material surface, and specifically, while applying a force in a direction substantially perpendicular to the base material surface. And a method (hook-pull method) of peeling the temporarily fixing material in order from the periphery to the center of the substrate. The meaning of the substantially vertical direction is as described in the step (3).

Examples of the cleaning treatment using a solvent include a method of immersing the substrate in the solvent, a method of spraying the solvent on the substrate, and a method of applying ultrasonic waves while immersing the substrate in the solvent. Although the temperature of a solvent is not specifically limited, Preferably it is 10-80 degreeC, More preferably, it is 20-50 degreeC. As a solvent, the solvent demonstrated in the column of manufacture of the composition for temporary fixing and an adhesive agent can be illustrated.
As described above, the substrate can be separated from the support.

3. Semiconductor device and manufacturing method thereof The semiconductor device of the present invention can be manufactured by processing the base material by the base material processing method of the present invention. In the present invention, a semiconductor device (eg, semiconductor element) obtained by processing a base material can be satisfactorily separated from the support, and the base material itself or each member (eg, bump) of the base material is damaged. Therefore, a semiconductor device having various performances can be manufactured.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the following description of Examples and the like, “part” is used to mean “part by mass” unless otherwise specified.

  The weight average molecular weight (Mw) of the polymer and the resin was measured using a GPC column (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) manufactured by Tosoh Corporation, and in terms of polystyrene, the measuring device “HLC-8220-GPC”. ”(Manufactured by Tosoh Corporation).

1. Manufacture of temporary fixing composition and adhesive
[Examples 1A-7A and Preparation Examples 1A-2A]
Production of Temporary Fixing Compositions (I-1) to (I-9) The components shown in Table 1 were mixed in the blending amounts shown in Table 1 to temporarily fix the compositions (I-1) to (I-9). ) Was manufactured. Details of each component in Table 1 are as described below.

Copolymer (A1): Hydrogenated triblock conjugated diene polymer consisting of styrene-butadiene-styrene (hydrogenation rate of double bond derived from butadiene = 99 mol% or more, styrene unit content ratio = 10% by mass, (Weight average molecular weight = 120,000)
Copolymer (A2): Hydrogenated triblock conjugated diene polymer consisting of styrene-isoprene-styrene (hydrogenation rate of double bond derived from isoprene = 99 mol% or more, styrene unit content ratio = 20 mass%, (Weight average molecular weight = 100,000)
Copolymer (A3): Styrene-isoprene random copolymer
(Styrene unit content ratio = 20 mass%, weight average molecular weight = 3500)
Copolymer (A4): Phenoxy resin
(Product name “EPICLON EXA-123”, manufactured by DIC Corporation)
Compound (B1): Compound having a dialkyl silicone structure and a polyoxyalkylene structure (trade name “TEGO WET 270”, manufactured by Evonik Degussa Japan Co., Ltd.)
Compound (B2): Compound having a dialkyl silicone structure and a polyoxyalkylene structure (trade name “Polyflow KL-700”, manufactured by Kyoeisha Chemical Co., Ltd.)
Compound (B3): Compound having a fluorinated alkenyl structure and a polyoxyalkylene structure (trade name “Factent 209F”, manufactured by Neos Co., Ltd.)
Ingredient (C1): Hindered phenol antioxidant
(Product name “Adeka Stub AO-60”, manufactured by ADEKA Corporation)
Component (C2): Polystyrene (weight average molecular weight = 2500)
Component (D1): Toluene Component (D2): Mesitylene Component (D3): Cyclohexanone

[Preparation Example 3A] Production of Adhesive (II-1) 100 parts of a hydrogenated triblock conjugated diene polymer composed of styrene-butadiene-styrene (copolymer (A1)) and 1 part of hindered Adhesive (II-1) was manufactured by mixing a phenolic antioxidant (trade name “ADK STAB AO-60”, manufactured by ADEKA Corporation) and 200 parts of mesitylene.

2. Evaluation
[Example 1B]
A temporary fixing composition (I-1) is applied on a 4-inch silicon wafer (base material) provided with a plurality of bumps by a spin coating method, and is heated at 160 ° C. in the air using a hot plate at 5 ° C. Then, the substrate was heated at 230 ° C. for 10 minutes under a nitrogen atmosphere to obtain a substrate having a temporary fixing material layer (I-1) having a thickness of 30 μm. The thickness of the temporary fixing material layer was measured with a stylus thickness meter. The same applies to the thicknesses of the other layers. The obtained substrate was cut into a length of 1 cm and a width of 1 cm to obtain a substrate 1 having a temporary fixing material (temporary fixing material layer (I-1)).

  The bumps have a size of 20 μm in length, 20 μm in width, and 20 μm in height, the lower half on the silicon wafer side is a pillar portion made of copper, and the upper half has a solder portion made of Sn—Ag alloy.

  The substrate 1 and the glass substrate (a glass substrate having a square surface of 2 cm × 2 cm; a support) are bonded to each other through a temporary fixing material, and a force of 0.05 MPa is applied at 180 ° C. using a die bonder device. Then, the silicon wafer and the glass substrate were temporarily fixed via a temporary fixing material.

  It was confirmed by visual observation that the glass substrate and the temporary fixing material were temporarily fixed without bubbles. In addition, using a universal bond tester (trade name “Daily 4000”, manufactured by Daisy), a shearing force (speed of 500 μm / second, 23 ° C.) was applied in a direction parallel to the substrate surface. It was confirmed that the silicon wafer and the glass substrate were held (temporarily fixed) without slipping even when the slab was added.

Next, using a universal bond tester (trade name “Digi 4000”, manufactured by Daisy) on the temporarily fixed substrate 1, a hook pull method (with respect to the z axis) in the direction perpendicular to the substrate surface (z axis). 0 °) force (500 μm / sec rate, 23 ° C.) was applied. As a result, the glass substrate could be peeled with a force of less than 0.2 MPa.
After the temporary fixing material residue on the substrate 1 after peeling was washed with mesitylene, the state of the bump was visually observed. As a result, it was found that the bump was not deformed and could be peeled well.

[Examples 2B-7B, Comparative Example 1B, Comparative Example 2B]
Example 1B was the same as Example 1B except that the temporary fixing composition was changed as shown in Table 2. The results are shown in Table 2.

[Example 8B]
The adhesive (II-1) is applied by spin coating on a 4-inch silicon wafer (base material) provided with a plurality of bumps, and heated at 160 ° C. for 5 minutes in the air using a hot plate. Subsequently, the substrate was heated at 230 ° C. for 10 minutes in a nitrogen atmosphere to obtain a substrate having an adhesive layer (II-1) having a thickness of 30 μm. The obtained substrate was cut into a length of 1 cm and a width of 1 cm to obtain a substrate 1 having an adhesive layer (II-1).

  The bumps have a size of 20 μm in length, 20 μm in width, and 20 μm in height, the lower half on the silicon wafer side is a pillar portion made of copper, and the upper half has a solder portion made of Sn—Ag alloy.

  In addition, the temporary fixing composition (I-1) was applied to a 4-inch glass substrate (support) by spin coating, heated at 160 ° C. for 5 minutes using a hot plate, and further at 200 ° C. for 10 minutes. Heating was performed to obtain a substrate having a uniform separation layer (I-1) having a thickness of 30 μm. The obtained substrate was cut into a length of 1 cm and a width of 1 cm to obtain a substrate 2 having a separation layer (I-1).

  The substrates 1 and 2 are bonded so that the separation layer (I-1) and the adhesive layer (II-1) are in contact with each other, and a force of 0.05 MPa is applied at 180 ° C. for 60 seconds using a die bonder device. The silicon wafer and the glass substrate were temporarily fixed via a temporary fixing material.

  Using a universal bond tester (trade name “Daily 4000”, manufactured by Daisy Co., Ltd.), a shearing force (speed of 500 μm / sec, 23 ° C.) was applied in a direction parallel to the substrate surface. However, it was confirmed that the silicon wafer and the glass substrate were held (temporarily fixed) without being displaced.

Next, using a universal bond tester (trade name “Digi 4000”, manufactured by Daisy) on the temporarily fixed substrate 1, a hook pull method (with respect to the z axis) in the direction perpendicular to the substrate surface (z axis). 0 °) force (500 μm / sec rate, 23 ° C.) was applied. As a result, the glass substrate could be peeled with a force of less than 0.2 MPa.
After the temporary fixing material residue on the substrate 1 after peeling was washed with mesitylene, the state of the bump was visually observed. As a result, it was found that the bump was not deformed and could be peeled well.

[Examples 9B to 10B, Comparative Example 3B]
In Example 8B, it was carried out similarly to Example 8B except having changed the composition for temporary fixing as described in Table 2. The results are shown in Table 2.

DESCRIPTION OF SYMBOLS 1 ... Laminated body 10 ... Support body 20 ... Temporary fixing material 21 ... Separation layer (I)
22 ... Adhesive layer (II)
30 ... Base material 31 ... Base material surface

Claims (10)

(1) A step of forming a laminate having a support, a temporary fixing material, and a base material, wherein the temporary fixing material comprises a conjugated diene compound (a1) and a polymerizable double bond-containing aromatic compound (a2). At least a layer (I) containing a copolymer and at least one component (A) selected from hydrogenated products of the copolymer and a compound (B) having a polysiloxane structure (b1) And;
(2) a step of processing the substrate and / or moving the laminate; and (3) the substrate and / or the support in a direction substantially perpendicular to the substrate surface of the substrate. Separating the substrate from the support by applying force;
A method for treating a substrate, comprising:   The method for treating a substrate according to claim 1, wherein the component (A) is a hydrogenated product of a copolymer of a conjugated diene compound (a1) and a polymerizable double bond-containing aromatic compound (a2).   The base material according to claim 1 or 2, wherein the compound (B) further has at least one structure (b2) selected from a polyoxyalkylene structure, a structure having a phosphate group, and a structure having a sulfo group. Processing method.   The processing method of the base material of any one of Claims 1-3 with which the said temporary fixing material further has the layer (II) which does not contain the said compound (B) substantially.   The processing method of the base material of Claim 4 with which the said laminated body has each element in order of the said support body, the said layer (I), the said layer (II), and the said base material as a layer structure. It is a laminate having a support, a layer (I) and a substrate in this order as a layer structure,
The layer (I) comprises at least one component (A) selected from a copolymer of a conjugated diene compound (a1) and a polymerizable double bond-containing aromatic compound (a2), and a hydrogenated product of the copolymer. And a compound (B) having a polysiloxane structure (b1). It is a laminate having a support, a layer (I), a layer (II) and a substrate in this order as a layer structure,
The layer (I) comprises at least one component (A) selected from a copolymer of a conjugated diene compound (a1) and a polymerizable double bond-containing aromatic compound (a2), and a hydrogenated product of the copolymer. And a compound (B) having a polysiloxane structure (b1),
The layered product, wherein the layer (II) does not substantially contain the compound (B).   The manufacturing method of a semiconductor device which processes a base material with the processing method of the base material of any one of Claims 1-5, and manufactures a semiconductor device.   A semiconductor device obtained by the manufacturing method according to claim 8. A copolymer of a conjugated diene compound (a1) and a polymerizable double bond-containing aromatic compound (a2), and at least one component (A) selected from hydrogenated products of the copolymer;
A composition for temporary fixing comprising a compound (B) having a polysiloxane structure (b1).

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