TWI765038B - Semiconductor device and method for manufacturing same - Google Patents

Abstract

A method for manufacturing a semiconductor device, including: preparing a semiconductor chip with a protective film in which at least a first protective film is provided on a first surface having bumps of the semiconductor chip or a second protective film is provided on a second surface of the semiconductor chip opposite to the first surface; and preparing a laminated structure in which the semiconductor chip with the protective film is bonded to the substrate via the bumps, wherein, in preparing the semiconductor chip with the protective film, the first protective film is formed so that the upper portion of the bumps protrudes through the first protective film, and the first protective film or the second protective film has a properties that the shear strength ratio of the laminated structure is 1.05 to 2 and the risk factor of fracture is -0.9 to 0.9.

Description

Semiconductor device and method of manufacturing the same

The present invention relates to a semiconductor device and a manufacturing method thereof.

This application claims priority based on Japanese Patent Application No. 2017-097994 for which it applied in Japan on May 17, 2017, and the content of the application is incorporated herein by reference.

In the past, when a multi-pin LSI (Large Scale Integration) package used in an MPU (Micro Processor Uint; microprocessor unit) or a gate array, etc., was packaged and mounted on a printed wiring board, The following flip-chip mounting method is employed in which bump electrodes (hereinafter, referred to as "bumps" in this specification) made of eutectic solder, high-temperature solder, gold, etc. are formed on the connection pads of the semiconductor chip. For the semiconductor wafer, by the so-called face down method, these bumps are brought into face-to-face contact with the corresponding terminal portions on the wafer mounting substrate, and fusion/diffusion bonding is performed.

Bumps are formed on the circuit surface of the semiconductor chip used in this mounting method. Further, depending on the purpose, a resin film may be formed on the circuit surface (in other words, the bump forming surface) of the semiconductor wafer or the back surface opposite to the circuit surface (see Patent Documents 1 to 3).

For example, the above-mentioned semiconductor wafer is obtained by dicing and singulating a semiconductor wafer having bumps formed on a circuit surface. In addition, the surface on the opposite side to the circuit surface (bump formation surface) in the above-mentioned semiconductor wafer may also be ground. In the process of obtaining such a semiconductor wafer, for the purpose of protecting the bump-forming surface and the bumps of the semiconductor wafer, a curable resin film is sometimes attached to the bump-forming surface, and the film is cured to form the bumps. A protective film is formed on the formation surface.

In addition, when the flip-chip mounting method is employed, the back surface of the semiconductor wafer on the opposite side to the circuit surface (bump formation surface) may be exposed. Therefore, in order to prevent the occurrence of cracks in the semiconductor wafer when the semiconductor wafer having bumps formed on the circuit surface is diced or the semiconductor wafer obtained by dicing is packaged to manufacture a semiconductor device, there are cases in which the semiconductor wafer is cracked. On the backside of the wafer, a resin film composed of an organic material is formed as a protective film.

Such a semiconductor wafer having the above-mentioned protective film as a resin film is commonly used in the manufacturing process of semiconductor devices, and is particularly important.

[Prior Art Literature]

[Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2012-169484.

Patent Document 2: Japanese Patent Laid-Open No. 2013-030766.

Patent Document 3: Japanese Patent No. 3957244.

On the other hand, in the case of manufacturing a semiconductor device or in the case of using the obtained semiconductor device, in a state where a semiconductor wafer provided with a protective film is bonded to a substrate, it is sometimes placed under high temperature conditions or low temperature conditions, and sometimes Exposure to severe temperature conditions. In this case, the bonding state of the semiconductor chip provided with the protective film and the substrate may be damaged due to such a temperature change. Therefore, for a semiconductor wafer provided with a protective film, it is desired that the bonding to the substrate is maintained in a stable state even under conditions of severe temperature changes.

However, it is not certain whether the semiconductor wafers described in Patent Documents 1 to 3 have such stability.

Therefore, an object of the present invention is to provide a semiconductor device and a method for manufacturing the same, which can maintain the bonding of the semiconductor wafer with the protective film to the substrate in a stable state even under conditions of severe temperature changes.

In order to solve the above-mentioned problems, the present invention includes the following aspects.

[1] A method of manufacturing a semiconductor device, comprising: producing a semiconductor wafer with a protective film, the semiconductor wafer with a protective film having at least a first protective film on a first surface of the semiconductor wafer having bumps, or on the semiconductor wafer The second surface on the opposite side of the first surface is provided with a second protective film; and a laminated structure is produced, the laminated structure is formed by bonding the semiconductor wafer with the protective film to the substrate through bumps; In the production of a semiconductor wafer with a protective film, the first protective film is formed so that the upper portion of the bumps protrudes through the first protective film; the first protective film or the second protective film is a protective film having the following characteristics : When the shear strength ratio and the fracture risk factor of the laminated structure were measured by the following method, the shear strength ratio was 1.05 to 2, and the fracture risk factor was -0.9 to 0.9.

<Shear strength ratio of laminated structure>

A test piece of the laminate structure in which the substrate is a copper substrate is produced, the copper substrate in the test piece of the laminate structure is fixed, and the edge of the semiconductor wafer with the protective film in the test piece of the laminate structure is relative to the above A force was applied in a direction parallel to the surface of the copper substrate, and the force when the bonding state of the semiconductor wafer with the protective film and the copper substrate was broken was set as the shear strength (N) of the laminated structure; This comparative test piece has the same structure as the test piece of the above-mentioned laminated structure except that it does not have the first protective film and the second protective film, and the above-mentioned test piece of the laminated structure is subjected to force in the same way The aforementioned force when the bonding state between the semiconductor wafer and the copper substrate of the comparative test piece is broken is referred to as the comparative shear strength (N) of the comparative laminated structure; The value of the [shear strength for comparison of the aforementioned laminated structure for comparison] is set as the shear strength ratio of the aforementioned laminated structure.

<Fracture Risk Factors of Laminated Structures>

A test piece having a width of 5 mm and a length of 20 mm for all the layers constituting the above-mentioned laminated structure was prepared, and all the above-mentioned test pieces were subjected to a heating and cooling test. ℃ and then cooled from 200 ℃ to -70 ℃ at a cooling rate of 5 ℃/min, and obtained the expansion amount Eμm of the test piece when the temperature was raised from 23 ℃ to 150 ℃, and the above-mentioned test when the temperature was decreased from 23 ℃ to -65 ℃. The total amount of the shrinkage amount S μm of the sheet, that is, the expansion and shrinkage amount ES μm, and then the value of [the expansion and shrinkage amount ES of the test piece]×[the thickness of the test piece], that is, the expansion and contraction parameter Pμm ² ; Next, obtain The value of [the expansion and contraction parameter P of the test piece of the substrate] - [the total value of the expansion and contraction parameters P of all the test pieces other than the substrate], that is, the difference between the expansion and contraction parameters ΔP1 μm ² ; The value of the expansion and contraction parameter P] - [the total value of the expansion and contraction parameters P of all test pieces except the substrate, the first protective film and the second protective film], that is, the expansion and contraction reference parameter difference ΔP0 μm ² ; The value of P1/ΔP0 is set as the fracture risk factor of the aforementioned laminated structure.

[2] A semiconductor device, comprising a layered structure in which a semiconductor wafer with bumps and a protective film is bonded to a substrate through the bumps; and the semiconductor chip with a protective film is at least one of the semiconductor chips in the semiconductor wafer. The first surface having bumps is provided with a first protective film, or the second surface of the semiconductor wafer on the opposite side to the first surface is provided with a second protective film; in the first protective film, the bumps are The upper part protrudes through the first protective film; the first protective film or the second protective film is a protective film having the following characteristics: when the shear strength ratio and the fracture risk factor of the laminated structure are measured by the following methods, the above The shear strength ratio becomes 1.05 to 2, and the aforementioned fracture risk factor becomes -0.9 to 0.9.

<Shear strength ratio of laminated structure>

A test piece of the laminate structure in which the substrate is a copper substrate is produced, the copper substrate in the test piece of the laminate structure is fixed, and the edge of the semiconductor wafer with the protective film in the test piece of the laminate structure is relative to the above A force was applied in a direction parallel to the surface of the copper substrate, and the force when the bonding state of the semiconductor wafer with the protective film and the copper substrate was broken was set as the shear strength (N) of the laminated structure; This comparative test piece has the same structure as the test piece of the above-mentioned laminated structure except that it does not have the first protective film and the second protective film, and the above-mentioned test piece of the laminated structure is subjected to force in the same way The aforementioned force when the bonding state between the semiconductor wafer and the copper substrate of the comparative test piece is broken is referred to as the comparative shear strength (N) of the comparative laminated structure; The value of the [shear strength for comparison of the aforementioned laminated structure for comparison] is set as the shear strength ratio of the aforementioned laminated structure.

<Fracture Risk Factors of Laminated Structures>

A test piece having a width of 5 mm and a length of 20 mm for all the layers constituting the above-mentioned laminated structure was prepared, and all the above-mentioned test pieces were subjected to a heating and cooling test. ℃ and then cooled from 200 ℃ to -70 ℃ at a cooling rate of 5 ℃/min, and obtained the expansion amount Eμm of the test piece when the temperature was raised from 23 ℃ to 150 ℃, and the above-mentioned test when the temperature was decreased from 23 ℃ to -65 ℃. The total amount of the shrinkage amount S μm of the sheet, that is, the expansion and shrinkage amount ES μm, and then the value of [the expansion and shrinkage amount ES of the test piece]×[the thickness of the test piece], that is, the expansion and contraction parameter Pμm ² ; Next, obtain The value of [the expansion and contraction parameter P of the test piece of the substrate] - [the total value of the expansion and contraction parameters P of all the test pieces other than the substrate], that is, the difference between the expansion and contraction parameters ΔP1 μm ² ; The value of the expansion and contraction parameter P] - [the total value of the expansion and contraction parameters P of all test pieces except the substrate, the first protective film and the second protective film], that is, the expansion and contraction reference parameter difference ΔP0 μm ² ; The value of P1/ΔP0 is set as the fracture risk factor of the aforementioned laminated structure.

According to the present invention, a semiconductor device and a method for manufacturing the same are provided, which can maintain the bonding of a semiconductor wafer with a protective film to a substrate in a stable state even under conditions of severe temperature changes.

1, 2, 3‧‧‧Laminated structure

9‧‧‧Laminated structure for comparison

10, 20, 30‧‧‧Semiconductor chip with protective film

11‧‧‧Semiconductor Chips

11a‧‧‧Side 1 of semiconductor chip

11b‧‧‧Side 2 of semiconductor wafer

12‧‧‧First protective film

13‧‧‧Second protective film

14‧‧‧Substrate

14a‧‧‧First side of the substrate

82‧‧‧Curable resin layer (curable resin film)

111‧‧‧Bumps

111a‧‧‧Bump surface

801, 802‧‧‧First protective film forming sheet

810, 820‧‧‧1st support film

810a, 820a, 812a‧‧‧The surface of the first support sheet

811‧‧‧First Substrate

812‧‧‧First adhesive layer

821‧‧‧Peeling film

821a‧‧‧Surface of release film

1110‧‧‧Top of bump

FIG. 1 is a cross-sectional view schematically showing an embodiment of a laminated structure produced by the production method of the present invention.

FIG. 2 is a cross-sectional view schematically showing an example of a laminated structure for comparison used when the production method of the present invention is applied.

FIG. 3 is a cross-sectional view schematically showing another embodiment of the laminated structure produced by the production method of the present invention.

FIG. 4 is a cross-sectional view schematically showing still another embodiment of the laminated structure produced by the production method of the present invention.

5 is a cross-sectional view schematically showing an example of the first protective film forming sheet used in the production method of the present invention.

6 is a cross-sectional view schematically showing another example of the sheet for forming a first protective film used in the production method of the present invention.

‧Manufacturing method of semiconductor device

A method of manufacturing a semiconductor device according to an embodiment of the present invention includes a step of manufacturing a semiconductor wafer with a protective film (in this specification, it may be abbreviated as "the production step of a semiconductor wafer with a protective film"), the protective film The semiconductor wafer is provided with a first protective film at least on a first surface of the semiconductor wafer having bumps, or a second protective film is provided on a second surface of the semiconductor wafer on the opposite side of the first surface; and a build-up structure is produced The step of forming the body (in this specification, sometimes abbreviated as "the step of fabricating the laminated structure"), the laminated structure is formed by bonding the semiconductor wafer with the protective film to the substrate through bumps; In the production of the wafer, when the semiconductor wafer with the protective film is provided with the first protective film, the first protective film is formed in such a way that the upper portion of the bump protrudes through the first protective film; the first protective film is formed. The film or the second protective film is a protective film having the following characteristics. That is, when the shear strength ratio and the fracture risk factor of the laminated structure are measured, the shear strength ratio is 1.05 to 2, and the fracture risk factor is - 0.9 to 0.9.

<Shear strength ratio of laminated structure>

A test piece of the laminate structure in which the substrate is a copper substrate is produced, the copper substrate in the test piece of the laminate structure is fixed, and the semiconductor wafer with the protective film in the test piece of the laminate structure is aligned along the opposite direction. When force is applied in a direction parallel to the surface of the copper substrate (that is, the upper surface of the copper substrate when the copper substrate is placed on a flat surface), the bonding state between the semiconductor chip with the protective film and the copper substrate is broken. The force is set as the shear strength (N) of the above-mentioned laminated structure; a laminated structure for comparison (also referred to as a test piece for comparison) is prepared, except that the laminated structure for comparison does not have the first protective film and the second protective film. Except for this aspect, the structure is the same as that of the above-mentioned laminated structure, and the force is applied by the same method as that of the above-mentioned laminated test piece, and the above-mentioned force when the bonding state of the semiconductor wafer and the copper substrate of the above-mentioned comparative test piece is broken is set as the above-mentioned comparative test piece. Shear strength (N) for comparison of the laminated structure; the value of [the shear strength of the laminated structure]/[the shear strength for comparison of the laminated structure for comparison] at this time is set as the laminated structure shear strength ratio.

<Fracture Risk Factors of Laminated Structures>

A test piece having a width of 5 mm and a length of 20 mm when viewed from above and a plan view of all the layers constituting the above-mentioned laminated structure was produced, and a heating and cooling test was performed on all the above-mentioned test pieces, that is, the temperature was increased from -70°C at a rate of temperature increase. The temperature was raised from 5°C/min to 200°C, the temperature was lowered from 200°C to -70°C at a cooling rate of 5°C/min. The total amount of shrinkage S μm of the test piece at −65° C., that is, the expansion and shrinkage amount ES μm, and the value of [expansion and shrinkage amount ES of the test piece]×[thickness of the test piece], that is, the expansion and shrinkage parameter. Pμm ² ; secondly, the value of [expansion-shrinkage parameter P of the test piece of the substrate]-[the total value of the expansion-shrinkage parameter P of all the test pieces other than the substrate], that is, the difference in expansion-shrinkage parameter ΔP1 μm ² is obtained; secondly, obtain The value of [expansion and shrinkage parameter P of the test piece of the substrate] - [the total value of the expansion and contraction parameter P of all the test pieces except the substrate, the first protective film and the second protective film], that is, the difference between the expansion and contraction reference parameters ΔP0 μm ² ; The value of ΔP1/ΔP0 at this time is set as the fracture risk factor of the aforementioned laminated structure.

In the method for manufacturing a semiconductor device of the present invention, a protective film having specific properties that satisfies the conditions of the above-mentioned laminated structure and the above-mentioned shear strength ratio and fracture risk factor is selected as the first layer constituting the semiconductor wafer with the protective film. The first protective film or the second protective film can obtain a semiconductor device in which the bonding of the semiconductor wafer with the protective film to the substrate is maintained in a stable state even under severe temperature changes.

The semiconductor device obtained by the manufacturing method of the present invention is not particularly limited as long as it includes the above-mentioned laminated structure.

‧Semiconductor chip with protective film

The semiconductor wafer with a protective film produced in the step of producing a semiconductor wafer with a protective film in the above-mentioned production method includes either a first protective film or a second protective film, or both of them. That is, the semiconductor wafer with the protective film may have the first protective film and not the second protective film, may have the second protective film and not have the first protective film, or may have both the first protective film and the second protective film. membrane.

The first protective film is a film formed on the first surface of the semiconductor wafer having bumps (in other words, the circuit surface or bump-forming surface of the semiconductor wafer), and is a resin film (curable resin layer described later). The first protective film protects the bumps and the first surface of the semiconductor wafer.

On the other hand, the second protective film is a film formed on the second surface (in other words, the back surface of the semiconductor wafer) opposite to the first surface of the semiconductor wafer, and is a resin film (curable resin layer described later). The second protective film prevents the semiconductor wafer from being damaged when the semiconductor wafer having bumps formed on the circuit surface is diced to manufacture the above-mentioned semiconductor wafer, or the semiconductor wafer obtained by dicing is packaged to manufacture a semiconductor device. Cracks occur.

Hereinafter, first, the laminated structure produced by the above-mentioned production method will be described.

‧Laminated structure

FIG. 1 is a cross-sectional view schematically showing an embodiment of the above-mentioned laminated structure produced by the above-mentioned manufacturing method. In addition, in the drawings used in the following description, in order to facilitate the understanding of the features of the present invention, and for convenience, the main part is sometimes shown enlarged, and the dimensional ratio of each component is not limited to the same as the actual one. .

The laminated structure 1 shown here is provided with the semiconductor wafer 10 and the board|substrate 14 with a protective film.

The semiconductor wafer 10 with a protective film includes the first protective film 12 on the first surface 11 a of the semiconductor wafer 11 and the second protective film 13 on the second surface 11 b of the semiconductor wafer 11 .

The semiconductor wafer 11 has a plurality of bumps 111 arranged on the first surface 11a of the semiconductor wafer 11 .

The first protective film 12 covers the first surface 11a of the semiconductor wafer 11 and the regions on the side closer to the first surface 11a of the semiconductor wafer 11 among the surfaces 111a of the bumps 111, and protects these covered regions.

The upper portion 1110 of the bump 111 , that is, the top portion of the bump 111 on the side away from the first surface 11 a of the semiconductor wafer 11 and its vicinity pass through the first protective film 12 and protrude from the surface (exposed surface) of the first protective film 12 . In addition, the surface of the substrate 14 facing the semiconductor wafer 10 with the protective film (in this specification, it may be referred to as the "first surface" of the substrate) 14a and the protruding portions of the bumps 111 (for example, the aforementioned top) contact, so that the substrate 14 is electrically connected to the semiconductor chip 10 with the protective film.

In this way, the semiconductor wafer 10 with the protective film attached to the laminated structure 1 is formed by being bonded to the substrate 14 via the bumps 111 .

Next, the aforementioned shear strength ratio of the laminated structure 1 will be described.

In the manufacturing method of the semiconductor device provided with the laminated structure 1, the shear strength of the laminated structure 1 in the case where the substrate 14 is a copper substrate means that the substrate 14 is fixed, and the semiconductor wafer 10 with the protective film is attached along the relative direction. The surface of the substrate 14 (that is, the upper surface of the substrate when the substrate is placed on a flat surface, for example, the first surface 14a ) is applied in a direction parallel to the direction, and the bonding state between the semiconductor wafer 10 with the protective film and the substrate 14 is broken. , the aforementioned force applied to the semiconductor wafer 10 with the protective film.

When the aforementioned force is applied to the semiconductor wafer 10 with the protective film, it is preferable to include the semiconductor wafer 11 in the region where the force is applied, for example, only the aforementioned force is applied to the semiconductor wafer 11 .

In the above-mentioned manufacturing method, as the laminated structure for comparison corresponding to the laminated structure 1 for obtaining the above-mentioned shear strength ratio, a structure except that the first protective film 12 and the second protective film 13 are not provided is used. The same laminated structure as Laminated Structure 1. An example of such a laminated structure for comparison is shown in FIG. 2 . FIG. 2 is a cross-sectional view schematically showing an example of a laminated structure for comparison with the aforementioned manufacturing method. In FIG. 2 , the reference numeral 9 denotes a laminated structure for comparison.

2 and later, the same components as those shown in FIG. 1 are denoted by the same reference numerals as in the case of FIG. 1, and detailed descriptions of the components are omitted.

In the aforementioned manufacturing method, the shear strength (N) for comparison of the laminated structure 9 for comparison means that the same method as in the case of the laminated structure 1 is used, that is, the substrate 14 is fixed, and the semiconductor wafer 11 is opposed along the A force (N) is applied in a direction parallel to the surface of the substrate 14 (that is, the upper surface of the substrate when the substrate is placed on a flat surface, for example, the first surface 14a), and the bonding state between the semiconductor chip 11 and the substrate 14 is broken. , the aforementioned force (N) applied to the semiconductor wafer 11 .

In the manufacturing method of the semiconductor device including the laminated structure 1, the value of [the shear strength of the laminated structure 1 (N)]/[the comparative shear strength (N) of the laminated structure 9 for comparison] is the value of the laminated structure. The shear strength ratio of Structure 1 was 1.05 to 2.

Next, the aforementioned fracture risk factor of the laminated structure 1 will be described.

In order to calculate the fracture risk factor of the laminated structure 1 , first, a test piece is prepared which comprises all the layers of the laminated structure 1 , that is, the semiconductor wafer 11 , the first protective film 12 , the second protective film 13 and the substrate 14 . It becomes a test piece with a width of 5 mm and a length of 20 mm when viewed from above and in a plan view. The thicknesses of the test pieces of these respective layers were set to be the same as the thicknesses of the respective layers in the laminated structure 1 .

Next, with respect to all these test pieces, a heating and cooling test was performed, that is, the temperature was increased from -70°C to 200°C at a temperature increase rate of 5°C/min, and the temperature was decreased from 200°C to -70°C at a temperature drop rate of 5°C/min, and the measurement The amount of expansion Eμm of the test piece when the temperature was raised from 23°C to 150°C (E>0), and the amount of shrinkage Sμm of the test piece when the temperature was lowered from 23°C to -65°C (S>0). Then, for each test piece, the total amount of the amount of expansion E and the amount of contraction S, that is, the amount of expansion and contraction ES μm was obtained.

Furthermore, for each test piece, the value of [expansion and shrinkage amount ES (μm) of the test piece]×[the thickness of the test piece (μm)], that is, the expansion and contraction parameter Pμm ² was obtained.

Next, the value of [expansion and shrinkage parameter P (μm ² ) of the test piece of the substrate 14 ] - [the total value of the expansion and contraction parameter P of all the test pieces other than the substrate 14 (μm ² )], that is, the difference in expansion and contraction parameter is obtained. ΔP1 μm ² .

More specifically, in the case of the laminated structure 1, the difference in expansion and contraction parameters ΔP1 μm ² is determined by [expansion and contraction parameter P (μm ² ) of the test piece of the substrate 14 ]−([the difference of the test piece of the semiconductor wafer 11 . Expansion and shrinkage parameter P(μm ² )]+[expansion and shrinkage parameter P(μm ² ) of the test piece of the first protective film 12]+[expansion and contraction parameter P(μm ² ) of the test piece of the second protective film 13 ]) and calculate.

Next, [the expansion and contraction parameter P of the test piece of the substrate 14 (μm ² )] - [the total value (μm ² ) of the expansion and contraction parameter P of all the test pieces except the substrate, the first protective film, and the second protective film is obtained. The value of ] is the reference parameter difference ΔP0 of expansion and contraction.

More specifically, in the case of the laminated structure 1, the difference ΔP0 μm ² in the reference parameter of expansion and contraction is determined by [expansion and contraction parameter P (μm ² ) of the test piece of the substrate 14 ]−[the difference of the test piece of the semiconductor wafer 11 . The expansion and contraction parameter P (μm ² )] was calculated.

In the manufacturing method of the semiconductor device provided with the laminated structure 1, the value of ΔP1/ΔP0, that is, the fracture risk factor of the laminated structure 1 is -0.9 to 0.9.

FIG. 3 is a cross-sectional view schematically showing another embodiment of the above-mentioned laminated structure produced by the above-mentioned manufacturing method.

The layered structure 2 shown here is the same as the layered structure 1 shown in FIG. 1 except that the second protective film 13 is not provided.

The laminated structure 2 is formed by bonding the semiconductor wafer 20 with the protective film to the substrate 14 via the bumps 111 .

In the manufacturing method of the semiconductor device provided with the laminated structure 2, the value of [the shear strength of the laminated structure 2 (N)]/[the comparative shear strength (N) of the laminated structure 9 for comparison] is the value of the laminated structure. The shear strength ratio of Structure 2 was 1.05 to 2.

In the manufacturing method of the semiconductor device provided with the laminated structure 2, the value of ΔP1/ΔP0, that is, the fracture risk factor of the laminated structure 2 is -0.9 to 0.9.

In the case of the laminated structure 2, the difference in expansion and contraction parameters ΔP1 μm ² is determined by [expansion and contraction parameter P (μm ² ) of the test piece of the substrate 14 ]−([the expansion and contraction parameter P of the test piece of the semiconductor wafer 11 ( μm ² )]+[expansion and contraction parameter P(μm ² )] of the test piece of the first protective film 12 ) was calculated.

On the other hand, in the case of the laminated structure 2, the difference ΔP0 μm ² in the reference parameter of expansion and contraction is the same as in the case of the laminated structure 1, by [expansion and contraction parameter P (μm ² ) of the test piece of the substrate 14 ] − [Expansion and contraction parameter P (μm ² ) of the test piece of the semiconductor wafer 11 ] is calculated.

FIG. 4 is a cross-sectional view schematically showing still another embodiment of the above-mentioned laminated structure produced by the above-mentioned manufacturing method.

The layered structure 3 shown here is the same as the layered structure 1 shown in FIG. 1 except that the first protective film 12 is not provided.

The laminated structure 3 is formed by bonding the semiconductor wafer 30 with the protective film to the substrate 14 via the bumps 111 .

In the manufacturing method of the semiconductor device including the laminated structure 3, the value of [the shear strength of the laminated structure 3 (N)]/[the comparative shear strength of the laminated structure 9 for comparison (N)] is the value of the laminated structure. The shear strength ratio of the structure 3 was 1.05 to 2.

In the manufacturing method of the semiconductor device provided with the laminated structure 3, the value of ΔP1/ΔP0, that is, the fracture risk factor of the laminated structure 3 is -0.9 to 0.9.

In the case of the laminated structure 3, the difference in expansion and contraction parameters ΔP1 μm ² is determined by [expansion and contraction parameter P (μm ² ) of the test piece of the substrate 14 ]−([the expansion and contraction parameter P of the test piece of the semiconductor wafer 11 ( μm ² )]+[expansion and contraction parameter P (μm ² )] of the test piece of the second protective film 13 ) was calculated.

On the other hand, in the case of the laminated structure 3, the difference ΔP0 μm ² in the reference parameter of expansion and contraction is the same as in the case of the laminated structure 1, and is determined by [expansion and contraction parameter P (μm ² ) of the test piece of the substrate 14 ] − [Expansion and contraction parameter P (μm ² ) of the test piece of the semiconductor wafer 11 ] is calculated.

The laminated structure produced by the above-mentioned manufacturing method is not limited to the laminated structure shown in FIG. 1 and FIGS. In the shown laminated structure, a part of the structure is changed, deleted or added.

For example, the aforementioned laminated structure may include layers other than the semiconductor wafer 11 , the first protective film 12 , the second protective film 13 , and the substrate 14 .

The said other layer is not specifically limited, According to the objective, it can select arbitrarily. As a preferable said other layer, the intermediate layer (1st intermediate layer, 2nd intermediate layer) mentioned later is mentioned, for example.

The other layer may be constituted by one layer (single layer), or may be constituted by a plurality of layers of two or more layers. When the aforementioned other layers are composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited as long as the effect of the present invention is not impaired.

Furthermore, in this specification, it is not limited to the case of the other layers mentioned above, and the so-called "multiple layers may be the same or different from each other" means "all layers may be the same, all layers may be different, or only a part of the layers may be the same", Furthermore, "multiple layers are different from each other" means "at least one of the constituent material and thickness of each layer is different from each other".

The above-mentioned layered structure may also include the other layers described above on any one of the semiconductor chip with a protective film (eg, the semiconductor chip with a protective film 10 , 20 or 30 ) and the substrate (eg, the substrate 14 ). Among them, in terms of easier adjustment of the above-mentioned shear strength ratio and fracture risk factor, it is preferable that any part of the semiconductor wafer with the protective film is provided with the above-mentioned other layers in a state of direct contact.

In the case of having a laminated structure of the other layers described above, when ΔP1 was obtained, the test pieces of the other layers were regarded as "all test pieces other than the substrate". Similarly, when ΔP0 is determined, the test pieces of the other layers described above are regarded as "all test pieces other than the substrate, the first protective film, and the second protective film".

In the aforementioned manufacturing method, the shear strength ratio of the aforementioned laminated structure is 1.05 to 2, preferably 1.1 to 1.65, more preferably 1.15 to 1.3. Since the shear strength ratio is above the lower limit value, the bonding of the semiconductor wafer with the protective film to the substrate is maintained in a stable state in the laminate structure in the semiconductor device even under severe temperature changes. effect becomes higher. On the other hand, when the shear strength ratio is equal to or less than the upper limit value, it is possible to prevent the bonding force between the semiconductor wafer with the protective film and the substrate from becoming excessively strong, for example, the reliability of the semiconductor device is further improved, and the semiconductor device ( The production of the aforementioned laminated structure) itself becomes easier.

The shear strength ratio of the laminated structure can be adjusted by adjusting the shear strength of the laminated structure. The shear strength of the above-mentioned laminated structure can be adjusted, for example, by adjusting the hardness (hardening degree) of the first protective film or the second protective film, and the hardness of the first protective film or the second protective film can be adjusted by these constituent materials, thickness, etc. For example, it is presumed that by increasing the hardness of the first protective film or the second protective film, the force (shearing force) applied to the semiconductor wafer with the protective film is more favorably dispersed in these protective films. As a result, the above-mentioned laminated structure is assumed to be The shear strength of the body is increased.

In the above-mentioned manufacturing method, the fracture risk factor of the above-mentioned laminated structure is -0.9 to 0.9, and may be any one of -0.8 to 0.8 and -0.5 to 0.5. Since the above-mentioned fracture risk factor is within this range, even under the conditions of severe temperature changes, in the above-mentioned laminated structure in the semiconductor device, the bonding of the semiconductor chip with the protective film to the substrate is maintained in a stable state. Becomes high. In particular, when the breakage risk factor is -0.9 or more, it is possible to further suppress the portion (root portion) on the first surface side of the semiconductor wafer in the bump, the top portion on the opposite side to the first surface side, and its vicinity. damage in.

Generally, in the above-mentioned laminated structure, when the temperature changes, the semiconductor chip is less likely to expand and contract than the substrate (the substrate is more likely to expand and contract than the semiconductor chip). On the other hand, the first protective film and the second protective film are usually more likely to expand and contract than the semiconductor wafer, so the semiconductor chip with the protective film is more likely to follow the expansion and contraction of the substrate when the temperature changes than the semiconductor chip alone. Therefore, the effect of the present invention can be obtained by the fracture risk factor being within the aforementioned range.

The said board|substrate is not specifically limited, According to the objective, it can select arbitrarily.

For example, the constituent materials of the substrate include metals such as copper, gold, and aluminum; resins such as polyimide and epoxy resin; ceramics such as alumina and glass.

The constituent material of the substrate may be only one type or two or more types, and in the case of two or more types, the combination and ratio of these may be arbitrarily selected. For example, as a board|substrate which consists of two or more types of constituent materials, the board|substrate which consists of a polymer alloy which uses 2 or more types of resin together, the board|substrate which consists of a resin component and a non-resin component material, such as glass epoxy resin, are mentioned. Among them, these are an example.

The thickness of the substrate is not particularly limited, but is preferably 10 m to 3000 m, more preferably 100 m to 2000 m, still more preferably 500 m to 1000 m. When the thickness of the substrate is within such a range, the effect of the present invention becomes higher.

The thickness of the first protective film is not particularly limited, but is preferably 1 μm to 100 μm, more preferably 5 μm to 75 μm, and particularly preferably 5 μm to 50 μm. When the thickness of the first protective film is equal to or greater than the aforementioned lower limit value, the first protective film can affect the first surface of the semiconductor wafer, the surface having bumps (circuit surface or bump-forming surface) of the semiconductor wafer, and the semiconductor wafer. And the protection ability of bumps of semiconductor wafers becomes higher. Moreover, since the thickness of a 1st protective film is below the said upper limit value, it can suppress that thickness becomes too thick.

In addition, in this specification, regarding the "semiconductor wafer having bumps on the surface", as in the case of the semiconductor wafer having bumps on the surface, the surface having bumps (the circuit surface of the semiconductor wafer) may be referred to as the (or bump formation surface) is called a 1st surface, and the surface on the opposite side to the 1st surface (in other words, the back surface of a semiconductor wafer) is called a 2nd surface.

The thickness of the second protective film is not particularly limited, but is preferably 1 μm to 100 μm, more preferably 5 μm to 75 μm, and particularly preferably 5 μm to 50 μm. When the thickness of the second protective film is equal to or more than the aforementioned lower limit value, the ability of the second protective film to protect the semiconductor wafer becomes higher. Moreover, since the thickness of a 2nd protective film is below the said upper limit value, it can suppress that thickness becomes too thick.

The thickness of the semiconductor wafer is not particularly limited, but is preferably 20 μm to 1000 μm, more preferably 40 μm to 500 μm, for example, 100 μm to 300 μm. When the thickness of the semiconductor wafer is within such a range, the effect of the present invention becomes higher.

In addition, in this specification, the "thickness of a semiconductor wafer" means "thickness of the part other than a bump in a semiconductor wafer" unless otherwise specified. That is, the thickness of the semiconductor wafer does not include the height of the bumps described later.

The type and arrangement form of the bumps in the semiconductor wafer can be arbitrarily selected according to the purpose, and are not particularly limited.

For example, the height of the bump is not particularly limited, but is preferably 120 μm to 300 μm, more preferably 150 μm to 270 μm, and particularly preferably 180 μm to 240 μm. When the height of the bump is equal to or more than the aforementioned lower limit value, the function of the bump can be further improved. In addition, when the height of the bump is equal to or less than the above-mentioned upper limit value, when the curable resin film for forming the first protective film is attached to the first surface of the semiconductor wafer, the curable resin film is suppressed from remaining on the upper portion of the bump. effect becomes higher.

In addition, in this specification, the "height of a bump" means the height which exists in the position which exists in the highest position from a semiconductor wafer or a 1st surface of a semiconductor chip in a bump.

The width of the bump is not particularly limited, but is preferably 170 μm to 350 μm, more preferably 200 μm to 320 μm, and particularly preferably 230 μm to 290 μm. By making the width of the bump more than the aforementioned lower limit value, the function of the bump can be further improved. In addition, when the width of the bump is equal to or less than the upper limit value, when the curable resin film for forming the first protective film is attached to the first surface of the semiconductor wafer, the curable resin film is suppressed from remaining on the upper portion of the bump. effect becomes higher.

Furthermore, in this specification, the so-called "bump width" refers to the difference in the bump surface when viewed from the semiconductor wafer or the first surface perpendicular to the first surface of the semiconductor wafer and viewed from the top. The maximum value of the line segment obtained by connecting two points of .

The distance between adjacent bumps is not particularly limited, but is preferably 250 μm to 800 μm, more preferably 300 μm to 600 μm, and particularly preferably 350 μm to 500 μm. By making the said distance more than the said lower limit value, the function of a bump can be improved further. Moreover, when the said distance is below the said upper limit value, when the curable resin film for forming the 1st protective film is attached to the 1st surface of the semiconductor wafer, the effect of suppressing the curable resin film remaining on the bump upper part is suppressed. become higher.

In addition, in this specification, the so-called "distance between adjacent bumps" means the minimum value of the distance between the surfaces of adjacent bumps.

Next, the above-mentioned production method will be described more specifically.

‧Semiconductor wafer fabrication steps with protective film

Regarding the above-mentioned manufacturing steps of the semiconductor wafer with a protective film, for example, a semiconductor wafer with a protective film with a first protective film on the first surface of the semiconductor wafer can be produced in the following manner, that is, for forming the first protective film After the curable resin film of the film is attached to the first surface (bump formation surface, circuit surface) of the semiconductor wafer, the curable resin film is cured to form a first protective film, and the first protective film is formed by dicing. The semiconductor wafer is singulated (divided) together with the protective film, or the semiconductor wafer is singulated (divided) together with the curable resin film by dicing, and then the curable resin film is cured to form 1st protective film.

A semiconductor wafer with a protective film provided with a second protective film on the second surface of the semiconductor wafer can also be produced by the following method, which is different from that provided with the first protective film on the first surface except that the protective film is formed at a different point. The same is true for semiconductor wafers with protective films.

For example, a semiconductor wafer with a protective film having a second protective film on the second surface can be produced by attaching a curable resin film for forming the second protective film to the semiconductor wafer. After the second surface, the curable resin film is cured to form a second protective film, and then the semiconductor wafer is singulated (divided) together with the second protective film by dicing, or the semiconductor wafer is diced together with the second protective film. After this curable resin film sings (divides) the semiconductor wafer together, the curable resin film is cured to form a second protective film.

In the case of producing a semiconductor wafer with a protective film including a first protective film and a second protective film together, the order of forming these protective films is not particularly limited. For example, the second protective film may be formed after the first protective film is formed, the first protective film may be formed after the second protective film is formed, or the first protective film and the second protective film may be formed simultaneously.

More specifically, for example, any one of attaching the curable resin film for forming the first protective film to the semiconductor wafer and attaching the curable resin film for forming the second protective film to the semiconductor wafer may be performed first. One can be carried out later and the other can be carried out at the same time.

In addition, the formation of the 1st protective film by hardening of a curable resin film, and the formation of the 2nd protective film by hardening of a curable resin film may be performed first, either one may be performed first, and the other may be performed at the same time.

The formation of the first protective film can be performed, for example, using a first protective film-forming sheet including a first support sheet and a curable resin for forming a first protective film on the first support sheet. made of membrane. In addition, in this specification, a "curable resin film" may be called a "curable resin layer".

When using the sheet for 1st protective film formation, the sheet for 1st protective film formation is stuck to the 1st surface of a semiconductor wafer via the curable resin layer (curable resin film) which comprises the sheet for 1st protective film formation. Then, by heating the above-mentioned curable resin layer after the sticking, the fluidity of the curable resin layer is increased, and it spreads between the bumps so as to cover the bumps, and is in close contact with the first part of the semiconductor wafer. The bumps are embedded in the curable resin layer so as to cover the surfaces of the bumps, especially the surfaces of the regions near the first surface of the semiconductor wafer. Thus, the formation of the curable resin layer on the first surface of the semiconductor wafer is completed. The first protective film is formed by curing the curable resin layer formed on the semiconductor wafer or the first surface of the semiconductor wafer by heating or irradiating energy rays at a target timing. The first protective film protects the semiconductor wafer or the first surface and bumps of the semiconductor wafer in a state of being in close contact with these.

The first support sheet in the sheet for forming the first protective film may be removed at a suitable time point before and after the curing of the curable resin layer.

The formation of the second protective film can be performed, for example, using a second protective film-forming sheet having a second supporting sheet and a curability for forming a second protective film disposed on the second supporting sheet. Resin film (curable resin layer).

When the second protective film forming sheet is used, the second protective film forming sheet is attached to the second surface of the semiconductor wafer via the curable resin layer (curable resin film) constituting the second protective film forming sheet. Thereby, the formation of the curable resin layer on the second surface of the semiconductor wafer is completed. A second protective film is formed by curing the curable resin layer formed on the semiconductor wafer or the second surface of the semiconductor chip by heating or irradiating energy rays at a target timing. The second protective film protects the semiconductor wafer or the second surface of the semiconductor wafer in a state of being in close contact with the second surface.

What is necessary is just to remove the 2nd support sheet in the sheet for 2nd protective film formation at a suitable time point before and after hardening of a curable resin layer. In addition, the second support sheet can also be used as a dicing sheet when dicing a semiconductor wafer having a curable resin layer or a second protective film serving as a cured product of the curable resin layer.

Furthermore, in this specification, when the curable resin layer hardens to become the first protective film, as long as the laminated structure of the first support sheet and the first protective film is maintained, the laminated product is also referred to as the first protective film. Sheet for film formation. Similarly, when the curable resin layer hardens and becomes a 2nd protective film, as long as the laminated structure of a 2nd support sheet and a 2nd protective film is maintained, this laminated body is also called the sheet for 2nd protective film formation.

Hereinafter, the structure of the sheet|seat for 1st protective film formation is demonstrated.

◇First protective film forming sheet

◎The first support film

The above-mentioned first support sheet may be constituted by one layer (single layer), or may be constituted by a plurality of layers of two or more layers. When the support sheet is composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited as long as the effect of the present invention is not impaired.

As a preferable first support sheet, for example, a sheet including a first base material, and a first adhesive layer is laminated on the first base material; and a sheet including a first base material, on the first base material The first intermediate layer is laminated and the first adhesive layer is laminated on the first intermediate layer; the sheet is composed of only the first base material; the sheet is composed of only the release film, etc.

In addition, the sheet for 1st protective film formation may be equipped with the energy ray hardened|cured material of the energy ray curable 1st adhesive bond layer mentioned later instead of a 1st adhesive bond layer.

○The first base material

The said 1st base material is a sheet shape or a film shape, and as a constituent material of the said base material, various resins are mentioned, for example.

Examples of the aforementioned resins include low-density polyethylene (abbreviated as LDPE; low-density polyethylene), linear low-density polyethylene (abbreviated as LLDPE; linear low-density polyethylene), and high-density polyethylene (abbreviated as HDPE; high-density polyethylene). Polyethylene such as polyethylene); Polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, bornene resin; Ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid Ethylene-based copolymers such as copolymers, ethylene-(meth)acrylate copolymers, and ethylene-bornene copolymers (that is, copolymers obtained by using ethylene as a monomer); polyvinyl chloride, vinyl chloride copolymers, etc. Vinyl chloride-based resins (that is, resins obtained using vinyl chloride as a monomer); polystyrene; polycyclic olefins; polyethylene terephthalate, polyethylene naphthalate, polyethylene terephthalate Polyesters such as butylene glycol, polyethylene isophthalate, polyethylene 2,6-naphthalenedicarboxylate, and wholly aromatic polyesters having aromatic cyclic groups in all structural units; 2 or more of the foregoing Polyester copolymer; poly(meth)acrylate; polyurethane; polyacrylate urethane; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified Quality polyphenylene ether; polyphenylene sulfide; polysilver; polyether ketone, etc.

Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and resin other than the said polyester, can also be mentioned, for example. The polymer alloy of the aforementioned polyester and the aforementioned resin other than the aforementioned polyester is preferably used in a relatively small amount of the resin other than the polyester.

Moreover, as said resin, the crosslinked resin which crosslinks one type or two or more types of the above-mentioned resins exemplified above, and the ion polymerization using one type or two or more types of the above-mentioned resins exemplified above can also be mentioned, for example. Modified resins, etc.

In addition, in this specification, the concept of "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid". The same is true for terms similar to (meth)acrylic acid, for example, the concept of "(meth)acrylate" includes both "acrylate" and "methacrylate", and "(meth)acryloyl" The concept includes both "acryloyl" and "methacryloyl".

The resin constituting the first base material may be only one type or two or more types, and in the case of two or more types, the combination and ratio of these may be arbitrarily selected.

The first base material may be only one layer (single layer), or may be a multi-layer of two or more layers. In the case of a multi-layer, these layers may be the same or different from each other, and the combination of these layers is not particularly limited.

The thickness of the first base material is preferably 5 μm to 1000 μm.

Here, the "thickness of the first base material" means the thickness of the entire first base material, for example, the thickness of the first base material composed of multiple layers means the total thickness of all the layers constituting the first base material .

The first base material may contain various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, softeners (plasticizers), etc., in addition to the main constituent materials such as the aforementioned resins. .

In order to improve the adhesion between the first base material and the layers such as the first adhesive layer and the layer provided in contact with the first base material, the first base material may have an adhesion promoting coating on the surface of the first base material, or the surface may be treated with Retrofit.

The first base material can be produced by a known method. For example, the 1st base material containing resin can be manufactured by shaping|molding the resin composition containing the said resin.

○Release film

The aforementioned release film may be a release film known in the art.

As a preferable release film, for example, a release film in which at least one surface of a resin film such as polyethylene terephthalate is subjected to release treatment by polysiloxane treatment or the like; at least one surface of the film is made of poly The release film of the release surface composed of olefin, etc.

The thickness of the release film is preferably the same as the thickness of the first base material.

○The first adhesive layer

The said 1st adhesive agent layer is a sheet shape or a film shape, and contains an adhesive agent.

Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber-based resins, polysiloxane-based resins, epoxy-based resins, polyvinyl ethers, and polycarbonates, preferably It is acrylic resin.

Furthermore, in the present invention, the concept of "adhesive resin" includes both resins with adhesiveness and resins with adhesiveness. And resins showing adhesiveness, or resins showing adhesiveness triggered by the presence of heat or water, etc.

The first adhesive layer may be only one layer (single layer), or may be a multi-layer of two or more layers. In the case of a multi-layer, these layers may be the same or different from each other, and the combination of these layers is not particularly limited.

The thickness of the first adhesive layer is preferably 1 μm to 1000 μm.

Here, the "thickness of the first adhesive layer" means the thickness of the entire first adhesive layer, for example, the thickness of the first adhesive layer composed of multiple layers means the entire thickness of the first adhesive layer. The total thickness of the layers.

The first adhesive layer may be a layer formed of an energy ray-curable adhesive or a layer formed of a non-energy ray-curable adhesive. The physical properties of the first adhesive layer formed of the energy ray-curable adhesive can be easily adjusted before and after curing.

In this specification, the term "energy rays" means electromagnetic waves or charged particle beams having energy quanta, and examples of the energy rays include ultraviolet rays, radiation, and electron beams.

The ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H-type lamp, a xenon lamp, a black light lamp, or an LED (Light Emitting Diode; light emitting diode) lamp or the like as an ultraviolet source. The electron beam may be irradiated with an electron beam generated by an electron beam accelerator or the like.

In addition, in this specification, "energy ray curability" means the property of hardening by irradiation with energy rays, and the "non-energy ray hardening property" means the property of not hardening even when irradiated with energy rays.

<<The first adhesive composition>>

The first adhesive layer may be formed of a first adhesive composition containing an adhesive. For example, the 1st adhesive agent composition can be coated on the surface of the formation object of a 1st adhesive agent layer, and it can be dried as needed, and a 1st adhesive agent layer can be formed in a target site|part.

What is necessary is just to coat the 1st adhesive composition by a well-known method, for example, the method using the following various coaters: air knife coater, knife coater, bar coater, gravure coater, roll coater, Coater, Roll Knife Coater, Curtain Coater, Die Coater, Knife Coater, Screen Coater, Meyer Bar Coater, Contact Coating machine etc.

The drying conditions of the first adhesive composition are not particularly limited, and the first adhesive composition containing the solvent described later is preferably dried by heating. The first adhesive composition containing the solvent is preferably dried, for example, under the conditions of 70°C to 130°C for 10 seconds to 5 minutes.

When the first adhesive layer is energy ray curable, as the first adhesive composition containing the energy ray curable adhesive, that is, the energy ray curable first adhesive composition, for example, the following adhesives can be exemplified: Agent composition, etc.: First adhesive composition (I-1), containing non-energy ray-curable adhesive resin (I-1a) (hereinafter, sometimes abbreviated as "adhesive resin (I-1a)") , and an energy ray-curable compound; an adhesive composition (I-2) containing an energy ray-curable first adhesive resin (I-2a) (hereinafter, sometimes referred to as "adhesive resin (I-2a)" ”), the adhesive resin (I-2a) has an unsaturated group introduced into the side chain of the non-energy ray-curable adhesive resin (I-1a); the first adhesive composition (I-3) contains the aforementioned Adhesive resin (I-2a), and energy ray curable low molecular weight compound.

As the first adhesive composition, in addition to the energy ray-curable adhesive composition, a non-energy ray-curable adhesive composition can also be used.

Examples of the non-energy ray-curable first adhesive composition include acrylic resins, urethane resins, rubber-based resins, polysiloxane-based resins, epoxy-based resins, polyvinyl ethers, The first adhesive composition (I-4) of the non-energy ray-curable adhesive resin (I-1a) such as polycarbonate and ester resin is preferably an adhesive composition containing an acrylic resin.

<<The manufacturing method of the 1st adhesive composition>>

The above-mentioned first adhesive compositions such as the first adhesive composition (I-1) to the first adhesive composition (I-4) are prepared by combining the above-mentioned adhesive and, if necessary, components other than the above-mentioned adhesive. It is obtained by compounding each component which comprises a 1st adhesive composition.

The order of addition at the time of preparing each component is not particularly limited, and two or more components may be added at the same time.

In the case of using a solvent, it can be used by mixing the solvent with any formulation ingredient other than the solvent to dilute the formulation ingredient in advance; it can also be used in the following manner, that is, without Any formulation components other than the solvent are diluted in advance, and the solvent is mixed with these formulation components.

The method of mixing the components during preparation is not particularly limited, and may be appropriately selected from the following well-known methods: a method of mixing by rotating a stirrer or a stirring blade, a method of mixing using a mixer, and a method of applying ultrasonic waves for mixing method etc.

The temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounded component is not degraded, and may be appropriately adjusted, and the temperature is preferably 15°C to 30°C.

○The first intermediate layer

The said 1st intermediate layer is a sheet shape or a film shape, and what is necessary is just to select suitably the constituent material of a 1st intermediate layer according to the objective, and it does not specifically limit.

The first intermediate layer may be only one layer (single layer), or may be a multi-layer of two or more layers. In the case of a multi-layer, these layers may be the same or different from each other, and the combination of these layers is not particularly limited.

The thickness of the first intermediate layer may be appropriately selected according to the purpose, and is not particularly limited.

Here, the "thickness of the first intermediate layer" means the thickness of the entire first intermediate layer, for example, the thickness of the first intermediate layer composed of multiple layers means the total thickness of all the layers constituting the first intermediate layer .

<<The composition for forming the first intermediate layer>>

The first intermediate layer can be formed from a composition for forming a first intermediate layer containing the constituent materials of the layer.

For example, the first intermediate layer can be formed at the target site by applying the composition for forming the first intermediate layer on the surface to be formed with the first intermediate layer, and drying it if necessary, or curing it by irradiating energy rays. .

<<Manufacturing method of the composition for forming a first intermediate layer>>

The composition for 1st intermediate layer formation was obtained by the same method as the case of the above-mentioned 1st adhesive agent composition except for the point that a compounding component differs.

◎Curable resin layer

The aforementioned curable resin layer may be any of a thermosetting resin layer (also referred to as a thermosetting resin film) and an energy ray curable resin layer (also referred to as an energy ray curable resin film).

The said curable resin layer forms a 1st protective film by hardening.

The curable resin layer may be only one layer (single layer), or may be a multi-layer of two or more layers. In the case of a multi-layer, these layers may be the same or different from each other, and the combination of these layers is not particularly limited.

○ Thermosetting resin layer

The thermosetting resin layer is preferably a layer containing, for example, the polymer component (A) and the thermosetting component (B). The polymer component (A) is a component formed by a polymerization reaction of a polymerizable compound. Moreover, a thermosetting component (B) is a component which can perform a hardening (polymerization) reaction by using heat as a trigger of a reaction. Furthermore, in the present invention, the polymerization reaction also includes a polycondensation reaction.

The thickness of the aforementioned thermosetting resin layer is preferably 1 μm to 100 μm, more preferably 5 μm to 75 μm, particularly preferably 5 μm to 50 μm. When the thickness of a thermosetting resin layer is more than the said lower limit, the 1st protective film with higher protection ability can be formed. Moreover, since the thickness of a thermosetting resin layer is below the said upper limit value, it can suppress that thickness becomes too thick.

Here, the "thickness of the thermosetting resin layer" means the thickness of the entire thermosetting resin layer, for example, the thickness of the thermosetting resin layer composed of multiple layers means the entire thickness of the thermosetting resin layer. The total thickness of the layers.

Regarding the curing conditions when the above-mentioned thermosetting resin layer is attached to the first surface of the semiconductor wafer and cured to form the first protective film, as long as the first protective film fully exhibits the function of the first protective film The degree of hardening is not particularly limited, and may be appropriately selected according to the type of the thermosetting resin layer.

For example, the heating temperature at the time of curing the thermosetting resin layer is preferably 100°C to 200°C, more preferably 110°C to 180°C, particularly preferably 120°C to 170°C. In addition, the heating time during the hardening is preferably 0.5 to 5 hours, more preferably 0.5 to 3.5 hours, and particularly preferably 1 to 2.5 hours.

<<The composition for forming a thermosetting resin layer>>

The thermosetting resin layer can be formed from a composition for forming a thermosetting resin layer containing a constituent material of the layer. For example, the thermosetting resin layer can be formed at the target site by applying the composition for forming a thermosetting resin layer to the surface to be formed of the thermosetting resin layer, and drying it if necessary.

What is necessary is just to apply|coat the composition for thermosetting resin layer formation by a well-known method, for example, it can carry out by the method similar to the case of application|coating of the said 1st adhesive composition.

Moreover, the drying conditions of the composition for thermosetting resin layer formation are not specifically limited, For example, it can be the same as the case of the above-mentioned 1st adhesive composition.

<Resin layer forming composition (III)>

Examples of the composition for forming a thermosetting resin layer include the composition (III) for forming a thermosetting resin layer containing a polymer component (A) and a thermosetting component (B) (in this specification, there may be It is only abbreviated as "resin layer forming composition (III)") and the like.

[Polymer component (A)]

The polymer component (A) is a polymer compound for imparting film-forming properties, flexibility, and the like to the thermosetting resin layer.

The polymer component (A) contained in the composition (III) for forming a resin layer and the thermosetting resin layer may be only one kind or two or more kinds, and in the case of two or more kinds, the combination of these and The ratio can be chosen arbitrarily.

As the polymer component (A), for example, polyvinyl acetal, acrylic resin, polyester, urethane resin, urethane acrylate resin, polysiloxane resin, and rubber resin may be mentioned. , phenoxy resin, thermosetting polyimide, etc., preferably polyvinyl acetal, acrylic resin.

As said polyvinyl acetal in a polymer component (A), well-known polyvinyl acetal is mentioned.

Among them, preferable examples of polyvinyl acetal include polyvinyl formal, polyvinyl butyral, and the like, and polyvinyl butyral is more preferable.

As a polyvinyl butyral, the polyvinyl butyral which has the structural unit represented by following formula (i)-1, (i)-2 and (i)-3 is mentioned.

(In the formula, l, m and n are each independently an integer of 1 or more)

The weight average molecular weight (Mw) of the polyvinyl acetal is preferably 5,000 to 200,000, more preferably 8,000 to 100,000. When the weight average molecular weight of the polyvinyl acetal is in this range, when the thermosetting resin layer is attached to the first surface, the thermosetting resin layer is suppressed from remaining on the upper part of the bump (the top part of the bump and the upper part of the bump). its nearby area) effect becomes higher.

In this specification, the "weight average molecular weight" refers to a polystyrene-equivalent value measured by a gel permeation chromatography (GPC; Gel Permeation Chromatography) method unless otherwise specified.

The glass transition temperature (Tg) of the polyvinyl acetal is preferably from 40°C to 80°C, more preferably from 50°C to 70°C. When the Tg of polyvinyl acetal is in such a range, when the thermosetting resin layer is attached to the first surface, the effect of suppressing the thermosetting resin layer remaining on the upper part of the bump becomes higher.

The ratio of three or more kinds of monomers constituting polyvinyl acetal can be arbitrarily selected.

As said acrylic resin in a polymer component (A), a well-known acrylic polymer is mentioned.

The weight average molecular weight (Mw) of the acrylic resin is preferably from 10,000 to 2,000,000, more preferably from 100,000 to 1,500,000. When the weight average molecular weight of the acrylic resin is equal to or more than the aforementioned lower limit value, the shape stability of the thermosetting resin layer (time stability during storage) is improved. In addition, when the weight-average molecular weight of the acrylic resin is equal to or less than the aforementioned upper limit value, the thermosetting resin layer can easily follow the uneven surface of the adherend, and the occurrence of generation between the adherend and the thermosetting resin layer can be further suppressed. Porosity (void), etc.

The glass transition temperature (Tg) of the acrylic resin is preferably -60°C to 70°C, more preferably -30°C to 50°C. When Tg of an acrylic resin is more than the said lower limit, the adhesive force of a 1st protective film and a 1st support sheet can be suppressed, and the peelability of a 1st support sheet improves. Moreover, since Tg of an acrylic resin is below the said upper limit, the adhesive force of a thermosetting resin layer, a 1st protective film, and a to-be-adhered body improves.

Examples of acrylic resins include polymers of one or more (meth)acrylates; other than (meth)acrylates, selected from (meth)acrylic acid, itaconic acid, and vinyl acetate , acrylonitrile, styrene, and N-methylol acrylamide, etc., one or two or more monomers are copolymerized to form copolymers, etc.

As said (meth)acrylate which comprises an acrylic resin, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate are mentioned, for example ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-butyl (meth)acrylate, 3-butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate (methyl)hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-octyl (meth)acrylate Nonyl ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (also known as (meth)acrylic acid) lauryl), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also known as myristyl (meth)acrylate), pentadecyl (meth)acrylate, Cetyl (meth)acrylate (also known as palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (also known as (meth)acrylate) base) stearyl acrylate), etc. The alkyl group constituting the alkyl ester is an alkyl (meth)acrylate with a chain structure of carbon number from 1 to 18; isobornyl (meth)acrylate, (meth)acrylic acid (meth)acrylic acid cycloalkyl esters such as dicyclopentyl ester; (meth)acrylic acid aralkyl esters such as benzyl (meth)acrylate; (meth)acrylic acid ring Alkenyl esters; (meth)acrylic acid cycloalkenyloxyalkyl esters such as dicyclopentenyloxyethyl ester; (meth)acrylimide; (meth)acrylic acid glycidyl ester, etc. (Meth)acrylate of glycidyl group; hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxy (meth)acrylate Propyl, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyl-containing (meth)acrylates; (methyl) Substituted amino group-containing (meth)acrylates such as N-methylaminoethyl acrylate, etc. Here, the "substituted amino group" means a group in which one or two hydrogen atoms of the amino group are substituted with a group other than a hydrogen atom.

Only one kind of the monomer constituting the acrylic resin may be used, or two or more kinds thereof may be used, and in the case of two or more kinds, the combination and ratio of these may be arbitrarily selected.

The acrylic resin may also have functional groups that can bond with other compounds, such as vinyl groups, (meth)acryloyl groups, amine groups, hydroxyl groups, carboxyl groups, and isocyanate groups. The functional group in the acrylic resin may be bonded to another compound via the crosslinking agent (F) described later, or may be directly bonded to the other compound without the crosslinking agent (F). There exists a tendency for the reliability of the package obtained using the sheet for 1st protective film formation to improve by making an acrylic resin couple|bond with another compound via the said functional group.

In one aspect, as the acrylic resin, it is preferable to use at least one monomer selected from the group consisting of butyl acrylate, methyl acrylate, glycidyl methacrylate, and 2-hydroxyethyl acrylate Acrylic resin obtained by copolymerization.

In the present invention, for example, as the polymer component (A), a thermoplastic resin other than polyvinyl acetal and acrylic resin may be used alone instead of polyvinyl acetal and acrylic resin (hereinafter, it may be simply abbreviated as: "Thermoplastic resin"), and can also be used in combination with polyvinyl acetal or acrylic resin. By using the aforementioned thermoplastic resin, sometimes the peelability of the first protective film from the first support sheet is improved, or the thermosetting resin layer becomes easy to follow the uneven surface of the adherend, thereby further suppressing the adhesion of the adherend and the adherend. A void or the like is generated between the thermosetting resin layers.

The weight average molecular weight of the aforementioned thermoplastic resin is preferably 1,000 to 100,000, more preferably 3,000 to 80,000.

The glass transition temperature (Tg) of the aforementioned thermoplastic resin is preferably -30°C to 150°C, more preferably -20°C to 120°C.

As said thermoplastic resin, polyester, a polyurethane, a phenoxy resin, a polybutene, a polybutadiene, a polystyrene etc. are mentioned, for example.

The above-mentioned thermoplastic resin contained in the composition (III) for forming a resin layer and the thermosetting resin layer may be only one type or two or more types, and in the case of two or more types, the combination and ratio of these may be arbitrary choose.

Regarding the content of the polymer component (A), irrespective of the type of the polymer component (A), it is relative to the total mass of all components other than the solvent in the composition (III) constituting the resin layer (that is, relative to the heat The total mass of the curable resin layer), preferably 5 to 85 mass %, more preferably 5 to 80 mass %, for example, 5 to 70 mass %, 5 to 60 mass %, Any one of 5 mass % to 50 mass %, 5 mass % to 40 mass %, and 5 mass % to 30 mass %. However, these contents in the composition (III) for resin layer formation are an example.

The polymer component (A) may also correspond to the thermosetting component (B). In the present invention, when the composition (III) for forming a resin layer contains such a component conforming to both of the polymer component (A) and the thermosetting component (B), the composition for forming a resin layer (III) It can be considered that the polymer component (A) and the thermosetting component (B) are contained.

[Thermosetting component (B)]

The thermosetting component (B) is a component for hardening the thermosetting resin layer to form a hard first protective film.

The composition (III) for forming a resin layer and the thermosetting component (B) contained in the thermosetting resin layer may be only one type or two or more types, and in the case of two or more types, the combination of these may be used. and the ratio can be arbitrarily selected.

As the thermosetting component (B), for example, epoxy-based thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, polysiloxane resins, etc. may be mentioned, and preferably Epoxy thermosetting resin.

(Epoxy thermosetting resin)

The epoxy-based thermosetting resin is composed of an epoxy resin (B1) and a thermosetting agent (B2).

The epoxy-based thermosetting resin contained in the composition (III) for forming a resin layer and the thermosetting resin layer may be only one type or two or more types, and in the case of two or more types, a combination of these may be used. and the ratio can be arbitrarily selected.

‧Epoxy resin (B1)

As epoxy resin (B1), well-known epoxy resins are mentioned, for example, polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, o-cresol novolak epoxy resins are mentioned. Resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, etc. compound.

As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group can also be used. The epoxy resin having an unsaturated hydrocarbon group has higher compatibility with the acrylic resin than the epoxy resin having no unsaturated hydrocarbon group. Therefore, the reliability of the package obtained using the sheet for 1st protective film formation improves by using the epoxy resin which has an unsaturated hydrocarbon group.

As an epoxy resin which has an unsaturated hydrocarbon group, the compound which replaced some epoxy groups of a polyfunctional epoxy resin with the group which has an unsaturated hydrocarbon group is mentioned, for example. Such a compound is obtained, for example, by subjecting (meth)acrylic acid or a derivative thereof to an addition reaction with an epoxy group.

Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group which has an unsaturated hydrocarbon group couple|bonded directly with the aromatic ring etc. which comprise an epoxy resin are mentioned, for example.

The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples of the unsaturated hydrocarbon group include ethylene (also called vinyl), 2-propenyl (also called allyl), (methyl) group) acrylyl group, (meth)acrylamide group, etc., preferably an acryl group.

The number average molecular weight of the epoxy resin (B1) is not particularly limited, but is preferably 300 to 30,000 in terms of the curability of the thermosetting resin layer and the strength and heat resistance of the first protective film after curing, More preferably, it is 400 to 10,000, and still more preferably, it is 500 to 3,000.

In this specification, unless otherwise specified, "number average molecular weight" means the number average molecular weight represented by the standard polystyrene conversion value measured by gel permeation chromatography (GPC).

The epoxy equivalent of the epoxy resin (B1) is preferably from 100 g/eq to 1000 g/eq, more preferably from 130 g/eq to 800 g/eq.

In this specification, "epoxy equivalent" means the number of grams (g/eq) of the epoxy compound containing 1 gram equivalent of an epoxy group, and can be measured according to the method of JIS K 7236:2001.

An epoxy resin (B1) may be used individually by 1 type, and may use 2 or more types together, and when using 2 or more types together, the combination and ratio of these can be selected arbitrarily.

‧Thermosetting agent (B2)

The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).

As a thermosetting agent (B2), the compound which has two or more functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and an acid group formed by an anhydride, and preferably a phenolic hydroxyl group, an amino group, or an acid group formed by an anhydride. The base formed is more preferably a phenolic hydroxyl group or an amine group.

Among the thermosetting agents (B2), examples of the phenol-based curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolak-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl-type phenol resins. Phenolic resin, etc.

Among the thermosetting agents (B2), as an amine-based curing agent having an amine group, dicyandiamine (in this specification, it may be abbreviated as "DICY") etc. are mentioned, for example.

The thermal hardener (B2) may have an unsaturated hydrocarbon group.

Examples of the thermosetting agent (B2) having an unsaturated hydrocarbon group include a compound in which a part of the hydroxyl groups of a phenol resin is substituted with a group having an unsaturated hydrocarbon group, and a group having an unsaturated hydrocarbon group directly bonded to the aromatic ring of the phenol resin. Compounds, etc.

The aforementioned unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the above-mentioned epoxy resin having an unsaturated hydrocarbon group.

In the case of using a phenol-based hardener as the thermosetting agent (B2), the thermosetting agent (B2) is preferably softening point or glass transition from the viewpoint of improving the releasability of the first protective film from the first support sheet High temperature phenolic hardener.

In the thermosetting agent (B2), the number average molecular weight of resin components such as polyfunctional phenol resin, novolac-type phenol resin, dicyclopentadiene-type phenol resin, aralkyl-type phenol resin is preferably 300 to 30,000, more Preferably, it is 400 to 10,000, and more preferably, it is 500 to 3,000.

In the thermosetting agent (B2), for example, the molecular weight of non-resin components such as biphenol and dicyandiamine is not particularly limited, but is preferably 60 to 500, for example.

The thermosetting agent (B2) may be used alone or in combination of two or more, and when two or more are used in combination, the combination and ratio of these may be arbitrarily selected.

In the composition (III) for forming a resin layer and the thermosetting resin layer, the content of the thermosetting agent (B2) is 100 parts by mass, preferably 0.1 parts by mass to 500 parts by mass, relative to the content of the epoxy resin (B1) in 100 parts by mass, More preferably, it is 1 part by mass to 200 parts by mass, and for example, it may be any of 1 part by mass to 100 parts by mass, 1 part by mass to 80 parts by mass, and 1 part by mass to 60 parts by mass. When the said content of a thermosetting agent (B2) is more than the said lower limit, a thermosetting resin layer becomes easy to harden|cure. Moreover, when the said content of a thermosetting agent (B2) is below the said upper limit, the moisture absorption rate of a thermosetting resin layer falls, and the reliability of the package obtained using the sheet for 1st protective film formation improves further.

In the composition (III) for forming a resin layer and the thermosetting resin layer, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) relative to the polymer The content of the component (A) is 100 parts by mass, preferably 50 parts by mass to 1000 parts by mass, more preferably 60 parts by mass to 950 parts by mass, particularly preferably 70 parts by mass to 900 parts by mass. When the said content of a thermosetting component (B) is such a range, the adhesive force of a 1st protective film and a 1st support sheet is suppressed, and the peelability of a 1st support sheet improves.

[Hardening accelerator (C)]

The composition (III) for resin layer formation and a thermosetting resin layer may contain a hardening accelerator (C). The hardening accelerator (C) is a component for adjusting the hardening rate of the resin layer-forming composition (III).

As preferable hardening accelerator (C), for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, etc. can be mentioned; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Imidazoles such as hydroxymethylimidazole (that is, imidazoles in which one or more hydrogen atoms are substituted by groups other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine (also That is, a phosphine in which one or more hydrogen atoms are substituted with an organic group); tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, and the like.

The composition for forming a resin layer (III) and the curing accelerator (C) contained in the thermosetting resin layer may be only one type or two or more types, and in the case of two or more types, the combination of these and The ratio can be chosen arbitrarily.

In the case of using a curing accelerator (C), in the composition (III) for forming a resin layer and the thermosetting resin layer, the content of the curing accelerator (C) is 100 mass with respect to the content of the thermosetting component (B) parts, preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass. When the said content of a hardening accelerator (C) is more than the said lower limit, the effect by which the hardening accelerator (C) is used can be obtained remarkably. In addition, when the content of the hardening accelerator (C) is below the above-mentioned upper limit, for example, the high-polarity hardening accelerator (C) is suppressed from being in contact with the adherend in the thermosetting resin layer under high temperature and high humidity conditions. Then, the effect of the interface side transfer and segregation becomes high, and the reliability of the package obtained by using the sheet for forming the first protective film is further improved.

[filler (D)]

The composition (III) for resin layer formation and a thermosetting resin layer may contain a filler (D). When the thermosetting resin layer contains the filler (D), the thermal expansion coefficient of the first protective film obtained by curing the thermosetting resin layer can be easily adjusted. And the reliability of the package obtained using the sheet for 1st protective film formation is further improved by making this thermal expansion coefficient optimal to the formation target object of a 1st protective film. Moreover, when a thermosetting resin layer contains a filler (D), the moisture absorption rate of a 1st protective film can also be reduced, or heat dissipation can also be improved.

The filler (D) may be any one of an organic filler and an inorganic filler, preferably an inorganic filler.

As preferred inorganic fillers, for example, powders of silica, alumina, talc, calcium carbonate, titanium dioxide, iron dan, silicon carbide, boron nitride, etc. can be mentioned; these inorganic fillers are spherical Beads; surface modification products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc.

Among these, the inorganic filler is preferably silica or alumina.

The composition (III) for forming a resin layer and the filler (D) contained in the thermosetting resin layer may be only one type or two or more types, and in the case of two or more types, the combination and ratio of these may be used Can be arbitrarily selected.

The average particle diameter of the filler (D) is not particularly limited, but is preferably 0.01 μm to 20 μm, more preferably 0.1 μm to 15 μm, and particularly preferably 0.3 μm to 10 μm. When the average particle diameter of the filler (D) is in such a range, the adhesiveness to the object to be formed of the first protective film can be maintained, and the decrease in the light transmittance of the first protective film can be suppressed.

In addition, in this specification, the "average particle size" means the particle size (D ₅₀ ) at 50% of the cumulative value in the particle size distribution curve obtained by the laser diffraction scattering method unless otherwise specified. value.

When the filler (D) is used, the content of the filler (D) (that is, the content of the filler (D) in the thermosetting resin layer) relative to the content of the resin layer-forming composition (III) The total mass of all components other than the solvent (that is, with respect to the total mass of the thermosetting resin layer) is preferably 3 to 60 mass %, more preferably 3 to 55 mass %. When the content of the filler (D) is in such a range, the above-mentioned thermal expansion coefficient can be more easily adjusted. Moreover, when content of a filler (D) is below the said upper limit, the infrared transmittance of a curable resin layer and a 1st protective film improves further.

[Coupling agent (E)]

The composition (III) for resin layer formation and the thermosetting resin layer may contain a coupling agent (E). By using a compound having a functional group reactive with an inorganic compound or an organic compound as the coupling agent (E), the adhesiveness and adhesiveness of the thermosetting resin layer to the adherend can be improved. Moreover, by using a coupling agent (E), the 1st protective film obtained by hardening a thermosetting resin layer improves water resistance without impairing heat resistance.

The coupling agent (E) is preferably a compound having a functional group capable of reacting with functional groups possessed by the polymer component (A), the thermosetting component (B), and the like, and is more preferably a silane coupling agent.

Examples of preferable silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyl Triethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethyl Oxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyl Diethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane Oxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, ethylene trimethoxysilane, vinyltriacetoxysilane, imidazolylsilane, etc.

The composition (III) for forming the resin layer and the coupling agent (E) contained in the thermosetting resin layer may be only one type or two or more types, and in the case of two or more types, the combination and ratio of these may be used Can be arbitrarily selected.

When the coupling agent (E) is used, the content of the coupling agent (E) in the composition (III) for forming the resin layer and the thermosetting resin layer is relative to the polymer component (A) and the thermosetting component (B) ) in 100 parts by mass, preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass. By the above-mentioned content of the coupling agent (E) being equal to or more than the above-mentioned lower limit value, the following effects brought about by the use of the coupling agent (E) can be obtained more significantly: the dispersibility of the filler (D) in the resin is improved, or The adhesion between the thermosetting resin layer and the adherend is improved, etc. Moreover, when the said content of a coupling agent (E) is below the said upper limit, generation|occurrence|production of outgas can be suppressed further.

[Crosslinker (F)]

In the case of using the above-mentioned acrylic resins having functional groups that can bond with other compounds, such as vinyl groups, (meth)acryloyl groups, amine groups, hydroxyl groups, carboxyl groups, isocyanate groups, etc., as the polymer component (A) In this case, the composition (III) for forming a resin layer and the thermosetting resin layer may contain a crosslinking agent (F). The cross-linking agent (F) is a component for cross-linking by bonding the above-mentioned functional groups in the polymer component (A) with other compounds, and by performing cross-linking in this way, the initial adhesion of the thermosetting resin layer can be adjusted. strength and cohesion.

Examples of the crosslinking agent (F) include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate-based crosslinking agents (crosslinking agents having a metal chelate structure), and aziridine-based crosslinking agents. agent (crosslinking agent with aziridine group), etc.

Examples of the organic polyvalent isocyanate compound include: aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, and alicyclic polyvalent isocyanate compounds (hereinafter, these compounds may be collectively referred to as "aromatic polyvalent isocyanate compounds, etc."); Trimers, isocyanurate compounds, and adducts of the aforementioned aromatic polyvalent isocyanate compounds, etc.; terminal isocyanate urethane prepolymers, etc. obtained by reacting the aforementioned aromatic polyvalent isocyanate compounds, etc. with a polyol compound, etc. . The aforementioned "adduct" means the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound, which is mixed with ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil, etc. Reactant for low molecular active hydrogen compounds. As an example of the said adduct, the xylylene diisocyanate adduct of trimethylolpropane mentioned later, etc. are mentioned. In addition, the "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and having an isocyanate group at a molecular terminal.

As said organic polyvalent isocyanate compound, more specifically, 2, 4- toluene diisocyanate; 2, 6- toluene diisocyanate; 1, 3- xylylene diisocyanate; 1, 4- xylene diisocyanate are mentioned, for example Isocyanates; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone Diisocyanate; Dicyclohexylmethane-4,4'-diisocyanate; Dicyclohexylmethane-2,4'-diisocyanate; All or part of the hydroxyl groups of polyols such as p-trimethylolpropane, added with toluene diisocyanate, Any one or two or more compounds of hexamethylene diisocyanate and xylylene diisocyanate; lysine diisocyanate, etc.

As said organic polyvalent imine compound, for example, N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-nitrogen Propidyl propionate, tetramethylolmethane-tri-beta-aziridinyl propionate, N,N'-toluene-2,4-bis(1-aziridinecarboxamide) tris-ethyl melamine, etc.

When an organic polyvalent isocyanate compound is used as the crosslinking agent (F), it is preferable to use a hydroxyl group-containing polymer as the polymer component (A). When the crosslinking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, the crosslinking structure can be easily introduced to the in the thermosetting resin layer.

The crosslinking agent (F) contained in the composition (III) for forming a resin layer and the thermosetting resin layer may be only one type or two or more types, and in the case of two or more types, the combination of these and The ratio can be chosen arbitrarily.

In the case of using a crosslinking agent (F), in the composition (III) for forming a resin layer, the content of the crosslinking agent (F) is preferably 0.01 mass parts with respect to 100 parts by mass of the content of the polymer component (A). parts to 20 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, particularly preferably 0.5 parts by mass to 5 parts by mass. When the said content of a crosslinking agent (F) is more than the said lower limit, the effect by using a crosslinking agent (F) is more remarkable. Moreover, since the said content of a crosslinking agent (F) is below the said upper limit, excessive use of a crosslinking agent (F) can be suppressed.

[Energy beam curable resin (G)]

The composition (III) for resin layer formation and the thermosetting resin layer may contain an energy ray-curable resin (G). Since the thermosetting resin layer contains the energy ray curable resin (G), the properties can be changed by irradiating the energy ray.

The energy ray curable resin (G) is obtained by polymerizing (hardening) an energy ray curable compound.

As said energy-beam curable compound, the compound which has at least 1 polymerizable double bond in a molecule|numerator is mentioned, for example, Preferably it is an acrylate type compound which has a (meth)acryloyl group.

As said acrylate type compound, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, base) acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate (Meth)acrylates containing chain-like aliphatic skeletons such as (meth)acrylates; (meth)acrylates containing cyclic aliphatic skeletons such as dicyclopentyl di(meth)acrylates; polyethylene glycol Polyalkylene glycol (meth)acrylates such as di(meth)acrylates; oligoester (meth)acrylates; (meth)acrylate urethane oligomers; epoxy modified (meth)acrylates base) acrylates; polyether (meth)acrylates other than the aforementioned polyalkylene glycol (meth)acrylates; itaconic acid oligomers, and the like.

The weight average molecular weight of the aforementioned energy ray curable compound is preferably from 100 to 30,000, more preferably from 300 to 10,000.

Only one type of the above-mentioned energy ray-curable compound used for polymerization may be used, or two or more types may be used, and in the case of two or more types, the combination and ratio of these may be arbitrarily selected.

The energy ray-curable resin (G) contained in the composition (III) for forming a resin layer may be only one type or two or more types, and in the case of two or more types, the combination and ratio of these may be arbitrarily selected .

When the energy ray curable resin (G) is used, the content of the energy ray curable resin (G) is relative to the total mass of all components other than the solvent in the composition for forming the resin layer (III) (that is, relative to In the total mass of the thermosetting resin layer), it is preferably 1 to 95 mass %, more preferably 5 to 90 mass %, particularly preferably 10 to 85 mass %.

[Photopolymerization initiator (H)]

When the composition (III) for resin layer formation and the thermosetting resin layer contain the energy ray curable resin (G), in order to efficiently carry out the polymerization reaction of the energy ray curable resin (G), light may be contained. Polymerization initiator (H).

Examples of the photopolymerization initiator (H) in the resin layer-forming composition (III) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, and benzoin benzene Benzoin compounds such as methyl formate, benzoin dimethyl ketal; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2 - Acetophenone compounds such as diphenylethane-1-one; bis(2,4,6-trimethylbenzyl) phenylphosphine oxide, 2,4,6-trimethylbenzyl Acylphosphine oxide compounds such as diphenylphosphine oxide; sulfide compounds such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; α-keto alcohol compounds such as 1-hydroxycyclohexyl phenyl ketone; azobis Azo compounds such as isobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone and 2,4-diethyl thioxanthone; peroxide compounds; diacetone and other diketone compounds; Benzodiol; Dibenzyl; Benzophenone; 1,2-Diphenylmethane; 2-Hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; 2-Chloranthraquinone, etc.

Moreover, as a photoinitiator (H), quinone compounds, such as 1-chloroanthraquinone, etc.; photosensitizers, such as an amine, etc. can also be used, for example.

The photopolymerization initiator (H) contained in the composition (III) for forming a resin layer may be only one type or two or more types, and in the case of two or more types, the combination and ratio of these may be arbitrarily selected .

In the case of using a photopolymerization initiator (H), in the composition (III) for forming a resin layer, the content of the photopolymerization initiator (H) is 100 parts by mass relative to the content of the energy ray-curable resin (G) , preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, particularly preferably 2 to 5 parts by mass.

[Colorant (I)]

The composition (III) for resin layer formation and the thermosetting resin layer may contain a colorant (I). The colorant (I) is, for example, a component for imparting appropriate light transmittance to the thermosetting resin layer and the first protective film.

The coloring agent (I) may be a known coloring agent, and may be, for example, any of a dye and a pigment.

For example, the dye may be any of acid dyes, reactive dyes, direct dyes, disperse dyes, cationic dyes, and the like.

The composition (III) for forming a resin layer and the coloring agent (I) contained in the thermosetting resin layer may be only one type or two or more types, and in the case of two or more types, the combination and ratio of these may be used Can be arbitrarily selected.

The content of the colorant (I) in the composition (III) for forming a resin layer may be appropriately adjusted so that the visible light transmittance and infrared transmittance of the thermosetting resin layer may become target values, and are not particularly limited. For example, the content of the coloring agent (I) may be appropriately adjusted according to the type of the coloring agent (I), or when two or more coloring agents (I) are used in combination, it may be appropriately adjusted according to the combination of these coloring agents (I), etc. Adjust it.

In the case of using the colorant (I), the content of the colorant (I) (that is, the content of the colorant (I) in the thermosetting resin layer) relative to the composition for forming the resin layer (III) The total content of all components other than the solvent is preferably 0.01% by mass to 10% by mass.

[General Additives (J)]

The composition (III) for resin layer formation and the thermosetting resin layer may contain a general-purpose additive (J) within a range that does not impair the effects of the present invention.

The general-purpose additive (J) may be a known additive, and can be arbitrarily selected according to the purpose without particular limitation. As the preferred general-purpose additive (J), for example, a plasticizer, an antistatic agent, an antioxidant, and a getter can be mentioned. (gettering agent), etc.

The general-purpose additive (J) contained in the composition (III) for forming a resin layer and the thermosetting resin layer may be only one type or two or more types, and in the case of two or more types, the combination and ratio of these may be used Can be arbitrarily selected.

The content of the general-purpose additive (J) in the composition (III) for forming a resin layer and the thermosetting resin layer is not particularly limited, and may be appropriately selected according to the purpose.

[solvent]

The resin layer-forming composition (III) preferably further contains a solvent. The solvent-containing resin layer-forming composition (III) has good handleability.

The aforementioned solvent is not particularly limited, and preferable examples of the aforementioned solvent include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropan-1-ol), 1 - Alcohols such as butanol; Esters such as ethyl acetate; Ketones such as acetone and methyl ethyl ketone; Ethers such as tetrahydrofuran; )Wait.

The solvent contained in the resin layer-forming composition (III) may be only one type or two or more types, and in the case of two or more types, the combination and ratio of these may be arbitrarily selected.

The solvent contained in the composition (III) for forming a resin layer is preferably methyl ethyl ketone or the like, since the components contained in the composition (III) for forming a resin layer can be mixed more uniformly.

The content of the solvent in the resin layer-forming composition (III) is not particularly limited, and may be appropriately selected, for example, depending on the types of components other than the solvent.

<<The manufacturing method of the composition for thermosetting resin layer formation>>

The composition for thermosetting resin layer formation, such as the composition for resin layer formation (III), is obtained by mix|blending each component which comprises this composition.

The order of addition at the time of preparing each component is not particularly limited, and two or more components may be added at the same time.

In the case of using a solvent, it can be used by mixing the solvent with any formulation ingredient other than the solvent to dilute the formulation ingredient in advance; it can also be used in the following manner, that is, without Any formulation components other than the solvent are diluted in advance, and the solvent is mixed with these formulation components.

The method of mixing the components during preparation is not particularly limited, and may be appropriately selected from the following well-known methods: a method of mixing by rotating a stirrer, a stirring blade, etc.; a method of mixing using a mixer; Methods of mixing, etc.

The temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounding component is not degraded, and may be appropriately adjusted, and the temperature is preferably 15°C to 50°C.

○Energy beam curable resin layer

As a preferable energy ray curable resin layer, the layer containing an energy ray curable component (a) is mentioned, for example.

The energy ray curable component (a) is preferably uncured, preferably has adhesiveness, and is more preferably uncured and has adhesiveness. Here, the so-called "energy ray" and "energy ray sclerosis" are as described above.

The thickness of the energy ray-curable resin layer is preferably 1 μm to 100 μm, more preferably 5 μm to 75 μm, and particularly preferably 5 μm to 50 μm. When the thickness of the energy-beam-curable resin layer is equal to or more than the aforementioned lower limit value, the first protective film with higher protective ability can be formed. In addition, when the thickness of the energy ray-curable resin layer is equal to or less than the above-mentioned upper limit value, excessive thickness can be suppressed.

Here, the "thickness of the energy ray curable resin layer" means the thickness of the entire energy ray curable resin layer, for example, the thickness of the energy ray curable resin layer composed of multiple layers means the thickness of the energy ray curable resin layer constituting the energy ray curable resin layer. The total thickness of all the resin layers.

Regarding the curing conditions when the energy ray curable resin layer is adhered to the first surface of the semiconductor wafer and cured to form the first protective film, as long as the function of the first protective film is sufficiently exhibited by the first protective film The degree of hardening is not particularly limited, and may be appropriately selected according to the type of the energy ray-curable resin layer.

For example, the illuminance of the energy ray during curing of the energy ray-curable resin layer is preferably 180 mW/cm ² to 280 mW/cm ² . In addition, the light intensity of the energy beam at the time of hardening is preferably 450 mJ/cm ² to 1000 mJ/cm ² .

<<The composition for forming an energy ray-curable resin layer>>

The energy ray-curable resin layer can be formed from a composition for forming an energy ray-curable resin layer containing the constituent materials of the layer. For example, the energy-ray-curable resin layer-forming composition is applied to the surface to be formed of the energy-ray-curable resin layer, and dried as necessary, whereby the energy-ray-curable resin layer can be formed at the target site.

What is necessary is just to apply|coat the composition for energy ray curable resin layer formation by a well-known method, for example, it can carry out by the same method as the case of application|coating of the said 1st adhesive composition.

Moreover, the drying conditions of the composition for energy ray-curable resin layer formation are not specifically limited, For example, it can be the same as the case of the above-mentioned 1st adhesive composition.

<Resin layer forming composition (IV)>

As the composition for forming an energy ray-curable resin layer, for example, the composition (IV) for forming an energy ray-curable resin layer containing the above-mentioned energy ray-curable component (a) (in this specification, it may be simply abbreviated as "" Resin layer forming composition (IV)") and the like.

[energy ray sclerosing component (a)]

The energy ray-curable component (a) is a component hardened by irradiation with an energy ray, and is also a component for imparting film-forming properties, flexibility, and the like to the energy ray-curable resin layer.

Examples of the energy ray curable component (a) include a polymer (a1) having an energy ray curable group and a weight average molecular weight of 80,000 to 2,000,000, and a compound having an energy ray curable group and a molecular weight of 100 to 80,000. (a2). The aforementioned polymer (a1) may be a polymer in which at least a part of the polymer (a1) is cross-linked by a cross-linking agent, or a polymer which is not cross-linked.

Examples of the polymer (a1) include an acrylic polymer having a functional group reactive with a group contained in another compound, an energy ray having a group reactive with the functional group, and an energy ray-hardenable double bond. Acrylic resins, etc., produced by the reaction of energy ray curable compounds of curable groups.

Examples of functional groups that can react with groups contained in other compounds include a hydroxyl group, a carboxyl group, an amino group, and a substituted amino group (a group in which one or two hydrogen atoms of the amino group are substituted with a group other than a hydrogen atom). group), epoxy group, etc. Among them, the functional group is preferably a group other than a carboxyl group from the viewpoint of preventing circuit corrosion of a semiconductor wafer, a semiconductor wafer, or the like.

Among these, the aforementioned functional group is preferably a hydroxyl group.

The above-mentioned polymer (a1) contained in the composition (IV) for forming a resin layer and the energy ray-curable resin layer may be only one type, or two or more types, and in the case of two or more types, a combination of these may be used. and the ratio can be arbitrarily selected.

Examples of the energy-ray-curable group of the compound (a2) having an energy-ray-curable group and a molecular weight of 100 to 80,000 include groups containing an energy-ray-curable double bond, and preferable examples of the group include (methyl base) acrylyl, vinyl, etc. Preferably, it is a low molecular weight compound which has a (meth)acryloyl group as an energy ray hardening group.

The compound (a2) is not particularly limited as long as it satisfies the above-mentioned conditions, and examples thereof include a low molecular weight compound having an energy ray curable group, an epoxy resin having an energy ray curable group, and a phenol resin having an energy ray curable group. Wait.

In the said compound (a2), as a low molecular weight compound which has an energy ray hardening group, a polyfunctional monomer, an oligomer, etc. are mentioned, for example, Preferably it is an acrylate type compound which has a (meth)acryloyl group.

The above-mentioned compound (a2) contained in the composition (IV) for forming a resin layer and the energy ray-curable resin layer may be only one kind or two or more kinds, and in the case of two or more kinds, the combination of these and The ratio can be chosen arbitrarily.

[Polymer (b) without energy ray curable group]

When the composition (IV) for resin layer forming and the energy ray curable resin layer contain the compound (a2) as the energy ray curable component (a), it is preferable to further contain a group without energy ray curable. of polymer (b).

At least a part of the said polymer (b) may be crosslinked by a crosslinking agent, and may not be crosslinked.

Examples of the polymer (b) not having an energy ray curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber-based resins, and acrylic urethane resins. Wait.

Among these, the aforementioned polymer (b) is preferably an acrylic polymer (hereinafter, abbreviated as "acrylic polymer (b-1)" in some cases).

In addition to the energy ray curable component (a), the composition (IV) for forming a resin layer may further contain any one selected from the group consisting of the energy ray curable component (a) and the polymer (b) that do not conform to the purpose, depending on the purpose. One or more of the group consisting of thermosetting components, photopolymerization initiators, colorants, fillers, coupling agents, cross-linking agents and general additives. For example, by using the composition (IV) for forming a resin layer containing the energy ray curable component and the thermosetting component, the adhesive force of the formed energy ray curable resin layer to the adherend is improved by heating, The intensity|strength of the 1st protective film formed with this energy-beam curable resin layer also improves.

Examples of the above-mentioned thermosetting components, photopolymerization initiators, colorants, fillers, coupling agents, crosslinking agents, and general-purpose additives in the composition (IV) for forming a resin layer include the composition for forming a resin layer, respectively. (III) Thermosetting component (B), photopolymerization initiator (H), colorant (I), filler (D), coupling agent (E), crosslinking agent (F) and general additives ( J) The same compounds.

In the composition (IV) for forming a resin layer, the above-mentioned thermosetting components, photopolymerization initiators, colorants, fillers, coupling agents, cross-linking agents and general additives may be used alone or in combination of two. As mentioned above, when two or more types are used together, the combination and ratio of these can be selected arbitrarily.

The contents of the above-mentioned thermosetting components, photopolymerization initiators, colorants, fillers, coupling agents, crosslinking agents and general additives in the composition (IV) for forming a resin layer may be appropriately adjusted according to the purpose, and there is no particular limited.

In the composition (IV) for resin layer formation, it is preferable to further contain a solvent from the viewpoint of improving the handleability of the composition by dilution.

As a solvent contained in the composition (IV) for resin layer formation, the same solvent as the solvent in the composition (III) for resin layer formation is mentioned, for example.

The solvent contained in the composition (IV) for forming a resin layer may be only one type or two or more types.

As one aspect, the resin layer-forming composition (IV) contains an energy ray-curable component (a), and optionally a polymer (b) that does not have an energy ray-curable group, a thermosetting component, a light At least one component in the group consisting of a polymerization initiator, a colorant, a filler, a coupling agent, a crosslinking agent, a general additive, and a solvent.

<<Method for producing energy ray-curable resin layer-forming composition>>

The composition for energy ray-curable resin layer formation, such as the composition for resin layer formation (IV), is obtained by mixing each component which comprises this composition.

The order of addition at the time of preparing each component is not particularly limited, and two or more components may be added at the same time.

In the case of using a solvent, it can be used by mixing the solvent with any preparation component other than the solvent to dilute the preparation component in advance; it can also be used by not mixing the solvent Any other formulation components are diluted in advance, and a solvent is mixed with these formulation components.

The method of mixing the components during the preparation is not particularly limited, and may be appropriately selected from the following well-known methods: a method of mixing by rotating a stirring bar or a stirring blade, a method of mixing using a mixer, and a method of applying ultrasonic waves for mixing method etc.

The temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounded component is not degraded, and may be appropriately adjusted, and the temperature is preferably 15°C to 30°C.

An example of the above-mentioned sheet for forming a first protective film will be described with reference to the drawings.

FIG. 5 is a cross-sectional view schematically showing an example of the first protective film-forming sheet.

The sheet 801 for 1st protective film formation shown here uses the sheet|seat which laminated|stacked the 1st adhesive bond layer on the 1st base material as a 1st support sheet. That is, the sheet 801 for forming a first protective film includes a first base material 811, a first adhesive layer 812 on the first base material 811, and a curable resin layer (curable resin layer) on the first adhesive layer 812. resin film) 82. As another aspect, the first support sheet includes a first base material 811 , a first adhesive layer 812 laminated on the first base material 811 , and a curable resin layer (cured) laminated on the first adhesive layer 812 resin film) 82.

The first support sheet 810 is a laminate of the first base material 811 and the first adhesive layer 812 , and a first adhesive layer is laminated on one surface 810 a of the first support sheet 810 , that is, in the first support sheet 810 On the surface 812a on the side of 812, the curable resin layer 82 is provided.

FIG. 6 is a cross-sectional view schematically showing another example of the first protective film-forming sheet.

The sheet 802 for 1st protective film formation shown here uses the sheet which consists only of a peeling film as a 1st support sheet. That is, the sheet 802 for 1st protective film formation is provided with the curable resin layer (curable resin film) 82 on the peeling film 821, and is comprised. As another aspect, the sheet|seat 802 for 1st protective film formation contains the peeling film 821 and the curable resin layer (curable resin film) 82 laminated|stacked on the peeling film 821.

The first support sheet 820 is a release film 821, and is provided on one surface 820a of the first support sheet 820, that is, one surface (in this specification, sometimes referred to as "the first surface") 821a of the release film 821. There is a curable resin layer 82 .

It is preferable that the 1st surface 821a of the peeling film 821 is a peeling process (peeling process surface).

In addition, the 1st sheet for protective film formation which the 1st support sheet consists of only the 1st base material also has the same structure as the sheet for 1st protective film formation shown in FIG. That is, in the sheet 802 for 1st protective film formation shown in FIG. 6, the code|symbol 821 is a 1st base material rather than a peeling film, and it is suitable also as a sheet for 1st protective film formation.

In any of the above-mentioned situations, the first protective film forming sheet can be the outermost surface layer (for example, the surface of the curable resin layer) on the opposite side with the side provided with the first supporting sheet in the first protective film forming sheet. ), and further includes a release film. Thus, the sheet for 1st protective film formation provided with a peeling film is easy to store and handle.

The release film in this case may be removed when the sheet for forming the first protective film is used. When the 1st support sheet is only made up of the peeling film as described above, as the peeling film of the 1st support sheet, and the peeling film that is provided with the outermost layer of the opposite side with the 1st support sheet can be identical to each other. different.

◇Manufacturing method of the sheet for 1st protective film formation

The composite sheet for 1st protective film formation can be manufactured by laminating|stacking the said each layer sequentially so that it may become a corresponding positional relationship. The formation method of each layer is as described above.

For example, a sheet for forming a first protective film (the first sheet for forming a protective film shown in FIG. 5 ) in which a first base material, a first adhesive layer, and a curable resin layer (curable resin film) are sequentially laminated in the thickness direction of these A sheet for protective film formation etc.) can be manufactured by the method shown below. That is, the above-mentioned 1st adhesive composition is apply|coated on a 1st base material, and it is made to dry as needed, and a 1st adhesive layer is laminated|stacked by this. Moreover, the curable resin layer is laminated|stacked by apply|coating the said composition for curable resin layer formation to the peeling process surface of a peeling film, and drying this as needed. Then, by bonding the curable resin layer on the release film and the first adhesive layer on the first base material, the first base material, the first adhesive layer, the curable resin layer and the release film are obtained in accordance with The sheet for 1st protective film formation which laminated|stacked these sequentially in the thickness direction. The release film may be removed when the first protective film forming sheet is used.

The above-mentioned sheet for 1st protective film formation can also be manufactured by the method shown below. That is, a 1st adhesive agent layer is laminated|stacked by apply|coating a 1st adhesive agent composition on the peeling process surface of a peeling film, and drying it as needed. Moreover, a curable resin layer was laminated|stacked on the peeling process surface of a peeling film by the same method as mentioned above separately. Then, the first adhesive layer on the release film is bonded to the first base material, and after removing the release film on the first adhesive layer, the surface on which the release film is laminated ( exposed surface), and pasted with the curable resin layer on the release film obtained above, thereby obtaining the first base material, the first adhesive layer, the curable resin layer and the release film. Laminate in this order in the thickness direction of these The obtained sheet for forming a first protective film.

The first protective film-forming sheet having layers other than the above-mentioned layers can be produced by appropriately adding additional layers in the above-mentioned production method so that the lamination position of the above-mentioned other layers becomes an appropriate position. The lamination steps of the other layers described above are carried out.

For example, when the first support sheet is formed by laminating the first base material, the first intermediate layer, and the first adhesive layer in this order in the thickness direction, the first protective film forming sheet can be as follows In the production, that is, in the above-mentioned production method, the lamination step of the first intermediate layer is additionally performed so as to arrange the first intermediate layer between the first base material and the first adhesive layer.

In addition, the sheet|seat for 1st protective film formation which does not have any arbitrary layer of the above-mentioned each layer can be manufactured by omitting the lamination|stacking process of the said arbitrary layer in the above-mentioned manufacturing method.

For example, the first protective film-forming sheet in the case where the first support sheet is composed of only the first base material can be produced by omitting the first adhesive layer in the above-mentioned production method. Layering step.

◇Second protective film forming sheet and method for producing the same

As a 2nd sheet for protective film formation, the same sheet as the sheet for 1st protective film formation mentioned above is mentioned, for example. However, since the function required for the second protective film forming sheet is different from that of the first protective film forming sheet, it is not necessary to be the same as the first protective film forming sheet.

In particular, the curable resin layer in the second sheet for forming a protective film may be composed of the same components as in the case of the curable resin layer in the sheet for forming a first protective film, and the content of each component in the curable resin layer is preferable. It is suitably adjusted so that a 2nd protective film may fully exhibit the target function.

In addition, in this specification, the 1st base material, the 1st intermediate layer and the 1st adhesive layer in the sheet for 1st protective film formation are called the 2nd base material, 1st intermediate layer and 1st adhesive layer in the 2nd sheet for protective film formation, respectively. The second intermediate layer and the second adhesive layer.

The 2nd sheet for protective film formation can be manufactured by the same method as the case of the above-mentioned sheet for 1st protective film formation.

‧Laminated structure fabrication steps

In the aforementioned layered structure fabrication step, the aforementioned semiconductor wafer with the protective film is bonded to a substrate via the bumps of the wafer, thereby fabricating the aforementioned layered structure.

The above-mentioned laminated structure is a novel laminated structure.

For example, in the above-mentioned manufacturing step of the laminated structure, flux is applied to the surface of the upper part of the bump in the semiconductor wafer with the protective film, and the upper part of the bump is brought into contact with the substrate, and the bump and the substrate are heated in this state, Thereby, the bumps are bonded to the substrate, and a laminated structure is produced. The heating conditions in this case are not particularly limited, but, for example, heating at 220° C. to 320° C. for 0.5 minutes to 10 minutes is preferable.

After the aforementioned layered structure fabrication step, a semiconductor device can be fabricated by the same method as the previous method using the obtained layered structure.

For example, the laminated structure can be sealed with resin to form a semiconductor package, and a target semiconductor device can be manufactured using the semiconductor package.

‧Semiconductor device

The semiconductor device obtained by the above-mentioned manufacturing method has the above-mentioned laminated structure, and is a novel semiconductor device.

That is, a semiconductor device as an embodiment of the present invention includes a layered structure in which a semiconductor wafer with a bump and a protective film is bonded to a substrate through the bumps; and the semiconductor chip with a protective film is bonded to a substrate through the bumps. A first protective film is provided on at least a first surface of the semiconductor wafer having bumps, or a second protective film is provided on a second surface of the semiconductor wafer on the opposite side to the first surface; When the wafer is provided with the first protective film, in the first protective film, the upper portions of the bumps protrude through the first protective film; the first protective film or the second protective film is a protective film having the following characteristics That is, when the shear strength ratio and the fracture risk factor of the laminated structure are measured by the following method, the shear strength ratio is 1.05 to 2, and the fracture risk factor is -0.9 to 0.9.

<Shear strength ratio of laminated structure>

A test piece of the laminate structure in which the substrate is a copper substrate is produced, the copper substrate in the test piece of the laminate structure is fixed, and the semiconductor wafer with the protective film in the test piece of the laminate structure is aligned along the opposite direction. A force was applied in a direction parallel to the surface of the copper substrate, and the force when the bonding state of the semiconductor wafer with the protective film and the copper substrate was broken was set as the shear strength (N) of the laminated structure; the laminated structure for comparison was produced. body (a test piece for comparison), the structure of the laminated structure for comparison is the same as that of the test piece of the laminated structure except that it does not have the first protective film and the second protective film, and the same structure as the laminated structure is used. The method of applying a force, the aforementioned force when the bonding state of the semiconductor wafer and the copper substrate of the aforementioned comparative test piece is broken is set as the aforementioned comparative shear strength (N) of the aforementioned laminated structure for comparison. The value of shear strength of body]/[shear strength for comparison of the aforementioned laminated structure for comparison] was set as the ratio of shear strength of the aforementioned laminated structure.

<Fracture Risk Factors of Laminated Structures>

A test piece having a width of 5 mm and a length of 20 mm was prepared for all the layers constituting the above-mentioned laminated structure, and all the above-mentioned test pieces were subjected to a heating and cooling test, that is, the temperature was raised from -70°C to 200°C at a heating rate of 5°C/min. The temperature was lowered from 200°C to -70°C at a cooling rate of 5°C/min, the expansion amount Eμm of the test piece when the temperature was raised from 23°C to 150°C and the difference between the test piece when the temperature was lowered from 23°C to -65°C were obtained. The total amount of shrinkage S μm, that is, the expansion and shrinkage ES μm, and then the value of [the expansion and contraction amount ES of the test piece]×[the thickness of the test piece], that is, the expansion and contraction parameter Pμm ² ; Next, obtain the [substrate The value of the expansion and contraction parameter P] of the test piece [the total value of the expansion and contraction parameters P of all the test pieces other than the substrate], that is, the expansion and contraction parameter difference ΔP1 μm ² ; Next, obtain the [expansion and contraction of the test piece of the substrate] The value of the parameter P]-[the total value of the expansion and contraction parameters P of all the test pieces except the substrate, the first protective film and the second protective film], that is, the expansion and contraction reference parameter difference ΔP0 μm ² ; the ΔP1/ The value of AP0 is set as the fracture risk factor of the aforementioned laminated structure.

The semiconductor device of the present invention may have the same configuration as the conventional semiconductor device except for the point of having the above-mentioned laminated structure.

[Example]

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited in any way by the examples shown below.

The components used for the production of the composition for forming a protective film are shown below.

[Polymer component (A)]

(A)-1: Polyvinyl butyral having structural units represented by the following formulae (i)-1, (i)-2 and (i)-3 (“S-LEC” manufactured by Sekisui Chemical Industry Co., Ltd. BL-10", weight average molecular weight 25000, glass transition temperature 59°C).

(A)-2: n-butyl acrylate (1 part by mass), methyl methacrylate (79 parts by mass), glycidyl methacrylate (5 parts by mass) and 2-hydroxyethyl acrylate (15 parts by mass) ) acrylic resin (weight average molecular weight 370000, glass transition temperature 7°C) obtained by copolymerization.

(in the formula, l ₁ is about 28, m ₁ is 1 to 3, and n ₁ is an integer of 68 to 74)

[Thermosetting component (B)]

‧Epoxy resin (B1)

(B1)-1: Liquid epoxy resin (an epoxy resin having a flexible skeleton introduced, "EXA4850-150" manufactured by DIC Corporation, molecular weight 900).

(B1)-2: Polyfunctional aromatic epoxy resin (“EPPN-502H” manufactured by Nippon Kayaku Co., Ltd.).

(B1)-3: Dicyclopentadiene-type epoxy resin (“Epiclon HP-7200HH” manufactured by DIC Corporation, epoxy equivalent: 274 g/eq to 286 g/eq).

(B1)-4: Bisphenol A epoxy resin (“BPA328” manufactured by Nippon Shokubai Corporation).

‧Thermosetting agent (B2)

(B2)-1: Novolak-type phenol resin (“BRG-556” manufactured by Showa Denko Corporation).

(B2)-2: Dicyandiamide (solid dispersion type latent hardener, "Adeka Hardener EH-3636AS" manufactured by ADEKA, active hydrogen amount 21 g/eq).

[Hardening accelerator (C)]

(C)-1: 2-phenyl-4,5-dihydroxymethylimidazole (“Curezol 2PHZ-PW” manufactured by Shikoku Chemical Industry Co., Ltd.).

[filler (D)]

(D)-1: A material obtained by physically crushing a fused silica filler (spherical silica (“SV-10” manufactured by Ronson Corporation), with an average particle size of 8 μm).

[Coupling agent (E)]

(E)-1: Silane coupling agent (oligomer type silane coupling agent containing epoxy group, methyl group and methoxy group, "X-41-1056" manufactured by Shin-Etsu Silicones, epoxy equivalent 280g/ eq).

(E)-2: 3-glycidyloxypropyltriethoxysilane (silane coupling agent, "KBE-403" manufactured by Shin-Etsu Silicones, methoxyl equivalent 8.1 mmol/g, molecular weight 278.4).

(E)-3: 3-glycidyloxypropyltrimethoxysilane (silane coupling agent, "KBM-403" manufactured by Shin-Etsu Silicones, methoxyl equivalent 12.7 mmol/g, molecular weight 236.3).

[Colorant (I)]

(I)-1: Carbon black (“MA600” manufactured by Mitsubishi Chemical Corporation, average particle size: 20 nm).

[Example 1]

<Production of Laminated Structures>

(Manufacture (1) of thermosetting resin layer forming composition)

Polymer component (A)-1, epoxy resin (B1)-1, epoxy resin (B1)-2, epoxy resin (B1)-3, thermosetting agent (B2)-1, and hardening accelerator (C)-1 was dissolved or dispersed in methyl ethyl ketone so that the content ratio of these became the values shown in Table 1, and stirred at 23° C. to obtain a composition for forming a thermosetting resin layer. , the composition (III)-1 for forming a resin layer having a solid content concentration of 55% by mass was obtained. In addition, when the column of the contained component in Table 1 is described as "-", it shows that the composition for thermosetting resin layer formation does not contain this component. In addition, the content of each component shown in Table 1 is all solid content content.

(Production of Adhesive Resin (I-2a))

Acrylic polymer (molecular weight about 700,000) obtained by copolymerizing 2-ethylhexyl acrylate (80 parts by mass) and 2-hydroxyethyl acrylate (hereinafter abbreviated as "HEA") (20 parts by mass) ), 2-methacryloyloxyethyl isocyanate (hereinafter, abbreviated as "MOI") was added (with respect to the total moles of hydroxyl groups derived from HEA in the aforementioned acrylic polymer, isocyanate The total number of moles of isocyanate groups in 2-methacryloyloxyethyl ester becomes 0.8 times the amount), and reacted at room temperature for 1 day to obtain an acrylic copolymer having a methacryloyloxy group in the side chain. UV-curable adhesive resin (I-2a).

(Manufacture of the first adhesive composition (I-2))

With respect to the above-obtained adhesive resin (I-2a) (100 parts by mass), an isocyanate-based crosslinking agent ("Coronate L" manufactured by Nippon Polyurethane Co., Ltd., toluene diisocyanate trimer of trimethylolpropane) was added. product) (2.0 parts by mass), a photopolymerization initiator (“Irgacure 184” manufactured by Ciba Speciality Chemicals, 1-hydroxycyclohexyl phenyl ketone) (0.1 parts by mass), and stirring to obtain an ultraviolet Curable first adhesive composition (I-2).

(Manufacture of the first support sheet)

The above-mentioned peeling-treated side was applied to the peeling-treated side of a peeling film (“SP-PET381031” manufactured by Lintec, thickness 38 μm) which was peeled by polysiloxane treatment on one side of a polyethylene terephthalate film. The obtained first adhesive composition (I-2) was heated and dried at 100° C. for 1 minute, thereby forming a first adhesive layer with a thickness of 10 μm.

Next, the first adhesive layer on the release film was bonded to the first base material (thickness: 400 μm) made of a polyacrylate urethane film to obtain the first base material and the first adhesive layer. And the 1st support sheet of a peeling film is provided on the 1st adhesive bond layer.

(Manufacture of the first protective film forming sheet)

The above-mentioned peeling-treated side was applied to the peeling-treated side of a peeling film (“SP-PET381031” manufactured by Lintec, thickness 38 μm) which was peeled by polysiloxane treatment on one side of a polyethylene terephthalate film. The obtained composition (III)-1 for forming a resin layer was heated and dried at 120° C. for 2 minutes to form a thermosetting resin film having a thickness of 30 μm.

Next, the release film was removed from the first support sheet, and the exposed first adhesive layer was bonded to the thermosetting resin film on the release film obtained above to obtain a first protection having the configuration shown in FIG. 5 . The sheet for film formation is formed by laminating a first base material, a first adhesive layer, a thermosetting resin film, and a release film in this order in the thickness direction of these.

(Manufacture (2) of thermosetting resin layer forming composition)

Polymer component (A)-2, epoxy resin (B1)-3, epoxy resin (B1)-4, thermosetting agent (B2)-2, hardening accelerator (C)-1, filler (D) )-1, coupling agent (E)-1, coupling agent (E)-2, coupling agent (E)-3, and coloring agent (I)-1, the content ratios of these become the values shown in Table 1 It was dissolved or dispersed in methyl ethyl ketone, and stirred at 23°C to obtain a composition for forming a resin layer (III) having a solid content concentration of 55% by mass as a composition for forming a thermosetting resin layer. )-2.

(Manufacture of the second support sheet)

The above-mentioned peeling-treated side of a peeling film (“SP-PET381031” manufactured by Lintec, thickness 38 μm) which was peeled by polysiloxane treatment on one side of a polyethylene terephthalate film was applied. The first adhesive composition (I-2) is heated and dried to form a first adhesive layer.

Next, the first adhesive layer on the release film and the second base material (thickness: 100 μm) made of a polyolefin film were bonded together, and the second base material, the first adhesive layer, and the release film were prepared in this order. A laminate formed by laminating in the thickness direction.

Next, from the release film side of the obtained laminate, the first adhesive layer was irradiated with ultraviolet rays under the conditions of an illuminance of 230 mW/cm ² and a light intensity of 120 mJ/cm ² to cure the first adhesive layer by ultraviolet rays. In this way, a second support sheet was obtained. The second support sheet was formed by laminating the ultraviolet cured product of the first adhesive layer with a thickness of 10 μm on the second substrate as the second adhesive layer, and further provided a release film on the second adhesive layer. .

(Manufacture of the second protective film forming sheet)

The above-mentioned peeling-treated side was applied to the peeling-treated side of a peeling film (“SP-PET381031” manufactured by Lintec, thickness 38 μm) which was peeled by polysiloxane treatment on one side of a polyethylene terephthalate film. The obtained composition (III)-2 for forming a resin layer was heated and dried at 120° C. for 2 minutes to form a thermosetting resin film having a thickness of 25 μm.

Next, the release film was removed from the second support sheet, and the exposed second adhesive layer was bonded to the thermosetting resin film on the release film obtained above to obtain a second composition having the configuration shown in FIG. 5 . The sheet for forming a protective film is formed by laminating a second base material, a second adhesive layer, a thermosetting resin film, and a release film in this order in the thickness direction.

(Manufacture of laminated structure)

As a semiconductor wafer, prepare the following silicon wafer (diameter 200mm, thickness 250μm), the silicon wafer is on the circuit surface of an 8-inch silicon wafer, and the distance between bumps is 400μm and has a large number of shapes as shown in Figure 1 The bumps are the same, with a height of 200 μm and a width of 250 μm.

Then, the release film was removed from the sheet for forming the first protective film obtained above, and while the thermosetting resin film was heated at 70° C., the newly generated exposed surface of the thermosetting resin film (with the The side of the first adhesive layer is the opposite side) is attached to the first surface (bump formation surface) of the above-mentioned silicon wafer, so that the thermosetting resin film is in close contact with the circuit surface and the surface of the bump.

Next, the first support sheet is removed from the thermosetting resin film.

On the other hand, the release film was removed from the sheet for forming a second protective film obtained above, and the newly generated exposed surface ( The surface opposite to the side provided with the second adhesive layer) is attached to the second surface (back surface) of the above-mentioned silicon wafer.

Through the above steps, a laminate in which the second base material, the second adhesive layer, the curable resin film, the semiconductor wafer, and the curable resin film are laminated in this order is obtained.

Next, the above-mentioned two-layer thermosetting resin film was heat-treated at 130° C. for 2 hours to be thermally cured to form a first protective film and a second protective film.

Next, using a dicing blade, the semiconductor wafer provided with the first protective film and the second protective film is diced and separated into pieces, thereby obtaining a size of 6 cm×6 cm, the first protective film is provided on the first surface, and the first protective film is provided on the first surface. A semiconductor wafer with a protective film having a second protective film on both sides.

Next, the semiconductor wafer with the protective film is pulled away from the laminated sheet (corresponding to a dicing sheet) of the second base material and the second adhesive layer and picked up.

Next, in the semiconductor wafer with the protective film, flux is applied to the surface of the upper portion of the bump that protrudes through the first protective film, and an organic substrate (glass epoxy resin) is placed on the upper portion of the bump. thickness 930 μm), in this state, the bumps and the organic substrate were heated on a heater at 300° C. for 1 minute, whereby the semiconductor wafer with the protective film was bonded to the organic substrate through the bumps to obtain a laminated structure. After heating, the obtained laminated structure was washed and the flux was removed. The laminate structure system obtained here is a laminate structure in which a semiconductor wafer with a protective film including a first protective film on the first surface and a second protective film on the second surface is bonded to an organic substrate via the bumps.

<Evaluation of Laminated Structures>

(Calculation of shear strength ratio)

By the same method as above, a semiconductor wafer with a protective film was obtained.

Next, in the semiconductor wafer with the protective film, a flux was applied to the surface of the upper portion of the bump protruding through the first protective film, a copper substrate (thickness 930 μm) was placed on the upper portion of the bump, and in this state, the The bumps and the copper substrate were heated on a heater at 300° C. for 1 minute, whereby the semiconductor wafer with the protective film was bonded to the copper substrate through the bumps to obtain a laminated structure. After heating, the obtained laminated structure was washed and the flux was removed. The layered structure obtained here is the same as the above-mentioned layered structure provided with the organic substrate except that it has a copper substrate instead of the organic substrate. Four such laminated structures were produced.

Next, using a bonding strength tester (“DAGE4000 Die shear tester” manufactured by Nordson Corporation), a wafer shear test was performed on the above-obtained laminate structure with a copper substrate, thereby measuring the semiconductor wafer with a protective film and copper The bonding strength of the substrate, that is, the shear strength.

More specifically, the shear strength was measured by the following method. That is, a laminated structure is installed in the bonding strength test machine, the copper substrate in the laminated structure is fixed, and a force is applied to the semiconductor wafer with the protective film in the laminated structure in a direction parallel to the surface of the copper substrate. At this time, as a tool for applying force to the semiconductor wafer with protective film, a tool of model "SHR-250-9000" was used, and as a load cell, a load cell of model "DS100" was used. The force was applied under the condition that the cutting height was 5 μm. Then, the force applied when the bonding state of the semiconductor wafer with the protective film and the copper substrate was broken was read, and the value of the force was defined as the shear strength (N) of the laminated structure. The shear strength of the four laminated structures was measured in this way, and the average value of the measured values at that time was used as the shear strength (N) of the laminated structure.

Four separate laminated structures for comparison were produced, and the laminated structures for comparison had the same structure as the above-mentioned laminated structures provided with the copper substrate except that they did not include the first protective film and the second protective film.

Next, a force was applied to the laminated structure for comparison by the same method as in the case of the above-mentioned laminated structure, the force applied when the bonding state between the semiconductor wafer and the copper substrate was broken was read, and the value of the force was set as a comparison Shear strength (N) was used for comparison with the laminated structure. With respect to the four comparative laminated structures, the comparative shear strengths were measured in this manner, and the average value of the measured values at this time was used as the comparative shear strength (N) of the comparative laminated structures.

Using these measured values of shear strength (N), the value of [shear strength of laminated structure (N)]/[shear strength of comparative laminated structure (N)] was calculated, and this value was set as Shear strength ratio of the laminated structure. The results are shown in Table 2.

(Calculation of Fracture Risk Factors for Laminated Structures)

All the layers constituting the above-described laminated structure including the organic substrate, that is, the substrate (organic substrate), the first protective film, the semiconductor wafer, and the second protective film were prepared. These test pieces have a width of 5 mm and a length of 20 mm, so that they are the same as the layers constituting the laminated structure except for the difference in size (width and length) (that is, the thickness of each test piece is the same as the thickness of each layer constituting the laminated structure). same thickness). Four test pieces were produced for each type.

Next, using a thermomechanical analyzer (“TMA4000SA” manufactured by NETCH Co., Ltd.), a heating and cooling test was performed on all the above-mentioned test pieces, that is, the temperature was raised from -70°C to 200°C at a heating rate of 5°C/min, and the temperature was increased from 200°C to 200°C. The temperature was lowered to -70°C at a cooling rate of 5°C/min, and the expansion amount Eμm of the test piece when the temperature was raised from 23°C to 150°C and the shrinkage amount Sμm of the test piece when the temperature was lowered from 23°C to -65°C were measured.

Then, for each test piece, the total amount (sum of absolute values) of these measured values, that is, the amount of expansion and contraction ES μm, was calculated, and [the amount of expansion and contraction of the test piece ES (μm)]×[the thickness of the test piece ( The value of μm)] is set as the expansion and contraction parameter Pμm ² . For the four test pieces, the expansion-contraction parameter Pμm ² was obtained in this way, and the average value of the expansion-contraction parameters was used as the expansion-contraction parameter Pμm ² of the test piece.

Next, the value of [expansion and shrinkage parameter P (μm ² ) of the test piece of the substrate] - [the total value of the expansion and contraction parameter P of all the test pieces other than the substrate (μm ² )], that is, the difference in expansion and contraction parameter ΔP1 μm is obtained. ² . Here, the term "all test pieces other than the substrate" refers to the test pieces of the semiconductor wafer, the first protective film, and the second protective film.

Next, [the expansion and contraction parameter P of the test piece of the substrate (μm ² )] - [the total value (μm ² ) of the expansion and contraction parameter P of all the test pieces except the substrate, the first protective film, and the second protective film] was obtained. The value is ΔP0 μm ² of the reference parameter difference of expansion and contraction. Here, the term "all test pieces other than the substrate, the first protective film, and the second protective film" refers to a test piece of a semiconductor wafer.

Next, the value of ΔP1/ΔP0 is calculated, and this value is used as the fracture risk factor of the laminated structure. The results are shown in Table 2.

(Reliability Evaluation)

For the above-mentioned laminated structure with organic substrate, according to JEDEC STANDERD 22-A104E, under condition C (-65°C to 150°C, exposure time 10 minutes), a temperature cycle test (sometimes abbreviated as TCT) was performed, and it was confirmed that the The number of cycles (times) until the bonding state of the semiconductor wafer with the protective film and the organic substrate is destroyed. The temperature cycle test was performed on four laminated structures, and the average value of the number of cycles was obtained, and this value was used as an index of the reliability of the laminated structures. The results are shown in Table 2.

<Production and Evaluation of Laminated Structures>

[Example 2]

A layered structure was obtained by the same method as in the case of Example 1 except that the second protective film was not formed. The laminate structure system obtained here is a laminate structure in which a semiconductor wafer with a protective film having a first protective film on the first surface and not having a second protective film on the second surface is bonded to a substrate via the bumps.

And the obtained laminated structure was evaluated by the same method as the case of Example 1. The results are shown in Table 2.

[Example 3]

As the semiconductor wafer, the following silicon wafer was prepared. The thickness of the silicon wafer was 500 μm instead of 250 μm, and other aspects were the same as the semiconductor wafer used in the second embodiment. Then, except for the point of using this silicon wafer, the same method as in the case of Example 2 was used to manufacture a layered structure and evaluate it. The results are shown in Table 2.

[Example 4]

As a semiconductor wafer, the following silicon wafer was prepared. The thickness of the silicon wafer was 500 μm instead of 250 μm, and other aspects were the same as the semiconductor wafer used in Example 1.

In addition, as shown in Table 1, except that the filler (D)-1 (230 parts by mass) was newly used, the heat The composition for forming a curable resin layer was obtained as a composition (III)-3 for forming a resin layer having a solid content concentration of 69% by mass.

And except for using these silicon wafers and the composition (III)-3 for resin layer formation, the laminated structure was manufactured by the same method as the case of Example 2, and it evaluated. The results are shown in Table 2.

[Example 5]

A layered structure was obtained by the same method as in the case of Example 1 except that the thickness of the second protective film was 43 μm instead of 25 μm and the first protective film was not formed. The laminated structure system obtained here is a laminated structure in which a semiconductor wafer with a protective film provided with the second protective film on the second surface and not provided with the first protective film on the first surface is bonded to a substrate via the bumps.

And the obtained laminated structure was evaluated by the same method as the case of Example 1. The results are shown in Table 3.

[Comparative Example 1]

A composition (IX)-1 for forming a resin layer was obtained as a composition for forming a thermosetting resin layer by the same method as in the case of Example 1 except that the curing accelerator (C)-1 was not used.

Further, except that the resin layer forming composition (IX)-1 was used in place of the resin layer forming composition (III)-1, a laminated structure was produced by the same method as in the case of Example 2, and This laminated structure was evaluated. The results are shown in Table 3.

[Comparative Example 2]

As a semiconductor wafer, the following silicon wafer was prepared. The thickness of the silicon wafer was 500 μm instead of 250 μm, and other aspects were the same as the semiconductor wafer used in Example 1.

Furthermore, except that the silicon wafer was used and the first protective film was not formed, a laminated structure was obtained by the same method as in the case of Example 1. The laminate structure system obtained here is a laminate structure in which a semiconductor wafer with a protective film having a second protective film on the second surface and not having the first protective film on the first surface is bonded to a substrate via the bumps.

And the obtained laminated structure was evaluated by the same method as the case of Example 1. The results are shown in Table 3.

<Production and Evaluation of Laminated Structures for Comparison>

[Experimental Example 1]

As the semiconductor wafer, the same semiconductor wafer (ie, an 8-inch silicon wafer) as the semiconductor wafer used in Example 1 was used, and a dicing sheet was attached to the second surface (back surface) of the semiconductor wafer.

Next, by the same method as in the case of Example 1, the semiconductor wafer that does not have both the first protective film and the second protective film is diced and singulated to form a semiconductor wafer, and the semiconductor is picked up. wafer.

Next, a laminate structure was obtained by the same method as in the case of Example 1, except that a semiconductor wafer without both the first protective film and the second protective film was used instead of the semiconductor wafer with the protective film described above. (Laminated structure for comparison). The laminated structure obtained here in which the semiconductor wafer for comparison is bonded to the substrate via the bump alone is different from the laminated structure for comparison provided with the copper substrate described above.

Next, the reliability evaluation of the laminated structure for comparison was performed by the same method as in the case of Example 1. The results are shown in Table 3.

According to the above results, in Examples 1 to 5, the shear strength ratio of the laminated structure was 1.15 to 2.00, and the fracture risk factor was 0.83 to 0.90. The number of cycles until the bonding state is broken is more than 300 times, and the bonding of the semiconductor wafer with the protective film to the substrate is stable over a long period of time even under conditions of severe temperature changes.

On the other hand, in Comparative Example 1, the shear strength ratio of the laminated structure was less than 1.05, and the fracture risk factor was greater than 0.9, resulting in a small number of cycles until the bonding state of the semiconductor wafer with the protective film and the organic substrate was broken. , Under the conditions of severe temperature changes, the bonding of the semiconductor chip with the protective film to the substrate is unstable.

In Comparative Example 2, the shear strength ratio of the laminated structure was greater than 2, and the fracture risk factor was greater than 0.9, resulting in a small number of cycles until the bonding state of the semiconductor wafer with the protective film and the organic substrate was destroyed, and the temperature changed drastically. Under such conditions, the bonding of the semiconductor wafer with the protective film to the substrate is unstable.

(Industrial Availability)

The present invention can be used to manufacture a semiconductor chip having bumps on a connection pad portion used in a flip-chip mounting method, and the like.

1‧‧‧Laminated structure

10‧‧‧Semiconductor chip with protective film

11‧‧‧Semiconductor Chips

11a‧‧‧Side 1 of semiconductor chip

11b‧‧‧Side 2 of semiconductor wafer

12‧‧‧First protective film

13‧‧‧Second protective film

14‧‧‧Substrate

14a‧‧‧First side of the substrate

111‧‧‧Bumps

111a‧‧‧Top of bump

1110‧‧‧Top of bump

Claims (2)

A method for manufacturing a semiconductor device, comprising: producing a semiconductor wafer with a protective film, wherein the semiconductor wafer with the protective film is provided with a first protective film at least on a first surface of the semiconductor wafer having bumps, or on the semiconductor wafer with a first protective film. The second surface on the opposite side of the first surface is provided with a second protective film; and a layered structure is produced, wherein the layered structure is formed by bonding the semiconductor wafer with the protective film to the substrate through bumps; and the semiconductor chip with the protective film is formed In the production of the wafer, the first protective film is formed in such a way that the upper part of the bump penetrates the first protective film and protrudes; the first protective film or the second protective film is a protective film having the following characteristics: using When the shear strength ratio and fracture risk factor of the laminated structure were measured by the following method, the shear strength ratio was 1.05 to 2, and the fracture risk factor was -0.9 to 0.9; Shear strength ratio of the laminated structure: production The test piece of the laminate structure in which the substrate is a copper substrate, the copper substrate in the test piece of the laminate structure is fixed, and the edge of the semiconductor wafer with the protective film in the test piece of the laminate structure is opposite to the copper substrate. A force was applied in a direction parallel to the surface of the substrate, and the force when the bonding state of the semiconductor wafer with the protective film and the copper substrate was broken was set as the shear strength N of the laminated structure; The test piece has the same structure as the test piece of the laminated structure, except that it does not have the first protective film and the second protective film, and the force is applied in the same way as the test piece of the laminated structure. The aforementioned force when the bonding state between the semiconductor wafer and the copper substrate of the test piece is broken is set as the comparative shear strength N of the laminated structure for comparison; The value obtained by comparing the shear strength of the above-mentioned laminated structure) was set as the shear strength ratio of the above-mentioned laminated structure; the fracture risk factor of the laminated structure: a test piece with a width of 5 mm and a length of 20 mm for all the layers constituting the laminated structure was prepared, All the above-mentioned test pieces were subjected to a heating-cooling test. The above-mentioned heating-cooling test was performed by raising the temperature from -70°C to 200°C at a heating rate of 5°C/min, and then cooling from 200°C to -70°C at a cooling rate of 5°C/min. The total amount of the expansion amount Eμm of the test piece when the temperature was raised from 23°C to 150°C and the shrinkage amount Sμm of the test piece when the temperature was lowered from 23°C to -65°C, that is, the expansion and shrinkage amount ES μm, was further obtained (the aforementioned The value obtained by the amount of expansion and shrinkage of the test piece ES × the thickness of the test piece), that is, the expansion and contraction parameter Pμm ² ; secondly, obtain (the expansion and contraction parameter of the test piece of the substrate P-the expansion and contraction parameters of all the test pieces except the substrate) The value obtained from the total value of P), that is, the difference in expansion and contraction parameters ΔP1 μm ² ; next, (the expansion and contraction parameter P of the test piece of the substrate - the value of all the test pieces other than the substrate, the first protective film, and the second protective film) was obtained. The value obtained from the total value of the expansion and contraction parameters P) is the expansion and contraction reference parameter difference ΔP0 μm ² ; The value of 1/ΔP0 was set as the fracture risk factor of the aforementioned laminated structure. A semiconductor device, comprising a laminated structure, wherein the laminated structure system has a semiconductor wafer with bumps and a protective film attached to a substrate through the bumps; the semiconductor wafer with a protective film is at least one of the semiconductor wafers with bumps. A first protective film is provided on the first surface, or a second protective film is provided on a second surface of the semiconductor wafer on the opposite side to the first surface, and in the first protective film, the upper portion of the bump penetrates through the first protective film. 1 protective film to protrude; the first protective film or the second protective film is a protective film having the following characteristics: when the shear strength ratio and the fracture risk factor of the laminated structure are measured by the following methods, the shear strength The ratio is 1.05 to 2, and the aforementioned fracture risk factor is -0.9 to 0.9; Shear strength ratio of the laminated structure: A test piece of the laminated structure whose substrate is a copper substrate is prepared, and the test piece of the laminated structure is placed in the test piece of the laminated structure. The above-mentioned copper substrate is fixed, and a force is applied to the semiconductor wafer with the protective film in the test piece of the above-mentioned laminated structure in a direction parallel to the surface of the above-mentioned copper substrate, and the above-mentioned semiconductor chip with the protective film is bonded to the above-mentioned copper substrate. The aforementioned force at the time of state failure is set as the shear strength N of the aforementioned laminated structure; The test piece of the laminated structure was the same, and the force was applied by the same method as the test piece of the laminated structure, and the force when the bonding state of the semiconductor wafer and the copper substrate of the test piece for comparison was broken was set as the laminated structure for comparison. The comparison shear strength N; the value obtained at this time (the shear strength of the aforementioned laminated structure/the comparative shear strength of the aforementioned laminated structure) is set as the shear strength ratio of the aforementioned laminated structure; For the fracture risk factor of the laminated structure, a test piece having a width of 5 mm and a length of 20 mm constituting all the layers of the laminated structure was prepared, and all the test pieces were subjected to a heating and cooling test, that is, a temperature increase rate from -70°C was performed The temperature was raised from 5°C/min to 200°C, the temperature was lowered from 200°C to -70°C at a cooling rate of 5°C/min. The total amount of shrinkage Sμm of the test piece at -65°C is the expansion and shrinkage amount ES μm, and the value obtained by (the expansion and shrinkage amount ES of the test piece × the thickness of the test piece), that is, the expansion and shrinkage parameter Pμm ² ; Next, obtain the value obtained by (the expansion and contraction parameter P of the test piece of the substrate - the total value of the expansion and contraction parameters P of all the test pieces except the substrate), that is, the expansion and contraction parameter difference ΔP1 μm ² ; Next, obtain ( The value obtained from the expansion and contraction parameter P of the test piece of the substrate - the total value of the expansion and contraction parameters P of all the test pieces other than the substrate, the first protective film and the second protective film), that is, the expansion and contraction reference parameter difference ΔP0 μm ² ; The value of ΔP1/ΔP0 at this time is set as the fracture risk factor of the above-mentioned laminated structure.

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