Resin composition, semiconductor device, and method for manufacturing a semiconductor device

Abstract

The present invention provides a resin composition for wafer-level chip-size package type semiconductor devices that can form a coating film with good high-frequency characteristics, minimal thickness variation, and reduced likelihood of semiconductor substrate warping, as well as a semiconductor device using the same and a method for manufacturing a semiconductor device. [Solution] A resin composition for wafer-level chip-size package type semiconductor device, comprising (A) a modified polyphenylene ether resin having an unsaturated double bond at its terminus, and (B) an elastomer having a butadiene skeleton, and optionally (C) a solvent; a semiconductor device using the same; and a method for manufacturing a semiconductor device.

Description

[Technical Field]

[0001] The present invention relates to a resin composition, a semiconductor device using the same, and a method for manufacturing a semiconductor device. [Background technology]

[0002] As electronic devices become smaller, lighter, and more functional, semiconductor packages mounted on these devices are also required to be smaller, lighter, and have higher density mounting on the substrate. In this context, a semiconductor packaging technology called wafer-level chip-size packaging (also known as "WL-CSP") has been proposed. Wafer-level chip-size packaging is a semiconductor package that does not use bonding wires for internal wiring, leaving a portion of the semiconductor substrate (silicon wafer) exposed, and is approximately the same size as the semiconductor substrate.

[0003] For example, Patent Documents 1 and 2 disclose WL-CSP. WL-CSP comprises a multilayer structure on a semiconductor substrate (silicon wafer) including electrodes, an insulating layer, a redistribution layer, and a sealing resin layer, as well as external terminals such as solder pumps. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2017-92152 [Patent Document 2] Japanese Patent Publication No. 2010-192938 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] With the increasing speed of information transmission and the increasing volume of information, high-frequency characteristics are required for electronic components, and WL-CSPs mounted on electronic components are also required to have high-frequency characteristics. For example, in the high-frequency region, specifically, it is required to have excellent electrical characteristics (low dielectric constant (ε), low dielectric tangent (tanδ)) in the frequency range of 1 GHz to 10 GHz.

[0006] In some cases, a resin composition is applied onto a semiconductor substrate (silicon wafer) using a rotary spin coater to form an interlayer insulating film for WL-CSP. However, depending on the resin material, when applying the resin composition onto the semiconductor substrate using a spin coater, a uniform coating film may not be formed on the semiconductor substrate, or warping may occur on the semiconductor substrate due to shrinkage during curing of the resin composition after application.

[0007] Therefore, an object of the present invention is to provide a resin composition for a wafer-level chip size package type semiconductor device, a semiconductor device using the same, and a method for manufacturing the semiconductor device, which have good high-frequency characteristics, little thickness variation even when applied onto a semiconductor substrate using a spin coater, and can form a coating film that is less likely to cause warping of the semiconductor substrate.

Means for Solving the Problems

[0008] The means for solving the above problems are as follows, and the present invention includes the following aspects.

[0009] [1] A resin composition for a wafer-level chip size package type semiconductor device, comprising (A) a modified polyphenylene ether resin having an unsaturated double bond at its terminal, and (B) an elastomer having a butadiene backbone. [2] The modified polyphenylene ether resin (A) having an unsaturated double bond at its terminal is represented by the following formula (1):

Chemical Formula

[10] The resin composition according to any one of [1] to [9] above, wherein the mass ratio of component (A) to component (B) is in the range of 10:90 to 80:20.

[11] The resin composition according to any one of [7] to

[10] , wherein the mass ratio of the total amount of component (A) and component (B) to component (C) is in the range of 5:95 to 80:20.

[12] A wafer-level chip-size package semiconductor device comprising a semiconductor substrate, electrodes disposed on the semiconductor substrate, wiring electrically connected to the electrodes, external terminals electrically connected to the electrodes via the wiring, and an interlayer insulating film sealing the side of the semiconductor substrate on which the electrodes and wiring are disposed, wherein the interlayer insulating film is disposed in contact with the wiring, and the resin composition is one of the above [1] to

[11] .

[13] The semiconductor device according to

[12] , comprising at least two layers: a first interlayer insulating film that seals the semiconductor substrate side of the wiring, and a second interlayer insulating film that seals the semiconductor substrate side of the wiring.

[14] The semiconductor device according to

[12] or

[13] , wherein the thickness of one of the interlayer insulating films, the first interlayer insulating film, or the second interlayer insulating film is in the range of 3 μm or more and 20 μm or less.

[15] The following ingredients (A) to (C): (A) Modified polyphenylene ether resin having an unsaturated double bond at the terminal, (B) Elastomers having a butadiene skeleton, and (C) Prepare a liquid resin composition containing a solvent, The process involves dropping the resin composition onto a semiconductor substrate, and then using a spin coater to rotate the semiconductor substrate around a vertical axis to coat the semiconductor substrate with the liquid resin composition. A method for manufacturing a wafer-level chip-size package type semiconductor device, comprising curing the liquid resin composition to form an interlayer insulating film.

[16] The method for manufacturing a semiconductor device according to

[15] , wherein the rotation speed of the spin coater is 1000 rpm to 3000 rpm and the rotation time is 5 seconds to 30 seconds.

[17] The method for manufacturing a semiconductor device according to

[15] or

[16] , wherein the liquid resin composition has a first viscosity of 300 mPa·s to 4000 mPa·s at 25°C and 10 rpm as measured by a rotational viscometer.

[18] The method for manufacturing a semiconductor device according to

[17] , wherein the liquid composition has a second viscosity of 500 mPa·s to 4200 mPa·s at 25°C and 1 rpm as measured by a rotational viscometer, and a thixotropy index TI, which is the ratio of the second viscosity to the first viscosity, of 0.8 to 1.2.

[19] The modified polyphenylene ether resin having an unsaturated double bond at the (A) terminus includes the polyphenylene ether resin represented by formula (1), The method for manufacturing a semiconductor device according to any one of the above

[15] to

[18] , wherein the elastomer having a butadiene skeleton (B) comprises at least one selected from the group consisting of styrene / butadiene / styrene copolymer, styrene / butadiene / butylene / styrene copolymer, butadiene polymer, styrene / butadiene copolymer, and acrylonitrile / butadiene copolymer. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a resin composition for wafer-level chip-size package type semiconductor devices that has good high-frequency characteristics, exhibits little variation in thickness even when applied to a semiconductor substrate using a spin coater, and forms a coating film that is less likely to cause warping of the semiconductor substrate, as well as a semiconductor device using the same and a method for manufacturing a semiconductor device. [Brief explanation of the drawing]

[0011] [Figure 1] Figure 1 is a schematic cross-sectional view showing a schematic configuration of a part of a WL-CSP type semiconductor device. [Modes for carrying out the invention]

[0012] The following description will be based on embodiments of the resin composition for wafer-level chip-size package type semiconductor devices, a semiconductor device using the same, and a method for manufacturing a semiconductor device according to this disclosure. However, the embodiments shown below are illustrative examples for embodying the technical concept of the present invention, and the present invention is not limited to the resin composition, semiconductor device using the same, and method for manufacturing a semiconductor device described below.

[0013] The resin composition according to the first embodiment of the present invention comprises a specific modified polyphenylene ether (also referred to as "component (A)") and an elastomer having a butadiene skeleton (also referred to as "component (B)"). Since the resin composition contains the modified polyphenylene ether of component (A), the relative permittivity (ε) of the coating film made from the cured product obtained by curing the resin composition constituting the interlayer insulating film is preferably 3.0 or less, more preferably 2.9 or less, even more preferably 2.8 or less, and particularly preferably 2.7 or less. The relative permittivity (ε) of the coating film made from the cured product obtained by curing the resin composition constituting the interlayer insulating film may be 1.0 or more, and preferably 1.5 or more. Furthermore, the dielectric loss tangent (tanδ) of the coating film made from the resin composition constituting the interlayer insulating film is preferably 0.015 or less, more preferably 0.014 or less, and even more preferably 0.013 or less. The dielectric loss tangent (tanδ) of the coating film made from the resin composition constituting the interlayer insulating film is preferably 0.001 or more. If the relative permittivity of a coating film made of a resin composition constituting the interlayer insulating film of a WL-CSP type semiconductor device is 3.0 or less and the dielectric loss tangent (tanδ) is 0.015 or less, it will have a low permittivity and low dielectric loss tangent, resulting in good electrical characteristics when used in high-frequency ranges. For example, a coating film with good electrical characteristics can be obtained even when semiconductor devices are used in high-frequency ranges such as the fifth-generation communication system "5G," where increased capacity and high-speed communication are expected.

[0014] Because the resin composition contains components (A) and (B), it shrinks uniformly during curing when applied to a semiconductor substrate, making warping of the semiconductor substrate less likely. Therefore, the resin composition containing components (A) and (B) is suitable for forming interlayer insulating films in WL-CSP type semiconductor devices.

[0015] The resin composition preferably further contains, if necessary, a solvent (C) (also referred to as "component (C)") along with components (A) and (B). Resin compositions containing both components (A) and (B) along with component (C) exhibit good thixotropy. Resin compositions containing both components (A) and (B) along with component (C) can form a coating film of substantially uniform thickness with little variation in thickness, even when applied to a semiconductor substrate using, for example, a spin coater.

[0016] The resin composition containing components (A), (B), and (C) preferably has a first viscosity measured by a rotational viscometer at 25°C and 10 rpm in the range of 300 mPa·s to 4000 mPa·s. If the first viscosity of the resin composition is in the range of 300 mPa·s to 4000 mPa·s, then even when applied to a semiconductor substrate using, for example, a spin coater, the variation in thickness will be small, a coating film of substantially uniform thickness can be formed, and warping of the semiconductor substrate during curing can be suppressed. The first viscosity of the resin composition is more preferably 400 mPa·s to 4000 mPa·s, and even more preferably 500 mPa·s to 2000 mPa·s. In this specification, the rotational viscometer can be measured using, for example, a TVE type viscometer (cone rotor: 1° 34' × R24, manufactured by Toki Sangyo Co., Ltd.).

[0017] The resin composition containing components (A), (B), and (C) preferably has a second viscosity measured by a rotational viscometer at 25°C and 1 rpm in the range of 500 mPa·s to 4200 mPa·s. If the second viscosity of the resin composition is in the range of 500 mPa·s to 4200 mPa·s, then even when applied to a semiconductor substrate using, for example, a spin coater, the thickness variation will be small, a coating film of substantially uniform thickness can be formed, and warping of the semiconductor substrate during curing can be suppressed. The second viscosity of the resin composition is more preferably in the range of 550 mPa·s to 4000 mPa·s, and even more preferably in the range of 550 mPa·s to 3500 mPa·s.

[0018] The resin composition containing components (A), (B), and (C) preferably has a thixotropy index TI, which is the ratio of the second viscosity to the first viscosity, in the range of 0.8 to 1.2, and possesses thixotropy close to that of a Newtonian fluid. Here, a Newtonian fluid is a fluid in which the shear stress is proportional to the shear rate. If the thixotropy index TI of the resin composition, which is the ratio of the second viscosity to the first viscosity, is in the range of 0.8 to 1.2, then even when applied to a semiconductor substrate using, for example, a spin coater, the variation in thickness will be small, a coating film of substantially uniform thickness can be formed, and warping of the semiconductor substrate during curing can be suppressed. The resin composition may also have a thixotropy index, which is the ratio of the second viscosity to the first viscosity, in the range of 0.90 to 1.10, or in the range of 1.00 to 1.10.

[0019] In the resin composition, the mass ratio of component (A) to component (B) is preferably in the range of 10:90 to 80:20, more preferably in the range of 20:80 to 75:25, and even more preferably in the range of 30:70 to 70:30. If the mass ratio of component (A) to component (B) in the resin composition is in the range of 10:90 to 80:20, a cured product can be obtained using the resin composition that has a low dielectric constant and a low dielectric loss tangent, and has good electrical properties when used in the high-frequency range. Furthermore, even when the resin composition is applied to a semiconductor substrate using, for example, a spin coater, the variation in thickness is small, and a coating film of substantially uniform thickness can be formed, resulting in a cured product that suppresses warping of the semiconductor substrate.

[0020] In the resin composition, the mass ratio of the total amount of component (A) and component (B) to component (C) is preferably in the range of 5:95 to 80:20, more preferably in the range of 10:90 to 70:30, even more preferably in the range of 12:88 to 40:60, and particularly preferably in the range of 18:82 to 50:50. If the mass ratio of the total amount of component (A) and component (B) to component (C) in the resin composition is in the range of 5:95 to 80:20, then even when the resin composition is applied to a semiconductor substrate using, for example, a spin coater, the variation in thickness will be small, a coating film of substantially uniform thickness can be formed, and a cured product with suppressed warping of the semiconductor substrate can be obtained.

[0021] Component (A) Modified polyphenylene ether Component (A) is preferably a polyphenylene ether resin having a functional group containing a carbon-carbon double bond at its terminal end. Modified polyphenylene ether (PPE) resin is also called component (A) or a modified PPE resin of component (A). Examples of functional groups containing a carbon-carbon double bond include terminal vinyl groups, vinylene groups, vinylidene groups, acryloyl groups, or methacryloyl groups. Component (A) is not particularly limited as long as it has a functional group containing a carbon-carbon double bond at its terminal end and a polyphenylene ether backbone. By including component (A), the resin composition can be given low dielectric properties and improved heat resistance and thermal expansion coefficient. Component (A) is preferably a thermosetting resin. Furthermore, component (A) is particularly preferably a polyphenylene ether resin having vinyl groups at its terminal end. Low dielectric properties can be obtained by having vinyl groups at the terminal end.

[0022] The modified PPE resin of component (A) preferably includes a PPE resin represented by the following formula (1). [ka] [In formula (1), X represents an unsubstituted or substituted aromatic hydrocarbon group with a p-value, Y is given by the following equation (2): [ka] [In formula (2), R 1 ~R 4 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an alkenylcarbonyl group.] represents an unsubstituted or substituted phenol repeating unit represented by, Z represents a functional group containing a terminal carbon-carbon double bond, a vinyl group, a vinylene group, the following formula (3): [Chemical formula] [In formula (3), R 5 represents a hydrogen atom or an alkyl group.] a (meth)acryloyl group represented by, or the following formula (4): [Chemical formula] [In formula (4), R 6 ~R 8 each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.] represents a styrene group represented by, m represents an integer from 1 to 100, n represents 0 or an integer from 1 to 6, p represents an integer from 1 to 4.]

[0023] The PPE resin of component (A) preferably contains at least one selected from the group consisting of a modified PPE resin represented by the following formula (5) and a modified PPE resin represented by the following formula (6).

[0024] [Chemical formula] [In formula (5), R 5 represents a hydrogen atom or an alkyl group, X represents a p-valent unsubstituted or substituted aromatic hydrocarbon group, Y represents an unsubstituted or substituted phenol repeating unit represented by the above formula (2), m represents an integer from 1 to 100, n represents 0 or an integer from 1 to 6, p represents an integer between 1 and 4.

[0025] [ka] [In formula (6), R 6 ~R 8 Each of these independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group. X represents an unsubstituted or substituted aromatic hydrocarbon group with a p-valence. Y represents an unsubstituted or substituted phenol repeating unit represented by formula (2) above, m represents an integer between 1 and 100. n represents 0 or an integer from 1 to 6. p represents an integer between 1 and 4.

[0026] In general, an x-valent hydrocarbon group (where x is an integer greater than or equal to 1) refers to a group with an x-valent status that is created by removing x hydrogen atoms from the carbon atoms of a hydrocarbon. X is a p-valent unsubstituted or substituted aromatic hydrocarbon group, and X refers to a group with a 1-4 valent status that is created by removing 1-4 hydrogen atoms from the carbon atoms of an aromatic hydrocarbon that may or may not be substituted.

[0027] The term "alkyl group" refers to a monovalent saturated hydrocarbon group. In this invention, the alkyl group is preferably C1-C 10 The alkyl group is more preferably a C1-C6 alkyl group, even more preferably a C1-C4 alkyl group, and particularly preferably a C1-C2 alkyl group. Examples of such alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl groups.

[0028] The term "alkenyl group" refers to a monovalent unsaturated hydrocarbon group having at least one carbon-carbon double bond. In the present invention, the alkenyl group is preferably C2-C 10The alkenyl group is more preferably a C2-C6 alkenyl group, and even more preferably a C2-C4 alkenyl group. Examples of such alkenyl groups include ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, isobutenyl group, 1-pentenyl group, 1-hexenyl group, and the like. The group -CR in formula (1) 1 =CR 2 R 3 It is also an alkenyl group.

[0029] The term "alkynyl group" refers to a monovalent unsaturated hydrocarbon group having at least one carbon-carbon triple bond. In the present invention, the alkynyl group is preferably C2-C 10 An alkynyl group, more preferably a C2-C6 alkynyl group, and even more preferably a C2-C4 alkynyl group. Examples of such alkynyl groups include ethynyl, 1-propynyl, 2-propynyl, butynyl, isobutynyl, pentynyl, and hexynyl groups.

[0030] The term "alkenylcarbonyl group" refers to a carbonyl group substituted with the above-mentioned alkenyl group, and examples of such groups include acryloyl and methacryloyl groups.

[0031] In component (A), in formula (1), (5), or (6), -(Y) m The portion represented by - corresponds to the main chain of the PPE resin. Preferably, R in the unsubstituted or substituted phenol repeating unit Y. 1 and R 3 represents a hydrogen atom, and R 2 and R 4 This represents a methyl group. In formula (1), -(Y) m One end of the part represented by - is bonded to the aromatic hydrocarbon group X via an oxygen atom, and the other end is bonded to the terminal group (Z) via n methylene groups. In formula (5), -(Y) mOne end of the part represented by - is bonded to an aromatic hydrocarbon group X via an oxygen atom, and the other end is bonded to a methacryloyl group via n methylene groups. In formula (6), -(Y) m One end of the part represented by - is bonded to an aromatic hydrocarbon group X via an oxygen atom, and the other end is bonded to a phenyl group via n methylene groups, forming an alkenyl group -CR. 6 =CR 7 R 8 The methylene group may be located in the ortho, meta, or para position. In one embodiment, n in formulas (1), (5), or (6) is 0 or an integer from 1 to 4. In one embodiment, n in formulas (1), (5), or (6) is 0, 1, or 2. In one embodiment, n in formula (1) is 0 or 1. In another embodiment, R in formula (6) 6 ~R 8 These are all hydrogen atoms.

[0032] Furthermore, the number m of Y in the repeating unit of formula (1), (5), or (6) is preferably 1 to 80, more preferably 1 to 30, and even more preferably 1 to 5.

[0033] In component (A), the aromatic hydrocarbon group X of formula (1), (5), or (6) each has p -(Y) atoms via an oxygen atom. m The parts represented by - are joined together. Preferably, p is 2 or 3. More preferably, p is 2. Also, X is preferably the following formula: [ka] [In the formula, R 11 ~R 18 Each of the elements has a structure represented by [a hydrogen atom or a C1-C6 alkyl group, respectively]. X is more preferably of the following formula: [ka] It has a structure represented by the following:

[0034] The main chain ends of the modified polyphenylene ether resin of component (A) may be polyphenylene ether resin having an average of 1.5 to 5 functional groups represented by formulas (1), (5), or (6) per molecule. The terminal functional groups are preferably methacryloyl groups and / or acryloyl groups from the viewpoint of providing even better heat resistance when the resin composition is cured, and more preferably methacryloyl groups from the viewpoint of providing even better resin fluidity during heat molding.

[0035] For example, from the viewpoint of ease of coating the resin composition onto a semiconductor substrate using a spin coater, electrical properties such as low dielectric properties and low dielectric loss tangent of the coating film made of the resin composition, and compatibility with other components contained in the resin composition, it is preferable that the number average molecular weight of component (A) is 500 or more and 5000 or less. More preferably, the number average molecular weight of component (A) is 750 or more and 3000 or less, and even more preferably 1000 or more and 2500 or less. If the number average molecular weight (Mn) of component (A) is too low, the toughness of the cured product obtained by curing the resin composition may decrease. On the other hand, if the number average molecular weight (Mn) of component (A) is too high, the compatibility of component (A) with the solvent of component (C) decreases, and for example, it may become difficult to coat the resin composition onto a semiconductor substrate using a spin coater. The number average molecular weight (Mn) of component (A) or component (B) can be measured, for example, from the polystyrene equivalent value obtained by gel permeation chromatography (GPC) measurement. In this specification, the number-average molecular weight (Mn) can be measured, for example, using high-performance liquid chromatography (e.g., LC-2OAD, manufactured by Shimadzu Corporation), a column (e.g., KF-802, manufactured by Showa Denko K.K.), and a tetrahydrofuran (THF) solution as the solvent.

[0036] The content of component (A) in the resin composition is preferably 5.0 to 40.0% by mass, more preferably 7.0 to 35.0% by mass, even more preferably 8.0 to 30.0% by mass, and particularly preferably 9.0 to 25.0% by mass, based on 100% by mass of the total amount of components (A), (B), and (C). When the content of component (A) in the resin composition is 5.0 to 40.0% by mass, a cured product with a low dielectric constant and low dielectric loss tangent is obtained, resulting in a cured product with good electrical properties suitable for use in the high-frequency range.

[0037] Component (A) can be a commercially available product. A commercially available modified PPE resin for component (A) represented by formula (5) can be, for example, NORYL SA9000 (manufactured by SABIC Innovative Plastics), which has 1.5 to 5 terminal methacryloyl groups per molecule represented by formula (3). A commercially available modified PPE resin for component (A) represented by formula (6) can be, for example, OPE 2St 1200 or OPE 2st 2200 (manufactured by Mitsubishi Gas Chemical Company, Inc.). Component (A) can be prepared by known methods. For example, X-(OH) p (In the formula, X and p have the same meanings as above.) Suitable p-valent phenols having the structure represented by the following formula (e.g., 2,2',3,3',5,5'-hexamethylbiphenyl-4,4'-diol) and the following formula [ka] [In the formula, R 1 ~R 4 Each of these has the same meaning as described above. Component (A) can be prepared by a method comprising oxidative copolymerization of a suitable monovalent phenol (such as 2,6-dimethylphenol) having the structure represented by by known methods to prepare a polyphenylene ether resin having hydroxyl groups at its termini, and then modifying the obtained resin by reaction with a suitable modifying agent, such as chloromethylstyrene.

[0038] Component (B) Elastomer having a butadiene skeleton The butadiene skeleton-containing elastomer of component (B) only needs to have a butadiene skeleton in its molecule, and may be a partially hydrogenated elastomer. Examples of butadiene skeleton-containing elastomers include block copolymers that contain at least one styrene or analogue block as a terminal block and at least one conjugated diene elastomer block as an intermediate block. The butadiene skeleton-containing elastomer of component (B) preferably contains at least one selected from the group consisting of styrene / butadiene / styrene copolymer (SBS), styrene / butadiene / butylene / styrene copolymer (SBBS), butadiene polymer (BR), styrene / butadiene copolymer (SBR), and acrylonitrile / butadiene copolymer (NBR). The butadiene skeleton-containing elastomer may be partially modified, for example, it may be a carboxylated nitrilobutadiene rubber (NBR) with carboxyl-modified terminals.

[0039] A resin composition containing a butadiene skeleton elastomer of component (B) along with component (A) shrinks more uniformly during curing, suppressing warping of semiconductor substrates. Furthermore, when using the solvent of component (C) in the resin composition, it dissolves more readily in the solvent of component (C), resulting in better thixotropy. For example, when applied to a semiconductor substrate using a spin coater, the thickness variation is reduced, and a coating film with a more uniform thickness can be formed. In particular, from the viewpoint of good electrical properties when used in the high-frequency range, styrene-based elastomers having double bonds are preferred. For example, styrene / butadiene / styrene copolymer (SBS), styrene / butadiene / butylene / styrene copolymer (SBBS), and styrene-based elastomers containing styrene / butadiene copolymers can be cited as preferred examples. In addition, component (B) may be a reactive elastomer to which functional groups such as amines have been added. By using a reactive elastomer to which functional groups have been added, the adhesive strength (peel strength) can be further improved. The weight-average molecular weight of component (B) is preferably 20,000 to 200,000, and more preferably 30,000 to 150,000. The weight-average molecular weight is determined by gel permeation chromatography (GPC) using a calibration curve based on standard polystyrene.

[0040] The elastomer having a butadiene skeleton of component (B) preferably contains at least one selected from the group consisting of styrene / butadiene / styrene block copolymer represented by the following formula (7) and acrylonitrile / butadiene copolymer represented by the following formula (8).

[0041] [ka] [In equation (7), q and r represent integers between 0 and 1, with at least one being non-zero; s represents an integer between 1 and 1200; and t represents an integer between 1 and 1000.]

[0042] [ka] [In equation (8), u represents an integer between 1 and 1200, and v represents an integer between 1 and 1000.]

[0043] The styrene / butadiene / styrene block copolymer (SBS) represented by formula (7) of component (B) is an unhydrogenated block copolymer. By including the styrene / butadiene / styrene block copolymer in component (B), the resin composition has improved flexibility and solvent solubility, allowing for good coating of the resin composition onto a semiconductor substrate using a spin coater. Similarly, even when a partially hydrogenated elastomer, such as styrene / butadiene / butylene / styrene copolymer (SBBS), is included, the resin composition can be good coated onto a semiconductor substrate. On the other hand, it is preferable that the resin composition or component (B) does not contain elastomers without double bonds. An example of an elastomer without double bonds is styrene / ethylene / butylene / styrene block copolymer (SEBS), which is obtained by fully hydrogenating styrene / butadiene / styrene block copolymer. With SEBS, the compatibility of component (C) with the solvent decreases, and the resin composition may not achieve the desired viscosity, making it difficult to coat the resin composition onto a semiconductor substrate using, for example, a spin coater. Although the details of the mechanism are not clear, it is presumed that styrene / butadiene / styrene block copolymers (SBS) and styrene / butadiene / butylene / styrene copolymers (SBBS) have improved solubility in solvents compared to styrene / ethylene / butylene / styrene block copolymers (SEBS) because they retain the double bond of butadiene. However, the present invention is not bound by this reasoning.

[0044] In equation (7), s may represent an integer between 1 and 1200, or an integer between 150 and 900. In equation (7), t may represent an integer between 1 and 1000, or an integer between 50 and 700.

[0045] Furthermore, when component (B) contains an acrylonitrile / butadiene copolymer (NBR) represented by formula (8), using the solvent of component (C) in the resin composition allows the NBR to dissolve more readily in the solvent of component (C), resulting in better thixotropy. For example, when applied to a semiconductor substrate using a spin coater, the thickness variation is reduced, and a coating film with a more nearly uniform thickness can be formed.

[0046] The styrene content of component (B) in the resin composition is preferably in the range of 10% to 70% by mass, more preferably in the range of 15% to 60% by mass, and even more preferably in the range of 20% to 55% by mass, based on 100% by mass of the resin composition. If the styrene content of component (B) in the resin composition is in the range of 10% to 70% by mass, based on 100% by mass of the resin composition, the elasticity of the resin composition during curing is good, and for example, when applied to a semiconductor substrate, warping of the semiconductor substrate during curing can be suppressed. The styrene content in component (B) of the resin composition can be measured using nuclear magnetic resonance (NMR). Specifically, by using tetrachloroethane as the solvent, the integral values ​​of the peaks in the range of 5.5 ppm to 6.5 ppm, which corresponds to styrene, and the integral values ​​of the peaks in other ranges can be determined, and the styrene content can be calculated from the obtained values.

[0047] The styrene / butadiene ratio (%) of component (B) may be 15 / 85 or higher, 20 / 80 or higher, preferably 70 / 30 or lower, 60 / 40 or lower, or 55 / 45 or lower. For example, when a resin composition is applied to a semiconductor substrate using a spin coater, considering the uniformity of the film thickness of the coating, the suppression of warping of the semiconductor substrate during curing of the resin composition, and the compatibility of component (C) with the solvent, the number average molecular weight (Mn) of component (B) is preferably 40,000 or more and 600,000 or less, more preferably 50,000 or more and 150,000 or less, and even more preferably 60,000 or more and 120,000 or less. The number average molecular weight (Mn) of component (B) can be measured by the same method as described above, for example, from the polystyrene equivalent value obtained by gel permeation chromatography (GPC) measurement.

[0048] The resin composition preferably contains a modified polyphenylene ether resin represented by formula (6) as component (A) and a styrene / butadiene / styrene copolymer (SBS) as component (B). Because the resin composition contains a modified PPE resin represented by formula (6) as component (A) and SBS as component (B), it shrinks uniformly when cured after being applied to a semiconductor substrate, making it less likely for the semiconductor substrate to warp. Therefore, the resin composition is suitable for forming interlayer insulating films in WL-CSP type semiconductor devices.

[0049] The content of component (B) in the resin composition is preferably 5.0 to 40.0% by mass, more preferably 7.0 to 35.0% by mass, even more preferably 8.0 to 30.0% by mass, and particularly preferably 9.0 to 25.0% by mass, based on 100% by mass of the total amount of components (A), (B), and (C). When the content of component (B) in the resin composition is 5.0 to 40.0% by mass, a cured product with a low dielectric constant and low dielectric loss tangent is obtained, resulting in a cured product with good electrical properties suitable for use in the high-frequency range. Furthermore, if the content of component (B) in the total amount of components (A), (B), and (C) in the resin composition is 5.0 to 40.0% by mass, then when the resin composition is applied to a semiconductor substrate using, for example, a spin coater, the variation in thickness is small, a coating film of approximately uniform thickness can be formed, and a cured product with suppressed warping of the semiconductor substrate can be obtained.

[0050] Component (B) can be a commercially available product. Examples of commercially available components (B) include the product names "TR2827", "TR2000", "TR2003", and "TR2250" from JSR Corporation, the product names "P1083", "P1500", "P5051", and "MP10" from Asahi Kasei Chemicals Corporation, and the product name "Nipol(trademark)1072" from Nippon Zeon Co., Ltd.

[0051] Ingredient (C) Solvent The resin composition preferably contains a solvent of component (C). The solvent of component (C) is preferably an organic solvent. The organic solvent is preferably one that readily dissolves or disperses components (A) and (B), and when the resin composition is applied to a semiconductor substrate using, for example, a spin coater, it is possible to form a coating film of substantially uniform thickness with little variation in thickness, and it is less likely to remain in the coating film, thus suppressing a decrease in dielectric properties. The organic solvent preferably contains at least one selected from the group consisting of aromatic solvents and ketone solvents. The solvent of component (C) is preferably at least one selected from the group consisting of toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanenone, cyclohexane, dimethyl carbonate, methylcyclohexanone, and γ-butyrolactone. The solvent of component (C) may be used alone or two or more in combination. The solvent of component (C) may be toluene or cyclohexanone, and among these, cyclohexanone is preferred from the viewpoint of toxicity. The resin composition can be used as a varnish by dissolving or dispersing components (A) and (B) in a solvent of component (C). A varnish made from a resin composition containing components (A), (B), and (C) preferably has the aforementioned first and second viscosities. Furthermore, a varnish made from a resin composition containing components (A), (B), and (C) preferably has the aforementioned thixotropy index TI.

[0052] The content of component (C) in the resin composition is preferably in the range of 20 to 90% by mass, based on 100% by mass of the total amount of components (A), (B), and (C). It may also be in the range of 30 to 86% by mass, 40 to 84% by mass, or 50 to 82% by mass. If the content of component (C) is in the range of 20 to 90% by mass based on 100% by mass of the total amount of components (A), (B), and (C), components (A) and (B) can be easily dissolved or dispersed in component (C). For example, when the resin composition is applied to a semiconductor substrate using a spin coater, the thickness variation is small, a coating film of substantially uniform thickness can be formed, residue in the coating film is less likely to remain, and a decrease in dielectric properties can be suppressed.

[0053] Component (C) can be a commercially available product. Examples of commercially available components for component (C) include toluene (toluene concentration 100% by mass, manufactured by Daishin Chemical Co., Ltd.) and anon (cyclohexanone) (cyclohexanone concentration 90-100% by mass, manufactured by Daishin Chemical Co., Ltd.).

[0054] The resin composition may contain component (A) and component (B), may contain component (C), may contain components other than components (A), components (B), and component (C), or may not contain components other than components (A), components (B), and component (C). The resin composition may consist only of components (A), components (B), and component (C).

[0055] The resin composition may contain a coupling agent to improve adhesion to the semiconductor substrate. The resin composition may also contain an organic peroxide to improve reactivity. The resin composition may contain at least one additive selected from the group consisting of organic peroxides, coupling agents, ion trapping agents, leveling agents, antioxidants, viscosity modifiers, and flame retardants. The coupling agent is a compound having two or more different functional groups in one molecule, one of which is a functional group that chemically bonds with an inorganic material, and the other is a functional group that chemically bonds with an organic material. Examples of coupling agents include at least one selected from the group consisting of silane coupling agents, aluminum coupling agents, and titanium coupling agents, and may also be a silane coupling agent. One coupling agent may be used, or two or more may be used in combination. Examples of functional groups in a silane coupling agent include alkoxy groups, vinyl groups, epoxy groups, styryl groups, methacrylic groups, acrylic groups, amino groups, isocyanurate groups, ureido groups, mercapto groups, sulfide groups, isocyanate groups, and the like.

[0056] The resin composition may contain an organic peroxide that initiates a radical polymerization reaction, taking into consideration the reactivity of components (A) and (B). Peroxycarbonate can be used as the organic peroxide. Perbutyl® Z, manufactured by NOF Corporation, can be used as the peroxycarbonate.

[0057] The content of additives in the resin composition may be 10.0% by mass or less, 8.0% by mass or less, or 5.0% by mass or less, based on 100% by mass of the resin composition. The content of additives in the resin composition may be 0.10% by mass or more, 0.20% by mass or more, 0.30% by mass or more, or 0.50% by mass or more. The additives may be commercially available products, and if the additive is a silane coupling agent, for example, 3-methacryloxypropyltrimethoxysilane KBM 503, vinyltrimethoxysilane KBM 1003 (manufactured by Shin-Etsu Silicone Co., Ltd.), or Coatsil MP200 Silane (manufactured by Momentive Performance Materials Japan) can be used.

[0058] This resin composition is for semiconductor devices in non-photosensitive wafer-level chip-size package form. Furthermore, it is preferable that this resin composition does not contain inorganic fillers such as silica. When forming an interlayer insulating film using a thermosetting insulating resin, a subsequent step involves laser irradiation to create holes in the interlayer insulating film to form via holes for wiring. In this case, if the interlayer insulating film contains inorganic fillers such as silica, the silica portion may not be properly removed during laser processing, making it difficult to properly copper plate the subsequent via holes. Therefore, it is preferable that the resin composition does not contain inorganic fillers such as silica. Here, "not containing inorganic fillers such as silica" means intentionally omitting inorganic fillers from the resin composition. The inorganic material may be present in an amount of 0.0001% to 0.01% per 100% by mass of the resin composition, or it may be 0% by mass, meaning no inorganic material is present at all.

[0059] Method for manufacturing resin compositions The resin composition can be manufactured by mixing component (A) and component (B), and optionally component (C). The resin composition may also be manufactured by mixing component (A) and component (B), and optionally component (C), together with additives, if necessary. However, the inclusion of fillers such as silicon dioxide or aluminum oxide may result in poor coating properties and is therefore undesirable. It is preferable that the resin composition does not contain silicon dioxide or aluminum oxide powder. The method for manufacturing the resin composition is not particularly limited. The resin composition can be manufactured by mixing the raw materials for each component using a mixer such as a spool mill, pot mill, three-roll mill, hybrid mixer, rotary mixer, or twin-screw mixer. These components may be mixed simultaneously, or some may be mixed first and the rest later. The above-mentioned apparatus may also be used in appropriate combinations to manufacture the resin composition.

[0060] The cured product obtained by curing the resin composition preferably has a relative permittivity (ε) of 3.0 or less, more preferably 2.8 or less, and even more preferably 2.7 or less. The dielectric loss tangent (tanδ) preferably has a dielectric loss tangent of 0.015 or less, more preferably 0.014 or less, and even more preferably 0.013 or less. Cured products having low dielectric constant and low dielectric loss tangent have good electrical properties when used in high-frequency ranges, and can therefore be used in electronic components, semiconductor devices, etc., used in high-frequency ranges. Furthermore, when the resin composition is applied to a semiconductor substrate using, for example, a spin coater, it cures sufficiently, and a thin film-like cured product with a substantially uniform film thickness and good electrical properties can be obtained even when semiconductor devices are used in high-frequency ranges such as the fifth-generation communication system "5G," where high capacity and high-speed communication are expected to advance. For this reason, the resin composition can be suitably used as a material for forming an interlayer insulating film that seals the side of the semiconductor substrate on which the electrodes and wiring are arranged, in a semiconductor device comprising a semiconductor substrate, electrodes arranged on the semiconductor substrate, wiring connected to the electrodes, external terminals electrically connected via the wiring, and an interlayer insulating film. This interlayer insulating film is positioned in contact with the wiring. In this specification, the "redistribution layer" includes the wiring and the interlayer insulating film. In some literature, "wiring" is described as the "redistribution layer," and "interlayer insulating film" is described as the "sealing resin layer." The resin composition can be suitably used as a material to form an interlayer insulating film that seals the semiconductor substrate side of the wiring and the opposite side of the wiring from the semiconductor substrate in a semiconductor device. The thickness of the redistribution layer can be about 5 to 30 μm. The thickness of the redistribution layer may also be 5 μm or more, or 10 μm or more. The thickness of the redistribution layer may also be 30 μm or less, or 20 μm or less.

[0061] The resin composition can be suitably used as a encapsulating resin for WL-CSP type semiconductor devices.

[0062] Next, a WL-CSP type semiconductor device using a resin composition will be described. The WL-CSP type semiconductor device comprises a semiconductor substrate, electrodes disposed on the semiconductor substrate, wiring connected to the electrodes, external terminals electrically connected via the wiring, and an interlayer insulating film that seals the side of the semiconductor substrate where the electrodes and wiring are located. The interlayer insulating film is made of a resin composition containing the aforementioned components (A), (B), and (C). The interlayer insulating film has an interlayer insulating film that is in contact with the wiring. Preferably, the WL-CSP type semiconductor device comprises at least two layers: a first interlayer insulating film (also called a "dielectric film") that seals the semiconductor substrate side of the wiring, and a second interlayer insulating film that seals the side of the wiring opposite the semiconductor substrate. Both the first interlayer insulating film (dielectric film) and the second interlayer insulating film are disposed in contact with the wiring and function as interlayer insulating films for the wiring.

[0063] Semiconductor equipment A WL-CSP type semiconductor device will be described based on the drawings. Figure 1 is a schematic cross-sectional view showing the schematic configuration of a WL-CSP type semiconductor device. The WL-CSP type semiconductor device is not limited to the example shown in Figure 1.

[0064] The WL-CSP type semiconductor device 10 comprises an electrode 2, wiring 4 connected to the electrode 2, and an external connection terminal 8 such as a conductive ball electrically connected to the wiring 4, on a semiconductor substrate 1. A protective layer 3 made of an oxide film or the like may be formed between the wiring 4 and the semiconductor substrate 1. The WL-CSP type semiconductor device 10 includes interlayer insulating films 5 and 6 that seal the side of the semiconductor substrate 1 where the electrode 2 and wiring 4 are located. The interlayer insulating films 5 and 6 are arranged in contact with the wiring 4. The film sealing the semiconductor substrate 1 side of the wiring 4 is a first interlayer insulating film (dielectric film) 5. The film sealing the opposite side of the wiring 4 from the semiconductor substrate 1 side is a second interlayer insulating film 6. The interlayer insulating films 5 and 6 may comprise at least two layers. Both the first interlayer insulating film (dielectric layer) 5 and the second interlayer insulating film 6 are arranged in contact with the wiring 4. By using the same resin composition for the first interlayer insulating film 5 and the second interlayer insulating film 6, lower dielectric properties are achieved, resulting in better electrical properties when used in the high-frequency range. The wiring 4, the first interlayer insulating film (dielectric film) 5, and the second interlayer insulating film 6 constitute the rewiring layer 7.

[0065] Manufacturing method for semiconductor devices Next, we will explain the manufacturing method for WL-CSP type semiconductor devices. Unless otherwise specified, the term "semiconductor device" hereafter refers to a WL-CSP type semiconductor device. The semiconductor substrate can be made of materials such as silicon, SiGe, or SOI. The electrodes can be formed by depositing an electrode material onto substantially the entire surface of the semiconductor substrate, for example by vacuum deposition or sputtering, and then patterning it using a method such as photolithography to form multiple electrodes at predetermined positions on the semiconductor substrate.

[0066] After forming electrodes on the surface of a semiconductor substrate, silicon nitride (SiN) can be deposited over the entire surface of the semiconductor substrate by, for example, a vapor deposition method, and then an oxide film (passivation film) can be formed on the surface of the silicon nitride to create a protective layer. The thickness of the semiconductor substrate, electrodes, and protective layer is not particularly limited.

[0067] Next, the resin composition is dropped onto the semiconductor substrate, and the semiconductor substrate is rotated around a vertical axis using a spin coater to coat the semiconductor substrate with the liquid resin composition, and the liquid resin composition is cured to form an interlayer insulating film. Specifically, the resin composition is dropped onto the electrodes and protective layer on the semiconductor substrate, and the semiconductor substrate is rotated around a vertical axis using a spin coater to coat the electrodes and protective layer on the semiconductor substrate with the liquid resin composition, and the liquid resin composition is cured to form a first interlayer insulating film (dielectric film).

[0068] When applying a resin composition to form an interlayer insulating film, the rotation speed of the spin coater is preferably 1000 rpm to 3000 rpm, and the rotation time is preferably 5 seconds to 30 seconds. If the rotation speed and rotation time of the spin coater are within the above range, the resin composition can be applied to the semiconductor substrate to a substantially uniform thickness, an interlayer insulating film having a desired substantially uniform thickness can be formed after curing, and warping of the semiconductor substrate during curing can be suppressed.

[0069] The interlayer insulating film can be formed using a resin composition containing the aforementioned components (A) and (B), and optionally component (C). By using the aforementioned resin composition, even when the resin composition is applied to a semiconductor substrate using a spin coater, it is possible to form a coating film of substantially uniform thickness with minimal variation in thickness, and to form a first interlayer insulating film (dielectric film) that suppresses warping of the semiconductor substrate during curing. A resin composition comprising the aforementioned components (A) and (B), and optionally component (C), can be used to form an interlayer insulating film. The interlayer insulating film may be a first interlayer insulating film (dielectric film) or a second interlayer insulating film. The aforementioned component (A) preferably comprises a modified PPE resin represented by formula (1), and it is preferable that component (A) comprises at least one selected from the group consisting of modified PPE resins represented by formula (5) and modified PPE resins represented by formula (6). The aforementioned component (B) preferably comprises at least one selected from the group consisting of SBS represented by formula (7) and NBR represented by formula (8).

[0070] The rotation speed of the spin coater is preferably 1000 rpm to 3000 rpm, and the rotation time is preferably 5 seconds to 30 seconds.

[0071] When applying the aforementioned resin composition to a semiconductor substrate using a spin coater, the first viscosity of the resin composition at 25°C and 10 rpm, measured with a rotational viscometer, is preferably 300 mPa·s to 4000 mPa·s, more preferably 400 mPa·s to 4000 mPa·s, and even more preferably 500 mPa·s to 2000 mPa·s. If the first viscosity of the aforementioned resin composition when applied to a semiconductor substrate using a spin coater is within the above range, the variation in thickness will be small, a coating film of substantially uniform thickness can be formed, and warping of the semiconductor substrate during curing can be suppressed.

[0072] When applying the aforementioned resin composition to a semiconductor substrate using a spin coater, it is preferable that the second viscosity of the resin composition measured by a rotational viscometer at 25°C and 1 rpm is in the range of 500 mPa·s to 4200 mPa·s, more preferably in the range of 550 mPa·s to 4200 mPa·s, even more preferably in the range of 550 mPa·s to 4000 mPa·s, and even more preferably in the range of 550 mPa·s to 3500 mPa·s. If the second viscosity of the aforementioned resin composition when applied to a semiconductor substrate using a spin coater is within the above range, it is possible to form a coating film of substantially uniform thickness with little variation in thickness, and warping of the semiconductor substrate during curing can be suppressed.

[0073] When applying the aforementioned resin composition to a semiconductor substrate using a spin coater, the thixotropy index TI, which is the ratio of the second viscosity to the first viscosity, is preferably in the range of 0.8 to 1.2, but may also be in the range of 0.9 to 1.1, or in the range of 1.0 to 1.1. If the ratio of the second viscosity to the first viscosity of the aforementioned resin composition when applied to a semiconductor substrate using a spin coater is within the above range, the variation in thickness will be small, a coating film of substantially uniform thickness can be formed, and warping of the semiconductor substrate during curing can be suppressed.

[0074] The interlayer insulating film, the first interlayer insulating film (dielectric film), or the second interlayer insulating film preferably has a thickness of 3 μm to 20 μm, but may also be in the range of 4 μm to 18 μm, or 5 μm to 17 μm. As long as the thickness of each layer of the interlayer insulating film, the first interlayer insulating film (dielectric film), or the second interlayer insulating film is within the range of 3 μm to 20 μm, the requirements for miniaturization and thinning of semiconductor devices can be satisfied even when multiple films are stacked.

[0075] In a method for manufacturing a semiconductor device, after applying a resin composition, drying and curing it, a first interlayer insulating film (dielectric film) with openings on the electrode surface can be formed by laser direct patterning, for example, using a laser direct patterning apparatus (manufactured by Mitsubishi Electric Corporation).

[0076] Next, a seed layer for forming wiring is formed on substantially the entire surface of the semiconductor substrate on which electrodes, a protective layer, and a first interlayer insulating film (dielectric film) are formed, by a vapor deposition method, sputtering method, chemical vapor deposition (CVD) method, electroless plating method, etc. The seed layer may contain copper, and may also contain copper oxide, a copper-chromium alloy, copper, tantalum, cobalt, titanium and its alloys. The seed layer may also have a laminated structure in which multiple layers are stacked. A resist is formed on this seed layer in a predetermined pattern, for example by photolithography, and wiring in a predetermined pattern is formed by electroplating or electroless plating using this resist film as a mask. After the wiring is formed, the resist film is peeled off, and the seed layer remaining in the areas where wiring is not formed is removed by etching or the like. The thickness of the wiring is not particularly limited, but the thickness of the wiring may be 0.1 μm or more, 15 μm or less, 12 μm or less, or 10 μm or less.

[0077] Next, the resin composition is applied to the wiring using a spin coater so that the surface height is substantially uniform, thereby forming a second interlayer insulating film. The second interlayer insulating film can be made using a resin composition containing the aforementioned components (A), (B), and (C), similar to the first interlayer insulating film, and can be applied to a semiconductor substrate using a spin coater with the same rotation speed and rotation time as the first interlayer insulating film, specifically applied to the wiring. After applying the resin composition, it can be dried and cured, and then, for example, using a laser direct patterning apparatus (manufactured by Mitsubishi Electric Corporation), a second interlayer insulating film can be formed by laser direct patterning, which opens the surface portion of the wiring where the external terminals described later will be placed. The second interlayer insulating film may also be formed by exposure and development to open the surface portion of the electrodes.

[0078] In some cases, the formation of a redistribution layer is achieved by combining the formation of the first interlayer insulating film (dielectric film), the formation of wiring, and the formation of the second interlayer insulating film.

[0079] Subsequently, external terminals such as solder balls can be formed in the openings of the redistribution layer by methods such as solder ball mounting, solder plating, solder paste, solder paste dispensing, and solder deposition, thereby forming a WL-CSP type semiconductor device. The WL-CSP type semiconductor device formed in this manner has a low dielectric constant and a low dielectric loss tangent because the first and second interlayer insulating films are made of resin compositions containing the aforementioned components (A), (B), and (C). Therefore, it exhibits good electrical characteristics even when used in high-frequency ranges such as the fifth-generation communication system "5G," where increased capacity and high-speed communication are expected.

[0080] The resin composition according to the embodiment of the present invention and the semiconductor device using the same can be used as electronic components in electronic devices such as mobile phones, smartphones, laptop computers, tablet devices, and camera modules. [Examples]

[0081] The present invention will be described in detail below with reference to examples. The present invention is not limited to these examples. In the following examples and comparative examples, unless otherwise specified, the numbers indicating the blending ratio of each component contained in the resin composition represent the ratio (mass (%)) with the total amount of the resin composition being 100% by mass. If the resin composition contains only components (A), (B), and (C), and no additives, the total amount of the resin composition represents the sum of the amounts of components (A), (B), and (C).

[0082] Component (A): Modified polyphenylene ether (PPE) resin A-1: OPE 2st 1200 (represented by formula (6), a modified polyphenylene ether resin having vinyl groups at both ends (a reaction product of 2,2',3,3',5,5'-hexamethylbiphenyl-4,4'-diol·2,6-dimethylphenol condensate and chloromethylstyrene), number average molecular weight (Mn) 1200) (manufactured by Mitsubishi Gas Chemical Company, Inc.) A-2: OPE 2st 2200 (represented by formula (6), a modified polyphenylene ether resin having vinyl groups at both ends (a reaction product of 2,2',3,3',5,5'-hexamethylbiphenyl-4,4'-diol·2,6-dimethylphenol condensate and chloromethylstyrene), number average molecular weight (Mn) 2200) (manufactured by Mitsubishi Gas Chemical Company, Inc.) A-3: NORYL SA9000 (Represented by formula (5), which has the group shown in formula (3) at the terminal end, and has methacryloyl groups at both ends; a modified polyphenylene ether resin with a number average molecular weight (Mn) of 1850-1950. (Manufactured by SABIC Innovative Plastics))

[0083] Component (B): Unhydrogenated styrene / butadiene / styrene block copolymer (SBS) B-1: Styrene / butadiene / styrene block copolymer (SBS) TR2827, styrene / butadiene ratio 24 / 76 (%), number average molecular weight (Mn) 130,000 (manufactured by JSR Corporation). B-2: Styrene / butadiene / styrene block copolymer (SBS) TR2003, styrene / butadiene ratio 43 / 57 (%), number average molecular weight (Mn) 100,000 (manufactured by JSR Corporation). B-3: Styrene / butadiene / styrene block copolymer (SBS) TR2250, styrene / butadiene ratio 52 / 48 (%), number average molecular weight (Mn) 100,000 (manufactured by JSR Corporation). B-4: Partially hydrogenated styrene / butadiene / butylene / styrene block copolymer (SBBS) P5051, styrene / butadiene ratio 47 / 53 (%), number average molecular weight (Mn) 53,000 (manufactured by Asahi Kasei Chemicals Corporation) B-5: Carboxylated carboxylated nitrilobutadiene rubber (NBR) Nipol (trademark) 1072, number average molecular weight (Mn) 500,000 (manufactured by Nippon Zeon Corporation)

[0084] Component (B'): Polytetrafluoroethylene resin B'-6: Tetrafluoroethylene resin Rubron (registered trademark) L-5F (manufactured by Daikin Industries, Ltd.).

[0085] Ingredient (C): Solvent C-1: Toluene (manufactured by Daishin Chemical Co., Ltd.) Boiling point: 110.6℃. C-2: Anone (cyclohexanenone, manufactured by Daishin Chemical Co., Ltd.), boiling point 155.65℃.

[0086] Additive: Organic peroxide Perbutyl® Z (manufactured by NOF Corporation)

[0087] Examples 1-12, Comparative Example 1 Components (A), (B) or (B'), and (C) were mixed and dissolved in a constant temperature water bath (SB-35, Tokyo Rikakikai Co., Ltd.) at a constant temperature of 70°C using a stirrer (SSR-112, AGC Technoglass Co., Ltd.) to produce the resin compositions of the examples and comparative examples. In Table 1, the symbol "-" indicates that the corresponding component is not included in the resin composition. Also in Table 1, "Mn" represents the number-average molecular weight.

[0088] [Table 1]

[0089] Evaluation of resin compositions The solubility and viscosity of each resin composition in the examples and comparative examples were measured, and the results are shown in Table 3. In Table 3, for Comparative Example 1, in which component (B') does not dissolve in the solvent of component (C), evaluation could not be performed because a coating film could not be formed, and it is indicated as NA (Not Available).

[0090] solubility For each resin composition, the solubility of component (A) and component (B) or component (B') was evaluated by heating the solvent of component (C) to 70°C. Resin compositions in which component (A) and component (B) or component (B') were visibly dissolved in the solvent of component (C) were evaluated as G (good), and resin compositions in which they were not visibly dissolved were evaluated as N (not-good).

[0091] viscosity For each resin composition, the first viscosity at 25°C and 10 rpm and the second viscosity at 25°C and 1 rpm were measured using a TVE type viscometer (cone rotor: 1° 34' × R24, manufactured by Toki Sangyo Co., Ltd.), and the thixotropy index TI (viscosity at 1 rpm / viscosity at 10 rpm) of the second viscosity relative to the first viscosity was measured.

[0092] Formation of interlayer insulating film Using the resin compositions of the examples and comparative examples, coating films that form interlayer insulating films were formed, and the cured products made from the resin compositions were heat-treated under the following conditions. The following evaluations were performed on the cured products. The results are shown in Table 3. Thickness of interlayer insulating film by spin coating As a semiconductor substrate, a silicon wafer with a diameter of 150 mm and a thickness of 0.525 mm was spin-coated with each of the resin compositions in the examples and comparative examples using a spin coater (MS-A200, manufactured by Mikasa Corporation). Spin coating was performed by operating the spin coater at 1000 rpm for 5 seconds, and then at 2000 rpm for 30 seconds, to spin-coat the resin composition onto the silicon wafer surface and form a coating film. Furthermore, as a semiconductor substrate, a silicon wafer with a diameter of 150 mm and a thickness of 0.525 mm was spin-coated with each of the resin compositions from the examples and comparative examples using a spin coater (MS-A200, manufactured by Mikasa Corporation). Spin coating was performed by operating the spin coater at 1000 rpm for 5 seconds, and then at 3000 rpm for 30 seconds, to spin-coat the resin composition onto the silicon wafer surface and form a coating film. Next, a silicon wafer having a thin film of the resin composition was preheated (dried) in a nitrogen atmosphere at 130°C for 10 minutes, and then heated to obtain a sample in which the resin composition coating film was dried. Subsequently, a sample in which the resin composition coating film was cured was obtained by heat treatment (curing) in a nitrogen atmosphere at 200°C for 60 minutes. The film thickness of the resin composition coating film was measured using a stylus-type profiling system (Surfcom 300B, manufactured by Tokyo Seimitsu Co., Ltd.). The film thickness of the interlayer insulating film can be approximately 5 μm to 30 μm. Furthermore, the film thickness of the interlayer insulating film may be 5 μm or more, or 10 μm or more. Furthermore, the film thickness of the interlayer insulating film may be 30 μm or less, or 20 μm or less.

[0093] Warping of semiconductor substrates As a semiconductor substrate, the warpage of the silicon wafer itself (before coating), with a diameter of 150 mm and a thickness of 0.525 mm, was measured using a 3D heated surface shape measuring device (Thermoray AXP2.0, manufactured by Akrometrix) (hereinafter referred to as "initial warpage"). 3 g of resin composition was dropped onto the center of this silicon wafer, and the resin compositions of the examples and comparative examples were spin-coated using a spin coater (MS-A200, manufactured by Mikasa Corporation). Spin coating was performed by operating the spin coater to spin-coat the resin composition onto the silicon wafer surface and form a coating film. Next, a silicon wafer having a thin film of the resin composition was preheated (dried) in a nitrogen atmosphere at 130°C for 10 minutes, and then heated to obtain a sample in which the resin composition coating film was dried. Subsequently, a sample in which the resin composition coating film was cured was obtained by heat treatment (curing) in a nitrogen atmosphere at 200°C for 60 minutes. Next, the warpage of the silicon wafer was measured using a 3D heated surface shape analyzer (Thermoray AXP2.0, manufactured by Akrometrix) (hereinafter referred to as "post-curing warpage"). Warpage refers to the value (height) obtained by subtracting the initial warpage from the "post-curing warpage." Hereafter, silicon wafers will also be simply referred to as "wafers." Warpage amount = (Warpage amount after hardening) - (Initial warpage amount) The amount of warpage is preferably in the range of -5mm to 5mm, more preferably in the range of -3mm to 3mm, and even more preferably in the range of -2mm to 2mm. When the amount of warpage is in the range of -5mm to 5mm, the wafer can be held by adsorption using a wafer holder with a vacuum adsorption mechanism (e.g., vacuum tweezers), and the wafer can be moved to the desired position by moving the wafer holder. However, if the wafer has a large warpage, it becomes impossible to adsorb the entire wafer, and only a portion of the wafer, for example, in the center, will be adsorbed. In this case, sufficient holding force cannot be obtained, and there is a risk that the wafer may detach from the vacuum tweezers and fall due to even a slight impact during wafer transfer. If the holding force becomes extremely small, it may become impossible to adsorb the wafer at all.

[0094] Strength (adhesion) measurement (cross-cut peel test) The strength (adhesion) was measured in accordance with ASTM D3359-97. Specifically, a silicon wafer spin coater (MS-A200, manufactured by Mikasa Corporation) with a diameter of 150 mm and a thickness of 0.525 mm was used as the semiconductor substrate to spin-coat each resin composition of the examples and comparative examples. Spin coating was performed by operating the spin coater to spin-coat the resin composition onto the silicon wafer surface and form a coating film. Next, a silicon wafer having a thin film of the resin composition was preheated (dried) in a nitrogen atmosphere at 130°C for 10 minutes, and then heated to obtain a sample in which the resin composition coating film was dried. Subsequently, a sample in which the resin composition coating film was cured was obtained by heat treatment (curing) in a nitrogen atmosphere at 200°C for 60 minutes. In this way, samples for the cross-cut peel test were prepared. On the surface of a sample containing a coating that functions as an interlayer insulating film, a cross-cut guide (manufactured by Gotec Co., Ltd.) was used to make a grid pattern of cuts that intersect in a cross shape. Then, cellophane tape (manufactured by Nichiban Co., Ltd.) was applied to the intersecting cuts, and the applied cellophane tape was quickly peeled off. The area of ​​the peeled coating was measured and judged on a scale of 0B to 5B as shown in Table 2 below.

[0095] [Table 2]

[0096] Relative permittivity (ε), dielectric loss tangent (tanδ) The measurement samples were prepared as follows. Each resin composition from the examples and comparative examples was applied to a polyethylene terephthalate (PET) support, preheated (dried) at 130°C for 10 minutes under a nitrogen atmosphere, heated to dry the resin composition, and then cured at 200°C for 60 minutes under a nitrogen atmosphere to obtain a coating film consisting of the resin composition with a thickness of 10 μm. The relative permittivity (ε) and dielectric loss tangent (tanδ) of the sample were measured at a dielectric resonance frequency of 5 GHz using the cavity resonator perturbation method. The relative permittivity (ε) is preferably 1.5 to 3.0, and the dielectric loss tangent (tanδ) is preferably 0.001 to 0.010.

[0097] [Table 3]

[0098] As shown in Tables 1 and 3, the resin compositions of Examples 1 to 12 exhibited good solubility of components (A) and (B) in component (C), and when applied to a semiconductor substrate using a spin coater, they were able to form a coating film with a substantially uniform thickness. Furthermore, the coating films obtained from the resin compositions of Examples 1 to 12 had a relative permittivity (ε) of 2.7 or less and a dielectric loss tangent (tanδ) of 0.015 or less, resulting in good electrical characteristics even when semiconductor devices are used in high-frequency ranges such as the fifth-generation communication system "5G," where increased capacity and high-speed communication are expected.

[0099] Furthermore, as shown in Tables 1 and 3, the resin compositions of Examples 1 to 12 had a first viscosity of 300 mPa·s to 4000 mPa·s at 25°C and 10 rpm measured on a rotational viscometer, a second viscosity of 500 mPa·s to 4200 mPa·s at 25°C and 1 rpm, and a thixotropy index TI, which is the ratio of the second viscosity to the first viscosity, was in the range of 0.8 to 1.2. The resin compositions of Examples 1 to 9 showed little variation in thickness when applied to semiconductor substrates using a spin coater, forming a coating film of substantially uniform thickness and suppressing warping of the semiconductor substrate during curing. In addition, the resin compositions of Examples 1 to 12 received a 5B rating in the cross-cut peel test, indicating 0% of the area removed, and also demonstrated good adhesion.

[0100] In Comparative Example 1, the resin composition containing tetrafluoroethylene resin did not dissolve in the solvent of component (C) due to the absence of SEBS or tetrafluoroethylene resin. As a result, the resin composition could not be applied to a semiconductor substrate, and a coating film could not be formed. [Industrial applicability]

[0101] The resin composition according to the present invention can be used in WL-CSP type semiconductor devices. The resin composition according to the embodiment of the present invention and the semiconductor device using the same can be used as electronic components in electronic devices such as mobile phones, smartphones, laptop computers, tablet terminals, and camera modules. [Explanation of Symbols]

[0102] 1: Semiconductor substrate, 2: Electrode, 3: Protective layer, 4: Wiring, 5: First interlayer insulating film (dielectric), 6: Second interlayer insulating film, 7: Redistribution layer, 8: External terminal, 10: Semiconductor device.

Claims

1. (A) Modified polyphenylene ether resin having an unsaturated double bond at the terminal, and (B) Elastomer having a butadiene skeleton, A resin composition for wafer-level chip-size package semiconductor device, wherein the (B) elastomer having a butadiene skeleton comprises at least one selected from the group consisting of a styrene / butadiene / styrene copolymer with a styrene / butadiene ratio of 15 / 85 or more, a styrene / butadiene / butylene / styrene copolymer with a styrene / butadiene ratio of 47 / 53 or more, a butadiene polymer, a styrene / butadiene copolymer with a styrene / butadiene ratio of 15 / 85 or more, and an acrylonitrile / butadiene copolymer.

2. The modified polyphenylene ether resin having an unsaturated double bond at the (A) terminus is given by the following formula (1): 【Chemistry 20】 [In formula (1), X represents an unsubstituted or substituted aromatic hydrocarbon group with a p-value, Y is given by the following equation (2): 【Chemistry 21】 [In formula (2), R １ ~R ４ Each of these independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an alkenylcarbonyl group. This represents an unsubstituted or substituted phenol repeating unit, Z represents a functional group containing a terminal carbon-carbon double bond, such as a vinyl group, vinylene group, or the following formula (3): 【Chemistry 22】 [In formula (3), R ５ [This represents a hydrogen atom or an alkyl group.] A (meth)acryloyl group represented by the following formula (4): 【Chemistry 23】 [In formula (4), R ６ ~R ８ Each of these independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group. This represents a styrene group, m represents an integer between 1 and 100. n represents 0 or an integer from 1 to 6. p represents an integer between 1 and 4. The resin composition according to claim 1, comprising a modified polyphenylene ether resin represented by [the specified symbol].

3. The modified polyphenylene ether resin having an unsaturated double bond at the (A) terminus is given by the following formula (5): 【Chemistry 24】 [In formula (5), R ５ This represents a hydrogen atom or an alkyl group. X represents an unsubstituted or substituted aromatic hydrocarbon group with a p-value. Y is given by the following equation (2): 【Chemistry 25】 [In formula (2), R １ ~R ４ Each of these independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an alkenylcarbonyl group. This represents an unsubstituted or substituted phenol repeating unit, m represents an integer between 1 and 100. n represents 0 or an integer from 1 to 6. p represents an integer between 1 and 4. A modified polyphenylene ether resin represented by the following formula (6): 【Chemistry 26】 [In formula (6), R ６ to R ８ each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, X represents an unsubstituted or substituted aromatic hydrocarbon group with a p-value. Y represents an unsubstituted or substituted phenol repeating unit represented by formula (2) above, m represents an integer between 1 and 100. n represents 0 or an integer from 1 to 6. p represents an integer between 1 and 4. The resin composition according to claim 1, comprising at least one selected from the group consisting of modified polyphenylene ether resins represented by .

4. The elastomer having the butadiene skeleton described above (B) is given by the following formula (7): 【Chemistry 27】 [In equation (7), q and r represent integers between 0 and 1, with at least one being non-zero; s represents an integer between 1 and 1200; and t represents an integer between 1 and 1000.] A styrene / butadiene / styrene block copolymer represented by the following formula (8): 【Chemistry 28】 [In equation (8), u represents an integer between 1 and 1200, and v represents an integer between 1 and 1000.] The resin composition according to claim 1, comprising at least one selected from the group consisting of acrylonitrile / butadiene copolymers represented by .

5. The modified polyphenylene ether resin having an unsaturated double bond at the (A) terminus is given by the following formula (6): 【Chemistry 29】 [In formula (6), R ６ ~R ８ Each of these independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group. X represents an unsubstituted or substituted aromatic hydrocarbon group with a p-value. Y is given by the following equation (2): 【Transformation 30】 [In formula (2), R １ ~R ４ Each of these independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an alkenylcarbonyl group. This represents an unsubstituted or substituted phenol repeating unit, m represents an integer between 1 and 100. n represents 0 or an integer from 1 to 6. p represents an integer between 1 and 4. It contains a modified polyphenylene ether resin represented by, The resin composition according to claim 1, wherein the (B) elastomer having a butadiene skeleton comprises a styrene / butadiene / styrene copolymer having a styrene / butadiene ratio of 15 / 85 or more.

6. (C) The resin composition according to claim 1, further comprising a solvent.

7. The resin composition according to claim 1, wherein the first viscosity measured by a rotary viscometer at 25°C and 10 rpm is in the range of 300 mPa·s to 4000 mPa·s.

8. The resin composition according to claim 7, wherein the second viscosity measured by a rotational viscometer at 25°C and 1 rpm is in the range of 500 mPa·s to 4200 mPa·s, and the thixotropy index TI, which is the ratio of the second viscosity to the first viscosity, is 0.8 to 1.

2.

9. The resin composition according to claim 1, wherein the mass ratio of component (A) to component (B) is in the range of 10:90 to 80:

20.

10. The resin composition according to claim 6, wherein the mass ratio of the total amount of component (A) and component (B) to component (C) is in the range of 5:95 to 80:

20.

11. The semiconductor substrate comprises an electrode disposed on the semiconductor substrate, wiring electrically connected to the electrode, an external terminal electrically connected to the electrode via the wiring, and an interlayer insulating film that seals the side of the semiconductor substrate on which the electrode and the wiring are disposed. A wafer-level chip-size packaged semiconductor device, wherein the interlayer insulating film is arranged in contact with the wiring, and the resin composition is as described in any one of claims 1 to 10.

12. The semiconductor device according to claim 11, comprising at least two layers: a first interlayer insulating film that seals the semiconductor substrate side of the wiring, and a second interlayer insulating film that seals the side of the wiring opposite to the semiconductor substrate.

13. The semiconductor device according to claim 11, wherein the thickness of one of the layers of the interlayer insulating film, the first interlayer insulating film, or the second interlayer insulating film is in the range of 3 μm or more and 20 μm or less.

14. The following ingredients (A) to (C): (A) Modified polyphenylene ether resin having an unsaturated double bond at the terminal, (B) Elastomers having a butadiene skeleton, and (C) Prepare a liquid resin composition containing a solvent, The process involves dropping the resin composition onto a semiconductor substrate, and then using a spin coater to rotate the semiconductor substrate around a vertical axis to coat the semiconductor substrate with the liquid resin composition. This includes curing the liquid resin composition to form an interlayer insulating film, A method for manufacturing a wafer-level chip-sized package semiconductor device, wherein the (B) elastomer having a butadiene skeleton comprises at least one selected from the group consisting of a styrene / butadiene / styrene copolymer having a styrene / butadiene ratio of 15 / 85 or more, a styrene / butadiene / butylene / styrene copolymer having a styrene / butadiene ratio of 47 / 53 or more, a butadiene polymer, a styrene / butadiene copolymer having a styrene / butadiene ratio of 15 / 85 or more, and an acrylonitrile / butadiene copolymer.

15. The method for manufacturing a semiconductor device according to claim 14, wherein the rotation speed of the spin coater is 1,000 rpm to 3,000 rpm and the rotation time is 5 seconds to 30 seconds.

16. The method for manufacturing a semiconductor device according to claim 14, wherein the liquid resin composition has a first viscosity of 300 mPa·s to 4000 mPa·s at 25°C and 10 rpm as measured by a rotary viscometer.

17. The method for manufacturing a semiconductor device according to claim 16, wherein the liquid composition has a second viscosity of 500 mPa·s to 4200 mPa·s at 25°C and 1 rpm as measured by a rotational viscometer, and a thixotropy index TI, which is the ratio of the second viscosity to the first viscosity, is 0.8 to 1.

2.

18. The modified polyphenylene ether resin having an unsaturated double bond at the (A) terminus is given by the following formula (1): 【Chemistry 31】 [In formula (1), X represents an unsubstituted or substituted aromatic hydrocarbon group with a p-value, Y is given by the following equation (2): 【Chemistry 32】 [In formula (2), R １ ~R ４ Each of these independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an alkenylcarbonyl group. This represents an unsubstituted or substituted phenol repeating unit, Z represents a functional group containing a terminal carbon-carbon double bond, such as a vinyl group, vinylene group, or the following formula (3): 【Transformation 33】 [In formula (3), R ５ [This represents a hydrogen atom or an alkyl group.] A (meth)acryloyl group represented by the following formula (4): 【Transformation 34】 [In formula (4), R ６ ~R ８ Each of these independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group. This represents a styrene group, m represents an integer between 1 and 100. n represents 0 or an integer from 1 to 6. p represents an integer between 1 and 4. A method for manufacturing a semiconductor device according to any one of claims 14 to 17, comprising a modified polyphenylene ether resin represented by .

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