WO2023058425A1 - 樹脂組成物、半導体装置及び半導体装置の製造方法 - Google Patents

樹脂組成物、半導体装置及び半導体装置の製造方法 Download PDF

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WO2023058425A1
WO2023058425A1 PCT/JP2022/034526 JP2022034526W WO2023058425A1 WO 2023058425 A1 WO2023058425 A1 WO 2023058425A1 JP 2022034526 W JP2022034526 W JP 2022034526W WO 2023058425 A1 WO2023058425 A1 WO 2023058425A1
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Prior art keywords
resin composition
group
component
formula
integer
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English (en)
French (fr)
Japanese (ja)
Inventor
広龍 五十嵐
真樹 吉田
敏行 佐藤
慎 寺木
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Namics Corp
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Namics Corp
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Priority to KR1020247010951A priority Critical patent/KR20240073043A/ko
Priority to JP2023552778A priority patent/JPWO2023058425A1/ja
Priority to DE112022004813.1T priority patent/DE112022004813T5/de
Priority to US18/689,720 priority patent/US20240360310A1/en
Publication of WO2023058425A1 publication Critical patent/WO2023058425A1/ja
Anticipated expiration legal-status Critical
Priority to JP2026001025A priority patent/JP2026062946A/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
    • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts

Definitions

  • the present invention relates to a resin composition, a semiconductor device using the same, and a method for manufacturing a semiconductor device.
  • a wafer-level chip-size package is a semiconductor package whose size is almost the same as that of a semiconductor substrate, with a portion of the semiconductor substrate (silicon wafer) exposed without internal wiring using bonding wires. .
  • Patent Documents 1 and 2 disclose WL-CSP.
  • a WL-CSP has a multi-layer structure including electrodes, an insulating layer, a rewiring layer, and a sealing resin layer on a semiconductor substrate (silicon wafer), and external terminals such as solder bumps.
  • High-frequency characteristics are required for electronic components as information transmission becomes ultra-high-speed and information-large-capacity.
  • it is required to have excellent electrical properties (low dielectric constant ( ⁇ ), low dielectric loss tangent (tan ⁇ )) in a high frequency range, specifically in a frequency range of 1 GHz to 10 GHz.
  • WL-CSP may form an interlayer insulating film by applying a resin composition onto a semiconductor substrate (silicon wafer) using a rotary spin coater.
  • a resin composition onto a semiconductor substrate (silicon wafer) using a rotary spin coater.
  • the resin composition when the resin composition is applied to the semiconductor substrate using a spin coater, it may not be possible to form a uniform coating film on the semiconductor substrate.
  • the semiconductor substrate may warp due to shrinkage or the like during curing.
  • the present invention provides a wafer that has good high-frequency characteristics, has little variation in thickness even when applied to a semiconductor substrate using a spin coater, and can form a coating film that does not easily warp the semiconductor substrate.
  • An object of the present invention is to provide a resin composition for a level chip size package type semiconductor device, a semiconductor device using the same, and a method for manufacturing a semiconductor device.
  • the means for solving the above problems are as follows, and the present invention includes the following aspects.
  • 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 end, and (B) an elastomer having a butadiene skeleton.
  • the (A) modified polyphenylene ether resin having an unsaturated double bond at the end is represented by the following formula (1): [In formula (1), X represents a p-valent unsubstituted or substituted aromatic hydrocarbon group, Y is the following formula (2): [In Formula (2), R 1 to R 4 each independently represent 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): [In formula (3), R 5 represents a hydrogen atom or an alkyl group. ] A (meth)acryloyl group represented by or the following formula (4): [In Formula (4), R 6 to R 8 each independently represent a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.
  • the (B) elastomer having a butadiene skeleton is a styrene/butadiene/styrene copolymer, a styrene/butadiene/butylene/styrene copolymer, a butadiene polymer, a styrene/butadiene copolymer, or an acrylonitrile/butadiene copolymer.
  • the (A) modified polyphenylene ether resin having an unsaturated double bond at the terminal is represented by the following formula (5): [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 formula (2), m represents an integer from 1 to 100, n represents an integer of 0 or 1 to 6, p represents an integer of 1 to 4; ]
  • styrene/butadiene/styrene block copolymer represented by the following formula (8) [In formula (8), u represents an integer of 1 to 1,200, and v represents an integer of 1 to 1,000. ]
  • the (A) modified polyphenylene ether resin having an unsaturated double bond at the end contains a modified polyphenylene ether resin represented by the formula (6), and the (B) elastomer having a butadiene skeleton comprises the The resin composition according to any one of [1] to [5] above, comprising a styrene/butadiene/styrene copolymer represented by formula (7).
  • the thixotropy index TI which is the ratio of the second viscosity to the first viscosity
  • the (A) modified polyphenylene ether resin having an unsaturated double bond at the end includes a polyphenylene ether resin represented by the formula (1)
  • the (B) elastomer having a butadiene skeleton comprises a styrene/butadiene/styrene copolymer, a styrene/butadiene/butylene/styrene copolymer, a butadiene polymer, a styrene/butadiene copolymer, and an acrylonitrile/butadiene copolymer.
  • the method for manufacturing a semiconductor device according to any one of [15] to [18], including at least one selected from the group.
  • the present invention it is possible to form a coating film that has good high-frequency characteristics, has little variation in thickness even when applied to a semiconductor substrate using a spin coater, and is less likely to warp the semiconductor substrate. It is possible to provide a resin composition for a level chip size package type semiconductor device, a semiconductor device using the same, and a method for manufacturing a semiconductor device.
  • FIG. 1 is a schematic cross-sectional view showing a schematic configuration of part of a WL-CSP type semiconductor device.
  • the resin composition for a wafer level chip size package type semiconductor device according to the present disclosure a semiconductor device using the resin composition, and a method for manufacturing a semiconductor device will be described based on embodiments.
  • the embodiments shown below are examples for embodying the technical idea of the present invention, and the present invention is not limited to the following resin compositions, semiconductor devices using the same, and semiconductor device manufacturing methods. .
  • 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 (B) an elastomer having a butadiene skeleton (also referred to as “component (B)” ), including Since the resin composition contains the modified polyphenylene ether of component (A), the dielectric constant ( ⁇ ) of the coating film formed by curing the resin composition constituting the interlayer insulating film is 3.0 or less. is preferably 2.9 or less, more preferably 2.8 or less, and particularly preferably 2.7 or less.
  • the dielectric constant ( ⁇ ) of the coating film made of the cured product obtained by curing the resin composition constituting the interlayer insulating film may be 1.0 or more, preferably 1.5 or more. Further, the dielectric loss tangent (tan ⁇ ) of the coating film made of the resin composition constituting the interlayer insulating film is preferably 0.015 or less, more preferably 0.014 or less, and 0.013 or less. is more preferred. The dielectric loss tangent (tan ⁇ ) of the coating film made of the resin composition constituting the interlayer insulating film is preferably 0.001 or more.
  • the dielectric constant of the coating film made of the resin composition constituting the interlayer insulating film of the WL-CSP type light emitting device is 3.0 or less and the dielectric loss tangent (tan ⁇ ) is 0.015 or less, the dielectric constant is low. It has a low dielectric loss tangent and good electrical characteristics when used in a high frequency region. For example, even when the semiconductor device is used in a high-frequency range such as the fifth-generation communication system "5G", which is expected to increase in capacity and speed, a coating film having good electrical characteristics can be obtained.
  • the resin composition contains component (A) and component (B), it shrinks uniformly when the resin composition applied to the semiconductor substrate is cured, and warping of the semiconductor substrate is less likely to occur. Therefore, the resin composition containing component (A) and component (B) is suitable for forming an interlayer insulating film of a WL-CSP type semiconductor device.
  • the resin composition preferably further contains component (A) and component (B) as well as (C) a solvent (also referred to as "component (C)") as necessary.
  • a resin composition containing component (C) as well as component (A) and component (B) has good thixotropy.
  • the resin composition containing component (C) together with component (A) and component (B) has little variation in thickness even when applied to a semiconductor substrate using, for example, a spin coater, and can be applied to a substantially uniform thickness. A film can be formed.
  • the resin composition containing component (A), component (B) and component (C) preferably has a first viscosity of 300 mPa s to 4000 mPa s at 25°C and 10 rpm with a rotational viscometer. . If the first viscosity of the resin composition is in the range of 300 mPa s to 4000 mPa s, the thickness variation is small even when applied to a semiconductor substrate using a spin coater, for example, and the coating has a substantially uniform thickness. A film 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, even more preferably 500 mPa ⁇ s to 2000 mPa ⁇ s.
  • the rotational viscometer can be measured using, for example, a TVE viscometer (cone rotor: 1° 34' x R24, manufactured by Toki Sangyo Co., Ltd.).
  • the resin composition containing component (A), component (B) and component (C) preferably has a second viscosity of 500 mPa s to 4200 mPa s at 25°C and 1 rpm with a rotational viscometer. . If the second viscosity of the resin composition is in the range of 500 mPa s to 4200 mPa s, the thickness variation is small even when applied to a semiconductor substrate using a spin coater, for example, and the coating has a substantially uniform thickness. A film 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, more preferably in the range of 550 mPa ⁇ s to 3500 mPa ⁇ s.
  • the resin composition containing the component (A), the component (B) and the component (C) has a thixotropic index TI, which is the ratio of the second viscosity to the first viscosity, in the range of 0.8 to 1.2, and Newtonian It preferably has a thixotropic property close to that of a fluid.
  • a Newtonian fluid is a fluid having a property in which the shear stress is proportional to the shear rate. If the thixotropy index TI, which is the ratio of the second viscosity to the first viscosity of the resin composition, is in the range of 0.8 to 1.2, even when applied to a semiconductor substrate using a spin coater, for example, the thickness can be reduced.
  • a coating film having a substantially uniform thickness can be formed with little variation, and warpage of the semiconductor substrate during curing can be suppressed.
  • the resin composition may have a thixotropic 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. .
  • the mass ratio of component (A) and component (B) is preferably within the range of 10:90 to 80:20, more preferably within the range of 20:80 to 75:25. Preferably, it is more preferably within the range of 30:70 to 70:30. If the mass ratio of the component (A) and the component (B) in the resin composition is within the range of 10:90 to 80:20, the resin composition has a low dielectric constant and a low dielectric loss tangent, A cured product having good electrical properties when used in a high frequency range can be obtained.
  • 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, and 10:90 to 70: It is more preferably within the range of 30, still more preferably within the range of 12:88 to 40:60, and particularly preferably within the range of 18:82 to 50:50. If the total amount of component (A) and component (B) in the resin composition and the component mass ratio is within the range of 5:95 to 80:20, the resin composition is applied to the semiconductor substrate using, for example, a spin coater. Even in this case, a coating film having a substantially uniform thickness can be formed with little variation in thickness, and a cured product in which warpage of the semiconductor substrate is suppressed can be obtained.
  • Component (A) Modified Polyphenylene Ether is preferably a polyphenylene ether resin having a functional group containing a carbon-carbon double bond at its end.
  • the modified polyphenylene ether (PPE) resin is also referred to as component (A) or the modified PPE resin of component (A).
  • Functional groups containing carbon-carbon double bonds include, for example, any of 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 and has a polyphenylene ether in its skeleton.
  • Component (A) is preferably a thermosetting resin. Further, the component (A) is preferably a polyphenylene ether resin having a terminal vinyl group. Low dielectric properties can be obtained by having a vinyl group at the end
  • the modified PPE resin of component (A) preferably contains a PPE resin represented by the following formula (1).
  • X represents a p-valent unsubstituted or substituted aromatic hydrocarbon group
  • Y is the following formula (2):
  • R 1 to R 4 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an alkenylcarbonyl group.
  • Z 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
  • R 5 represents a hydrogen atom or an alkyl group.
  • R 6 to R 8 each independently represent a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.
  • m represents an integer from 1 to 100
  • n represents an integer of 0 or 1 to 6
  • p represents an integer of 1 to 4;
  • 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). .
  • 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 formula (2)
  • m represents an integer from 1 to 100
  • n represents an integer of 0 or 1 to 6
  • p represents an integer of 1 to 4;
  • R 6 to R 8 each independently represent a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, X represents a p-valent unsubstituted or substituted aromatic hydrocarbon group, Y represents an unsubstituted or substituted phenol repeating unit represented by the formula (2), m represents an integer from 1 to 100, n represents an integer of 0 or 1 to 6, p represents an integer of 1 to 4; ]
  • an x-valent (x represents an integer of 1 or more) hydrocarbon group refers to an x-valent group produced by removing x hydrogen atoms from a hydrocarbon carbon atom.
  • X is a p-valent unsubstituted or substituted aromatic hydrocarbon group, X is by removing 1 to 4 hydrogen atoms from the carbon atoms of the aromatic hydrocarbon, which may or may not be substituted Refers to the resulting mono- to tetravalent groups.
  • alkyl group means a monovalent saturated hydrocarbon group.
  • alkyl groups are preferably C 1 -C 10 alkyl groups, more preferably C 1 -C 6 alkyl groups, still more preferably C 1 -C 4 alkyl groups, particularly preferably C 1 -C 2 alkyl groups.
  • alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl groups.
  • alkenyl group means a monovalent unsaturated hydrocarbon group having at least one carbon-carbon double bond.
  • alkenyl groups are preferably C 2 -C 10 alkenyl groups, more preferably C 2 -C 6 alkenyl groups, and even more preferably C 2 -C 4 alkenyl groups.
  • alkenyl groups include ethenyl (vinyl), 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, isobutenyl, 1-pentenyl and 1-hexenyl groups. be able to.
  • the group —CR 1 ⁇ CR 2 R 3 in formula (1) is also an alkenyl group.
  • alkynyl group means a monovalent unsaturated hydrocarbon group having at least one carbon-carbon triple bond.
  • alkynyl groups are preferably C 2 -C 10 alkynyl groups, more preferably C 2 -C 6 alkynyl groups, and even more preferably C 2 -C 4 alkynyl groups.
  • alkynyl groups include ethynyl, 1-propynyl, 2-propynyl, butynyl, isobutynyl, pentynyl and hexynyl groups.
  • alkenylcarbonyl group means a carbonyl group substituted with the above alkenyl group, and examples thereof include an acryloyl group and a methacryloyl group.
  • component (A) the portion represented by -(Y) m - in formula (1), (5) or (6) corresponds to the main chain of the PPE resin.
  • R 1 and R 3 in the unsubstituted or substituted phenol repeating unit Y represent hydrogen atoms and R 2 and R 4 represent methyl groups.
  • one end of the moiety represented by -(Y) m - is bonded to an aromatic hydrocarbon group X via an oxygen atom, and the other end is attached to n methylene groups. via the terminal group (Z).
  • n in formula (1), (5) or (6) is 0 or an integer of 1-4.
  • n is 0, 1 or 2 in formula (1), (5) or (6).
  • n in formula (1) is 0 or 1.
  • all of R 6 to R 8 in formula (6) are hydrogen atoms.
  • the number m of Y in the repeating unit of formula (1), (5) or (6) is preferably 1-80, more preferably 1-30, still more preferably 1-5.
  • p moieties represented by —(Y) m — are bound to the aromatic hydrocarbon group X of formula (1), (5) or (6) through oxygen atoms, respectively. are doing.
  • p is 2 or 3. More preferably, p is two.
  • X is preferably the following formula: [wherein R 11 to R 18 each independently represent a hydrogen atom or a C 1 -C 6 alkyl group].
  • X is more preferably of the following formula: It has a structure represented by
  • the main chain end of the modified polyphenylene ether resin of component (A) is a polyphenylene ether resin having an average of 1.5 to 5 functional groups per molecule represented by formula (1), (5) or (6). It can be.
  • the terminal functional group is preferably a methacryloyl group and/or an acryloyl group from the viewpoint of imparting even better heat resistance when the resin composition is cured, and from the viewpoint of further excellent resin fluidity during heat molding. Therefore, it is more preferably a methacryloyl group.
  • the number average molecular weight of component (A) is preferably 500 or more and 5000 or less.
  • the number average molecular weight of component (A) is more preferably 750 or more and 3000 or less, still 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.
  • the number average molecular weight (Mn) of component (A) or component (B) can be measured, for example, from polystyrene conversion values by gel permeation chromatography (GPC) measurement.
  • the number average molecular weight (Mn) for example, using high-performance liquid chromatography (eg LC-2OAD, manufactured by Shimadzu Corporation), column (eg KF-802, manufactured by Showa Denko KK), tetrahydrofuran ( THF) solution can be used as a solvent for measurement.
  • high-performance liquid chromatography eg LC-2OAD, manufactured by Shimadzu Corporation
  • column eg KF-802, manufactured by Showa Denko KK
  • THF tetrahydrofuran
  • the content of component (A) in the resin composition is preferably 5.0 to 40.0% by mass with respect to 100% by mass of the total amount of component (A), component (B) and component (C). , more preferably 7.0 to 35.0% by mass, still more preferably 8.0 to 30.0% by mass, and particularly preferably 9.0 to 25.0% by mass.
  • the content of component (A) in the total amount of 100% by mass of component (A) and component (B) and component (C) in the resin composition is 5.0 to 40.0% by mass, low A cured product having a dielectric constant and a low dielectric loss tangent can be obtained, and a cured product having good electrical properties suitable for use in a high frequency region can be obtained.
  • component (A) A commercial item can be used for the component (A).
  • Commercially available products of component (A) are modified PPE resins represented by formula (5), for example modified PPE resins having 1.5 to 5 terminal methacryloyl groups represented by formula (3) per molecule.
  • NORYL SA9000 manufactured by SABIC Innovative Plastics
  • Component (A) is a commercially available modified PPE resin represented by formula (6), 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, by preparing an appropriate p-hydric phenol (2 , 2′,3,3′,5,5′-hexamethylbiphenyl-4,4′-diol, etc.) and the following formula [In the formula, R 1 to R 4 each have the same meaning as described above. ]
  • a suitable monohydric phenol such as 2,6-dimethylphenol having a structure represented by is oxidatively copolymerized by known methods to prepare a hydroxyl-terminated polyphenylene ether resin and obtained
  • Component (A) can be prepared by a method comprising modifying the resin by reaction with a suitable modifier such as chloromethylstyrene.
  • the component (B) elastomer having a butadiene skeleton may have a butadiene skeleton in the molecule, and may be a partially hydrogenated elastomer.
  • Elastomers having a butadiene backbone include, for example, block copolymers containing blocks of styrene or analogues thereof as at least one terminal block and elastomeric blocks of conjugated dienes as at least one intermediate block.
  • Elastomers having a butadiene skeleton of component (B) include styrene/butadiene/styrene copolymers (SBS), styrene/butadiene/butylene/styrene copolymers (SBBS), butadiene copolymers (BR), styrene/butadiene copolymers. It preferably contains at least a species selected from the group consisting of polymers (SBR) and acrylonitrile/butadiene copolymers (NBR).
  • SBR polymers
  • NBR acrylonitrile/butadiene copolymers
  • the elastomer having a butadiene skeleton may be partially modified, for example, carboxylated nitrilobutadiene rubber (NBR) modified with carboxyl at the end.
  • component (C) when the solvent of component (C) is used in the resin composition, it is easily dissolved in the solvent of component (C), and the thixotropic property becomes more favorable. It is possible to form a coating film having a substantially uniform thickness with less variation in the thickness.
  • styrene elastomers having double bonds are preferred, such as styrene/butadiene/styrene copolymer (SBS), styrene/butadiene/butylene/
  • SBS styrene/butadiene/styrene copolymer
  • Preferable examples include styrene-based elastomers including styrene copolymers (SBBS) and styrene/butadiene copolymers.
  • SBBS styrene copolymers
  • the component (B) may also be a reactive elastomer to which a functional group such as amine has been added.
  • Adhesive strength can be further improved by using a reactive elastomer to which a functional group is added.
  • the weight average molecular weight of component (B) is preferably 20,000 to 200,000, more preferably 30,000 to 150,000.
  • the weight average molecular weight is determined by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.
  • the elastomer having a butadiene skeleton of component (B) is selected from the group consisting of a styrene/butadiene/styrene block copolymer represented by the following formula (7) and an acrylonitrile/butadiene copolymer represented by the following formula (8). It is preferable to include at least one selected.
  • q and r represent an integer of 0 to 1, at least one of which is not 0, s represents an integer of 1 to 1,200, and t represents an integer of 1 to 1,000. ]
  • u represents an integer of 1 to 1,200, and v represents an integer of 1 to 1,000.
  • the styrene/butadiene/styrene block copolymer (SBS) of component (B) represented by formula (7) is an unhydrogenated block copolymer. Since the resin composition contains a styrene/butadiene/styrene block copolymer as the component (B), the flexibility and solubility in solvents are improved, and the resin composition can be applied well to a semiconductor substrate using a spin coater. can be applied. Also, even if the resin composition contains a styrene/butadiene/butylene/styrene copolymer (SBBS), which is a partially hydrogenated elastomer, the resin composition can be applied well to the semiconductor substrate.
  • SBBS styrene/butadiene/butylene/styrene copolymer
  • the resin composition or component (B) preferably does not contain elastomers having no double bonds.
  • elastomers having no double bonds include styrene/ethylene/butylene/styrene block copolymers (SEBS) obtained by completely hydrogenating styrene/butadiene/styrene block copolymers. SEBS reduces the compatibility with the solvent of component (C), and the resin composition does not have the desired viscosity. For example, it may be difficult to apply the resin composition to a semiconductor substrate using a spin coater. be.
  • SBS styrene/butadiene/styrene block copolymers
  • SBBS styrene/butadiene/butylene/styrene copolymers
  • s may represent an integer of 1-1200, or an integer of 150-900.
  • t may represent an integer of 1-1000, or an integer of 50-700.
  • the component (B) contains an acrylonitrile/butadiene copolymer (NBR) represented by the formula (8)
  • NBR acrylonitrile/butadiene copolymer
  • the styrene content contained in the component (B) in the resin composition is preferably in the range of 10% by mass or more and 70% by mass or less, and 15% by mass or more and 60% by mass with respect to 100% by mass of the resin composition. % or less, more preferably 20 mass % or more and 55 mass % or less. If the styrene content contained in the component (B) in the resin composition is within the range of 10% by mass or more and 70% by mass or less with respect to 100% by mass of the resin composition, the expansion and contraction of the resin composition during curing For example, when applied to a semiconductor substrate, warping of the semiconductor substrate can be suppressed during curing.
  • the styrene content contained in component (B) in the resin composition can be measured using nuclear magnetic resonance (NMR). Specifically, using tetrachloroethane as a solvent, the integrated value of the peak in the range of 5.5 ppm to 6.5 ppm corresponding to styrene and the integrated value of the peak in other ranges were obtained, and from the obtained values can be calculated.
  • NMR nuclear magnetic resonance
  • the styrene/butadiene ratio (%, mass ratio) of component (B) may be 15/85 or more, 20/80 or more, preferably 70/30 or less, 60/40 or less, or 55/45. It can be below.
  • the uniformity of the film thickness of the coating film, the suppression of warping of the semiconductor substrate when the resin composition is cured, and the compatibility of the component (C) solvent Considering the above, 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 60 ,000 or more and 120,000 or less.
  • the number average molecular weight (Mn) of component (B) can be measured in the same manner as described above, for example, from polystyrene conversion values by gel permeation chromatography (GPC) measurement.
  • 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). Since the resin composition contains the modified PPE resin represented by formula (6) as component (A) and contains SBS as component (B), the resin composition applied to the semiconductor substrate shrinks uniformly when cured, Warping of the semiconductor substrate is less likely to occur. Therefore, the resin composition is suitable for forming an interlayer insulating film of a WL-CSP type semiconductor device.
  • SBS styrene/butadiene/styrene copolymer
  • the content of component (B) in the resin composition is preferably 5.0 to 40.0% by mass with respect to 100% by mass of the total amount of component (A) and component (B) and component (C). , more preferably 7.0 to 35.0% by mass, still more preferably 8.0 to 30.0% by mass, and particularly preferably 9.0 to 25.0% by mass.
  • the content of component (B) in the total amount of 100% by mass of component (A) and component (B) and component (C) in the resin composition is 5.0 to 40.0% by mass, low A cured product having a dielectric constant and a low dielectric loss tangent can be obtained, and a cured product having good electrical properties suitable for use in a high frequency region can be obtained.
  • component (B) in the total amount of 100% by mass of component (A) and component (B) and component (C) in the resin composition is 5.0 to 40.0% by mass.
  • a resin composition is applied to a semiconductor substrate using a spin coater, there is little variation in thickness, a coating film with a substantially uniform thickness can be formed, and a cured product that suppresses warping of the semiconductor substrate is obtained. can get.
  • a commercially available product can be used for the component (B).
  • Commercially available products of component (B) include, for example, trade names “TR2827,” “TR2000,” “TR2003,” and “TR2250” manufactured by JSR Corporation, and trade names “P1083,” “P1500,” and “ P5051”, “MP10”, and trade name “Nipol (trademark) 1072” manufactured by Nippon Zeon Co., Ltd. can be mentioned.
  • the resin composition preferably contains a component (C) solvent.
  • the solvent of component (C) is preferably an organic solvent.
  • the organic solvent easily dissolves or disperses the component (A) and the component (B).
  • 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 at least one selected from the group consisting of toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, cyclohexane, dimethyl carbonate, methylcyclohexanone and ⁇ -butyrolactone. preferable.
  • the solvent of component (C) may be used alone or in combination of two or more. Toluene and cyclohexanone may be used as the solvent for component (C), and cyclohexanone is preferably used from the viewpoint of toxicity.
  • the resin composition can be used as a varnish by dissolving or dispersing the component (A) and the component (B) in the solvent of the component (C).
  • a varnish made of a resin composition containing component (A), component (B) and component (C) preferably has the first and second viscosities described above.
  • the varnish comprising the resin composition containing the component (A), the component (B) and the component (C) preferably has the thixotropy index TI described above.
  • the content of component (C) in the resin composition is in the range of 20 to 90% by mass with respect to 100% by mass of the total amount of component (A), component (B) and component (C). Preferably, it may be in the range of 30-86% by mass, it may be in the range of 40-84% by mass, and it may be in the range of 50-82% by mass.
  • component (C) is within the range of 20 to 90% by mass with respect to 100% by mass of the total amount of component (A) and component (B) and component (C), component (A) and component (B) is easily dissolved or dispersed in the component (C), and when the resin composition is applied to a semiconductor substrate using, for example, a spin coater, there is little variation in thickness and a coating film having a substantially uniform thickness is formed. can be formed, it is difficult to remain in the coating film, and the deterioration of the dielectric properties can be suppressed.
  • a commercially available product can be used for the component (C).
  • Commercially available products of component (C) include, for example, toluene (toluene concentration 100% by mass, manufactured by Daishin Chemical Co., Ltd.), anone (cyclohexanone) (cyclohexanone concentration 90 to 100% by mass, manufactured by Daishin Chemical Co., Ltd.), etc. can be done.
  • the resin composition may contain component (A) and component (B), may contain component (C), and may contain components other than component (A) and component (B) and component (C). It may contain components other than component (A), component (B) and component (C).
  • the resin composition may consist of only component (A), component (B) and component (C).
  • the resin composition may contain a coupling agent to improve adhesion with the semiconductor substrate. Moreover, the resin composition may contain an organic peroxide in order to increase 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.
  • a 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 be silane coupling agents. Coupling agents may be used alone or in combination of two or more. Examples of functional groups possessed by silane coupling agents include alkoxy groups, vinyl groups, epoxy groups, styryl groups, methacryl groups, acrylic groups, amino groups, isocyanurate groups, ureido groups, mercapto groups, sulfide groups, isocyanate groups, and the like. can be mentioned.
  • the resin composition may contain an organic peroxide that initiates a radical polymerization reaction.
  • Peroxycarbonate or the like can be used as the organic peroxide.
  • Perbutyl (trademark) Z manufactured by NOF Corporation can be used as the peroxycarbonate.
  • the content of the additive contained 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 with respect to 100% by mass of the resin composition. good too.
  • the content of the additive contained 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.
  • Additives may be commercially available products, and when the additive is a silane coupling agent, for example, 3-methacryloxypropyltrimethoxysilane KBM 503, vinyltrimethoxysilane KBM 1003 (manufactured by Shin-Etsu Silicone Co., Ltd.), Coatsil MP200 Silane (manufactured by Momentive Performance Materials Japan) can be used.
  • silane coupling agent for example, 3-methacryloxypropyltrimethoxysilane KBM 503, vinyltrimethoxysilane KBM 1003 (manufactured by Shin-Etsu Silicone Co., Ltd.), Coatsil MP200 Silane (manufactured by Momentive Performance Materials Japan) can be used.
  • This resin composition is a non-photosensitive resin composition for a wafer level chip size package type semiconductor device. Moreover, it is preferable that the present resin composition does not contain an inorganic filler such as silica.
  • the interlayer insulating film is formed using a thermosetting insulating resin, the interlayer insulating film is drilled by laser irradiation in a subsequent step to form via holes for wiring. At this time, if the interlayer insulating film contains an inorganic filler such as silica, the silica portion cannot be satisfactorily scraped during the laser treatment, and it may be difficult to satisfactorily copper-plate the via hole thereafter. Therefore, it is preferable not to include an inorganic filler such as silica.
  • not containing an inorganic filler such as silica means that an inorganic filler is not intentionally added to the resin composition. % or more and 0.01 mass % or less.
  • the resin composition can be produced by mixing the component (A), the component (B), and optionally the component (C).
  • the resin composition may be produced by mixing the component (A), the component (B), and optionally the component (C) together with additives as necessary.
  • a filler such as silicon dioxide or aluminum oxide
  • the resin composition does not contain silicon dioxide or aluminum oxide powder.
  • the method for producing the resin composition is not particularly limited.
  • the resin composition can be produced by mixing raw materials for each component with a mixer such as a lykai machine, a pot mill, a three-roll mill, a hybrid mixer, a rotary mixer, or a twin-screw mixer. These components may be mixed at the same time, or a part may be mixed first and the rest may be mixed later.
  • the resin composition may be produced by appropriately combining the devices described above.
  • the cured product obtained by curing the resin composition preferably has a dielectric constant ( ⁇ ) of 3.0 or less, more preferably 2.8 or less, and preferably 2.7 or less. More preferred.
  • the dielectric loss tangent (tan ⁇ ) is preferably 0.015 or less, more preferably 0.014 or less, even more preferably 0.013 or less.
  • a cured product having a low dielectric constant and a low dielectric loss tangent has good electrical properties when used in a high frequency range, and thus can be used for electronic components, semiconductor devices, etc. used in a high frequency range.
  • the resin composition when the resin composition is applied to a semiconductor substrate using, for example, a spin coater, it is sufficiently cured, and for example, the fifth generation communication system "5G" etc., which is expected to increase capacity and high speed communication.
  • a cured product in the form of a thin film having good electrical characteristics and a substantially uniform film thickness can be obtained even when the semiconductor device is used in the high frequency region of . Therefore, the resin composition is a semiconductor comprising a semiconductor substrate, an electrode arranged on the semiconductor substrate, a wiring connected to the electrode, an external terminal electrically connected via the wiring, and an interlayer insulating film.
  • the "rewiring layer” includes wiring and an interlayer insulating film.
  • wiring may be described as “rewiring layer”
  • interlayer insulating film may be described as "sealing resin layer”.
  • the resin composition can be suitably used as a material for forming an interlayer insulating film that seals the wiring on the semiconductor substrate side and the wiring on the opposite side of the semiconductor substrate in a semiconductor device.
  • the film thickness of the rewiring layer can be about 5 to 30 ⁇ m.
  • the film thickness of the rewiring layer may be 5 ⁇ m or more, or may be 10 ⁇ m or more.
  • the film thickness of the rewiring layer may be 30 ⁇ m or less, or may be 20 ⁇ m or less.
  • the resin composition can be suitably used as a sealing resin for a WL-CSP type semiconductor device.
  • a WL-CSP type semiconductor device includes a semiconductor substrate, electrodes arranged on the semiconductor substrate, wirings connected to the electrodes, external terminals electrically connected via the wirings, electrodes of the semiconductor substrate and An interlayer insulating film is provided for sealing the side where the wiring is arranged, and the interlayer insulating film is formed using the resin composition containing the above-described component (A), component (B), and component (C).
  • a WL-CSP type semiconductor device having an interlayer insulating film arranged so as to be in contact with wiring has a first interlayer insulating film (also referred to as a “dielectric film”) that seals the semiconductor substrate side of the wiring.
  • Both the first interlayer insulating film (dielectric film) and the second interlayer insulating film are arranged so as to be in contact with the wiring, and function as interlayer insulating films for the wiring.
  • FIG. 1 is a schematic cross-sectional view showing a schematic configuration of a WL-CSP type semiconductor device.
  • the WL-CSP type semiconductor device is not limited to the example shown in FIG.
  • a WL-CSP type semiconductor device 10 has, on a semiconductor substrate 1, electrodes 2, wirings 4 connected to the electrodes 2, external connection terminals 8 such as conductive balls electrically connected to the wirings 4, Prepare.
  • a protective layer 3 made of an oxide film or the like may be formed between the wiring 4 and the semiconductor substrate 1 .
  • a WL-CSP type semiconductor device 10 includes interlayer insulating films 5 and 6 that seal the sides of a semiconductor substrate 1 on which electrodes 2 and wirings 4 are arranged. Interlayer insulating films 5 and 6 are arranged so as to be in contact with wiring 4 .
  • a film that seals the semiconductor substrate 1 side of the wiring 4 is a first interlayer insulating film (dielectric film) 5 .
  • the film sealing the wiring 4 opposite to the semiconductor substrate 1 side is the second interlayer insulating film 6.
  • the interlayer insulating films 5 and 6 may have at least two layers.
  • the first interlayer insulating film (dielectric layer) 5 and the second interlayer insulating film 6 are arranged so that both layers are in contact with the wiring 4 .
  • the dielectric characteristics can be further lowered, and the electrical characteristics can be improved when used in a high frequency region.
  • the wiring 4 , the first interlayer insulating film (dielectric film) 5 and the second interlayer insulating film 6 constitute a rewiring layer 7 .
  • a semiconductor device means a WL-CSP type semiconductor device.
  • a semiconductor substrate made of a material such as silicon, SiGe, or SOI can be used as the semiconductor substrate.
  • Electrodes are formed by forming a film of an electrode material on substantially the entire surface of a semiconductor substrate by, for example, vacuum deposition or sputtering, and then patterning by, for example, photolithography to form a plurality of electrodes at predetermined positions on the semiconductor substrate. can be done.
  • a silicon nitride (SiN) film is formed on the entire surface of the semiconductor substrate by, for example, vapor deposition, and an oxide film (passive film) is formed on the surface of the silicon nitride to form a protective layer.
  • an oxide film passive film
  • the thicknesses of the semiconductor substrate, electrodes and protective layer are not particularly limited.
  • the resin composition is dropped onto the semiconductor substrate, the semiconductor substrate is rotated around the vertical axis using a spin coater, the liquid resin composition is applied onto the semiconductor substrate, and the liquid resin composition is cured. Then, an interlayer insulating film is formed. Specifically, the resin composition is dropped onto the electrodes and the protective layer on the semiconductor substrate, and the semiconductor substrate is rotated around the vertical axis using a spin coater to coat the electrodes and the protective layer on the semiconductor substrate. A liquid resin composition is applied to the substrate and cured to form a first interlayer insulating film (dielectric 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 ranges, the resin composition can be applied to a substantially uniform thickness on the semiconductor substrate, and an interlayer insulating film having a desired substantially uniform thickness after curing can be obtained. can be formed, and warpage of the semiconductor substrate can be suppressed during curing.
  • the interlayer insulating film can be formed using a resin composition containing the components (A) and (B) described above, and optionally containing the component (C).
  • a resin composition containing the components (A) and (B) described above, and optionally containing the component (C) By using the resin composition described above, even when the resin composition is applied to a semiconductor substrate using a spin coater, it is possible to form a coating film having a substantially uniform thickness with little variation in thickness, and curing.
  • a first interlayer insulating film (dielectric film) can be formed that suppresses warping of the semiconductor substrate.
  • the resin composition containing the components (A) and (B) described above and optionally containing the component (C) can be used to form a correlation insulating film, and the interlayer insulating film is the first interlayer insulating film.
  • the aforementioned component (A) preferably contains a modified PPE resin represented by formula (1), and component (A) includes a modified PPE resin represented by formula (5) and a modified PPE resin represented by formula (6). It preferably contains at least one selected from the group consisting of modified PPE resins.
  • the aforementioned component (B) preferably contains at least one selected from the group consisting of SBS represented by formula (7) and NBR represented by formula (8).
  • 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.
  • the above-mentioned resin composition When applied to a semiconductor substrate using a spin coater, the above-mentioned resin composition preferably has a first viscosity of 300 mPa s to 4000 mPa s at 25 ° C. and 10 rpm with a rotary viscometer, and 400 mPa s. It is more preferably 500 mPa ⁇ s to 2000 mPa ⁇ s, more preferably 500 mPa ⁇ s to 2000 mPa ⁇ s.
  • the first viscosity of the resin composition is within the above range when applied to a semiconductor substrate using a spin coater, it is possible to form a coating film having a substantially uniform thickness with little variation in thickness. It is possible to suppress warpage of the semiconductor substrate during curing.
  • the above-mentioned resin composition When applied to a semiconductor substrate using a spin coater, the above-mentioned resin composition preferably has a second viscosity at 25° C. and 1 rpm in the range of 500 mPa s to 4200 mPa s with a rotary viscometer. , more preferably in the range of 550 mPa s to 4200 mPa s, more preferably in the range of 550 mPa s to 4000 mPa s, more preferably in the range of 550 mPa s to 3500 mPa s More preferred.
  • the second viscosity of the resin composition is within the above range when applied to a semiconductor substrate using a spin coater, it is possible to form a coating film having a substantially uniform thickness with little variation in thickness. It is possible to suppress warpage of the semiconductor substrate during curing.
  • the resin composition When applied to a semiconductor substrate using a spin coater, the resin composition 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. Preferably, it may be within the range of 0.9 to 1.1, and may be within the range of 1.0 to 1.1. If the second viscosity relative to the first viscosity of the resin composition described above is within the above range when applied to a semiconductor substrate using a spin coater, there is little variation in thickness, and a coating film having a substantially uniform thickness can be obtained. It is possible to suppress warpage of the semiconductor substrate during curing.
  • TI thixotropy index
  • the interlayer insulating film, the first interlayer insulating film (dielectric film), or the second interlayer insulating film preferably has a thickness of 3 ⁇ m or more and 20 ⁇ m or less, even if it is in a range of 4 ⁇ m or more and 18 ⁇ m or less. It may be in the range of 5 ⁇ m or more and 17 ⁇ m or less.
  • the interlayer insulating film, the first interlayer insulating film (dielectric film), or the second interlayer insulating film has a thickness of 3 ⁇ m or more and 20 ⁇ m or less. It can also satisfy the demand for miniaturization and thinning of semiconductor devices.
  • the surface portion of the electrode is opened by laser direct patterning using, for example, a laser direct patterning device (manufactured by Mitsubishi Electric Corporation).
  • a first interlayer insulating film (dielectric film) can be formed.
  • a vapor deposition method, a sputtering method, a chemical vapor deposition (CVD) method, an electroless plating method, or the like is applied to substantially the entire surface of the semiconductor substrate on which the electrode, the protective layer, and the first interlayer insulating film (dielectric film) are formed. , forming a seed layer for forming the wiring.
  • the seed layer contains copper and may contain copper oxide, copper and chromium alloys, copper, tantalum, cobalt, titanium and alloys thereof.
  • a resist is formed on the seed layer in a predetermined pattern by, for example, photolithography, and the resist film is used as a mask to form wiring in a predetermined pattern by electroplating or electroless plating.
  • the thickness of the wiring is not particularly limited, the thickness of the wiring may be 0.1 ⁇ m or more, 15 ⁇ m or less, 12 ⁇ m or less, or 10 ⁇ m or less.
  • the second interlayer insulating film can use a resin composition containing the above-described component (A), component (B), and component (C).
  • a spin coater with a rotation speed and rotation time of .
  • the resin composition is applied, dried and cured, for example, using a laser direct patterning device (manufactured by Mitsubishi Electric Corporation), by laser direct patterning, the wiring of the part where the external terminal described later is arranged.
  • a second interlayer insulating film having an open surface portion can be formed.
  • the second interlayer insulating film may be formed by opening the surface portion of the electrode by exposure and development.
  • the rewiring layer is formed by combining the formation of the first interlayer insulating film (dielectric film), the formation of the wiring, and the formation of the second interlayer insulating film.
  • solder balls are formed in the openings of the rewiring layer by a solder ball mounting method, solder plating method, solder paste method, solder paste dispensing method, solder vapor deposition method, etc., and a WL-CSP type semiconductor is formed.
  • a device can be formed.
  • the first interlayer insulating film and the second interlayer insulating film are made of the resin composition containing the above component (A), component (B) and component (C).
  • the semiconductor device Since it is used, it has a low dielectric constant and a low dielectric loss tangent, and the semiconductor device is used in a high frequency region such as the 5th generation communication system "5G", which is expected to increase capacity and high speed communication.
  • the electrical characteristics are good even in the case.
  • the resin composition of the embodiment of the present invention and a semiconductor device using the same can be used for electronic components of electronic devices such as mobile phones, smart phones, notebook computers, tablet terminals, and camera modules.
  • the numbers indicating the blending ratio of each component contained in the resin composition are the ratios (mass (%)) based on the total amount of the resin composition being 100% by mass. represents When the resin composition contains only the component (A), the component (B) and the component (C) and does not contain additives etc., the total amount of the resin composition is the component (A) and the component It represents the total amount of (B) and component (C).
  • Modified polyphenylene ether (PPE) resin A-1 OPE 2st 1200 (modified polyphenylene ether resin represented by formula (6) and having vinyl groups at both ends (2,2′,3,3′, Reaction product of 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.
  • PPE Modified polyphenylene ether
  • resin A-1 OPE 2st 1200 (modified polyphenylene ether resin represented by formula (6) and having vinyl groups at both ends (2,2′,3,3′, Reaction product of 5,5′-hexamethylbiphenyl-4,4′-diol/2,6-dimethylphenol condensate and chloromethylstyrene), number average molecular weight (Mn) 1200) (manufactured by Mitsubishi Gas Chemical
  • A-2 OPE 2st 2200 (modified polyphenylene ether resin represented by formula (6) and having vinyl groups at both ends (2,2′,3,3′,5,5′-hexamethylbiphenyl-4,4 Reaction product of '-diol/2,6-dimethylphenol condensate and chloromethylstyrene), number average molecular weight (Mn) 2200) (manufactured by Mitsubishi Gas Chemical Company, Inc.)
  • A-3 NORYL SA9000 (modified polyphenylene ether resin represented by formula (5) having groups represented by formula (3) at the ends and having methacryloyl groups at both ends, number average molecular weight (Mn) 1850-1950. (Manufactured by SABIC) (SABIC Innovative Plastics)
  • SBS Styrene/butadiene/styrene block copolymer
  • 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 Co., Ltd.
  • B-5 Carboxyl-modified carboxylated nitrilobutadiene rubber (NBR) Nipol (trademark) 1072, number average molecular weight (Mn) 500,000 (manufactured by Nippon Zeon Co., Ltd.)
  • B'-6 tetrafluoroethylene resin Lubron (registered trademark) L-5F (manufactured by Daikin Industries, Ltd.).
  • Solubility For each resin composition, the solubility of component (A) and component (B) or component (B') was evaluated by setting the solvent of component (C) to 70°C.
  • G (good) is a resin composition in which component (A) and component (B) or component (B') are visually dissolved in the solvent of component (C), and visually not dissolved.
  • the resin composition that was found was rated as N (not-good).
  • Viscosity For each resin composition, a TVE viscometer (cone rotor: 1° 34' x R24, manufactured by Toki Sangyo Co., Ltd.) was used to measure the first viscosity at 25 ° C. and 10 rpm, and the second viscosity at 25 ° C. and 1 rpm. and the thixotropy index TI of the second viscosity relative to the first viscosity (viscosity at 1 rpm/viscosity at 10 rpm).
  • a TVE viscometer cone rotor: 1° 34' x R24, manufactured by Toki Sangyo Co., Ltd.
  • a spin coater was operated at 1000 rpm for 5 seconds and then at 2000 rpm for 30 seconds to spin coat the resin composition on the silicon wafer surface to form a coating film.
  • a silicon wafer having a diameter of 150 mm and a thickness of 0.525 mm was spin-coated with each resin composition of Examples and Comparative Examples using a spin coater (MS-A200, manufactured by Mikasa Co., Ltd.).
  • a spin coater was operated at 1000 rpm for 5 seconds and then at 3000 rpm for 30 seconds to spin coat the resin composition on the silicon wafer surface to form a coating film.
  • the silicon wafer having the thin film of the resin composition was subjected to preheat treatment (drying) in a nitrogen atmosphere at 130° C. for 10 minutes and then heated to obtain a sample in which the coating film of the resin composition was dried. Thereafter, heat treatment (curing) was performed at 200° C. for 60 minutes in a nitrogen atmosphere to obtain a cured sample of the coating film of the resin composition.
  • the film thickness of the coating film of the resin composition was measured with a stylus type profiling system (Surfcom 300B, manufactured by Tokyo Seimitsu Co., Ltd.). Note that the film thickness of the interlayer insulating film can be about 5 ⁇ m to 30 ⁇ m.
  • the film thickness of the interlayer insulating film may be 5 ⁇ m or more, or may be 10 ⁇ m or more. Also, the film thickness of the interlayer insulating film may be 30 ⁇ m or less, or may be 20 ⁇ m or less.
  • Warpage of Semiconductor Substrate As a semiconductor substrate, the warpage of a silicon wafer itself (before coating) having a diameter of 150 mm and a thickness of 0.525 mm was measured with a 3D heating surface profile measuring device (Thermoray AXP2.0, manufactured by akrometrix) (hereinafter referred to as referred to as “initial warp amount”). 3 g of the resin composition was dropped onto the center of this silicon wafer, and each resin composition of Examples and Comparative Examples was spin-coated using a spin coater (MS-A200, manufactured by Mikasa Corporation). For spin coating, a spin coater was operated to spin coat the resin composition on the silicon wafer surface to form a coating film.
  • a spin coater was operated to spin coat the resin composition on the silicon wafer surface to form a coating film.
  • the silicon wafer having the thin film of the resin composition was subjected to preheat treatment (drying) in a nitrogen atmosphere at 130° C. for 10 minutes and then heated to obtain a sample in which the coating film of the resin composition was dried. Thereafter, heat treatment (curing) was performed at 200° C. for 60 minutes in a nitrogen atmosphere to obtain a cured sample of the coating film of the resin composition.
  • the warpage of the silicon wafer was measured using a 3D heating surface profile measuring device (Thermoray AXP2.0, manufactured by Akrometrix) (hereinafter referred to as "the amount of warpage after curing").
  • the amount of warpage refers to the value (height) obtained by subtracting the amount of initial warpage from the amount of warpage after curing.
  • the silicon wafer is also simply referred to as "wafer”.
  • Amount of warp (amount of warp after curing) - (amount of initial warp)
  • the amount of warpage is preferably in the range of -5 mm to 5 mm, more preferably in the range of -3 mm to 3 mm, and even more preferably in the range of -2 mm to 2 mm.
  • the wafer When the amount of warpage is in the range of -5 mm to 5 mm, the wafer is held by suction using a wafer holder having a vacuum suction mechanism (for example, vacuum tweezers), and the wafer is moved by moving the wafer holder. can be moved to the desired location.
  • a vacuum suction mechanism for example, vacuum tweezers
  • the wafer has a large warp, the entire surface of the wafer cannot be sucked, and for example, only the central portion of the wafer is partially sucked. In this case, a sufficient holding force cannot be obtained, and there is a risk that the wafer may fall off the vacuum tweezers due to a slight impact during wafer transfer. If the holding force becomes extremely small, it may become impossible to suck the wafer.
  • Strength (adhesion) measurement (cross-cut peel test) Strength (adhesion) was measured according to ASTM D3359-97. Specifically, a silicon wafer spin coater (MS-A200, manufactured by Mikasa Co., Ltd.) having a diameter of 150 mm and a thickness of 0.525 mm was used as a semiconductor substrate, and each resin composition of Examples and Comparative Examples was spin-coated. . For spin coating, a spin coater was operated to spin coat the resin composition on the silicon wafer surface to form a coating film. Next, the silicon wafer having the thin film of the resin composition was subjected to preheat treatment (drying) in a nitrogen atmosphere at 130° C.
  • preheat treatment drying
  • a sample for the cross-cut peel test was produced.
  • a cross-cut guide manufactured by Gotec Co., Ltd.
  • a cellophane tape manufactured by Nichiban Co., Ltd.
  • the area of the peeled coating film was measured and judged on a scale of 0B to 5B shown in Table 2 below.
  • Relative permittivity ( ⁇ ), dielectric loss tangent (tan ⁇ ) A measurement sample was prepared as follows. Each resin composition of Examples and Comparative Examples is applied to a support made of polyethylene terephthalate (PET), subjected to preheat treatment (drying) at 130° C. for 10 minutes in a nitrogen atmosphere, and heated to remove the resin composition. It was dried and treated (cured) at 200° C. for 60 minutes in a nitrogen atmosphere to obtain a coating film of the resin composition having a thickness of 10 ⁇ m.
  • the dielectric constant ( ⁇ ) and dielectric loss tangent (tan ⁇ ) of the measurement sample were measured at a dielectric resonance frequency of 5 GHz by the cavity resonator perturbation method.
  • the dielectric constant ( ⁇ ) is preferably 1.5 to 3.0
  • the dielectric loss tangent (tan ⁇ ) is preferably 0.001 to 0.010.
  • the resin compositions of Examples 1 to 12 had good solubility of component (A) and component (B) in component (C), and a semiconductor was prepared using a spin coater. When applied to a substrate, a coating film having a substantially uniform thickness could be formed. Further, the coating films obtained from the resin compositions of Examples 1 to 12 have a dielectric constant ( ⁇ ) of 2.7 or less and a dielectric loss tangent (tan ⁇ ) of 0.015 or less. Also, when the semiconductor device is used in a high-frequency range such as the fifth-generation communication system "5G" in which high-speed communication is expected to advance, the electrical characteristics are good.
  • a high-frequency range such as the fifth-generation communication system "5G" in which high-speed communication is expected to advance
  • the resin compositions of Examples 1 to 12 had a first viscosity at 25° C. and 10 rpm in the range of 300 mPa s to 4000 mPa s with a rotational viscometer, The second viscosity at 25° C. and 1 rpm was 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, was in the range of 0.8 to 1.2. .
  • the resin compositions of Examples 1 to 9 have little variation in thickness even when applied to a semiconductor substrate using a spin coater, and can form a coating film with a substantially uniform thickness. It was possible to suppress the warpage of the substrate.
  • the resin compositions of Examples 1 to 12 were evaluated as 5B, which means that the removed area was 0%, in the cross-cut peel test, and the adhesion was also good.
  • the resin composition according to the present invention can be used for WL-CSP type semiconductor devices.
  • the resin composition of the embodiment of the present invention and a semiconductor device using the same can be used for electronic components of electronic devices such as mobile phones, smart phones, notebook computers, tablet terminals, and camera modules.
  • 1 semiconductor substrate
  • 2 electrode
  • 3 protective layer
  • 4 wiring
  • 5 first interlayer insulating film (dielectric)
  • 6 second interlayer insulating film
  • 7 rewiring layer
  • 8 external terminal
  • 10 Semiconductor device.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
PCT/JP2022/034526 2021-10-04 2022-09-15 樹脂組成物、半導体装置及び半導体装置の製造方法 Ceased WO2023058425A1 (ja)

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DE112022004813.1T DE112022004813T5 (de) 2021-10-04 2022-09-15 Harzzusammensetzung, halbleitervorrichtung, und verfahren zur herstellung einer halbleitervorrichtung
US18/689,720 US20240360310A1 (en) 2021-10-04 2022-09-15 Resin composition, semiconductor device, and method for producing semiconductor device
JP2026001025A JP2026062946A (ja) 2021-10-04 2026-01-06 樹脂組成物、半導体装置及び半導体装置の製造方法

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Citations (4)

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JP2016079354A (ja) * 2014-10-22 2016-05-16 ナミックス株式会社 樹脂組成物、それを用いた絶縁フィルムおよび半導体装置
WO2019103086A1 (ja) * 2017-11-24 2019-05-31 ナミックス株式会社 熱硬化性樹脂組成物、絶縁性フィルム、層間絶縁性フィルム、多層配線板、および半導体装置
JP2019172803A (ja) * 2018-03-28 2019-10-10 三井金属鉱業株式会社 樹脂組成物、樹脂付銅箔、プリント配線板、及び樹脂付銅箔の処理方法
WO2020017412A1 (ja) * 2018-07-20 2020-01-23 三菱瓦斯化学株式会社 樹脂組成物、プリプレグ、金属箔張積層板、樹脂シートおよびプリント配線板

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JP2010192938A (ja) 2010-06-07 2010-09-02 Fujikura Ltd 半導体装置
JP2015090926A (ja) * 2013-11-06 2015-05-11 日立化成株式会社 半導体装置製造用フィルム、これを用いた半導体装置、及び半導体装置の製造方法
JP2017092152A (ja) 2015-11-05 2017-05-25 日立化成デュポンマイクロシステムズ株式会社 多層体、その製造方法及び半導体装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016079354A (ja) * 2014-10-22 2016-05-16 ナミックス株式会社 樹脂組成物、それを用いた絶縁フィルムおよび半導体装置
WO2019103086A1 (ja) * 2017-11-24 2019-05-31 ナミックス株式会社 熱硬化性樹脂組成物、絶縁性フィルム、層間絶縁性フィルム、多層配線板、および半導体装置
JP2019172803A (ja) * 2018-03-28 2019-10-10 三井金属鉱業株式会社 樹脂組成物、樹脂付銅箔、プリント配線板、及び樹脂付銅箔の処理方法
WO2020017412A1 (ja) * 2018-07-20 2020-01-23 三菱瓦斯化学株式会社 樹脂組成物、プリプレグ、金属箔張積層板、樹脂シートおよびプリント配線板

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