CN111801781B - Adhesive for semiconductor and method for manufacturing semiconductor device using the same - Google Patents
Adhesive for semiconductor and method for manufacturing semiconductor device using the same Download PDFInfo
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- CN111801781B CN111801781B CN201980016195.XA CN201980016195A CN111801781B CN 111801781 B CN111801781 B CN 111801781B CN 201980016195 A CN201980016195 A CN 201980016195A CN 111801781 B CN111801781 B CN 111801781B
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- Prior art keywords
- semiconductor
- adhesive
- chip
- semiconductor device
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 236
- 239000000853 adhesive Substances 0.000 title claims abstract description 106
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- 238000000034 method Methods 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 19
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- SZUPZARBRLCVCB-UHFFFAOYSA-N 3-(2-undecylimidazol-1-yl)propanenitrile Chemical compound CCCCCCCCCCCC1=NC=CN1CCC#N SZUPZARBRLCVCB-UHFFFAOYSA-N 0.000 description 2
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- 229910052618 mica group Inorganic materials 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
- H01L25/03—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes
- H01L25/04—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers
- H01L25/065—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers the devices being of a type provided for in group H01L27/00
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
- H01L25/03—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes
- H01L25/04—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers
- H01L25/07—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers the devices being of a type provided for in group H01L29/00
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
- H01L25/18—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof the devices being of types provided for in two or more different subgroups of the same main group of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
- H01L2224/161—Disposition
- H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/16245—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73201—Location after the connecting process on the same surface
- H01L2224/73203—Bump and layer connectors
- H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Computer Hardware Design (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Wire Bonding (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Die Bonding (AREA)
Abstract
The adhesive for a semiconductor of the present invention is an adhesive for a semiconductor used for sealing at least a part of a connection portion in a semiconductor device, wherein the semiconductor device is a semiconductor device in which electrodes of the connection portion of a semiconductor chip and a wiring circuit board are electrically connected to each other, or a semiconductor device in which electrodes of the connection portion of a plurality of semiconductor chips are electrically connected to each other, and the thixotropic value of the adhesive for a semiconductor is 1.0 to 3.1, and the thixotropic value is the following value: the thixotropic value is obtained by measuring the viscosity of a sample having a semiconductor adhesive laminated to a thickness of 400 μm under a constant condition at 120℃with a shear viscosity measuring device so as to continuously change the frequency from 1Hz to 70Hz, and dividing the viscosity value at 7Hz by the viscosity value at 70 Hz.
Description
Technical Field
The present disclosure relates to an adhesive for a semiconductor and a method for manufacturing a semiconductor device using the same.
Background
Conventionally, a wire bonding method using a thin metal wire such as a gold wire has been widely used for connecting a semiconductor chip to a substrate. On the other hand, in order to meet the demands for higher functionality, higher integration, higher speed, and the like of semiconductor devices, flip chip connection (FC connection) has been developed in which conductive bumps called bumps are formed on a semiconductor chip or a substrate and direct connection is performed between the semiconductor chip and the substrate.
As flip chip connection methods, the following methods are known: a method of joining metals using solder, tin, gold, silver, copper, or the like; a method of applying ultrasonic vibration to join metals; a method of maintaining mechanical contact by the shrinkage force of the resin, etc., but a method of joining metals using solder, tin, gold, silver, copper, etc. is generally used from the viewpoint of reliability of the connection portion.
For example, in connection between a semiconductor Chip and a substrate, a COB (Chip On Board) connection system widely used for BGA (Ball Grid Array), CSP (Chip Size Package), and the like is also a flip Chip connection system. Flip Chip connection is widely used for forming connection portions (bumps or wirings) On semiconductor chips and for connecting the semiconductor chips to each other by a COC (Chip On Chip) connection method (for example, refer to patent document 1 below).
A chip stack package, POP (Package On Package, stack package), TSV (Through-Silicon Via), and the like, in which the above connection method is laminated and multi-staged, are also becoming widely popular, with a strong demand for further miniaturization, thinning, and high functionality. Since packages can be reduced by being arranged not in a planar shape but in a three-dimensional shape, these techniques are widely used, and are also effective for improving the performance of semiconductors, reducing noise, reducing mounting area, and saving power, and have been attracting attention as next-generation semiconductor wiring techniques.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication 2016-102165
Disclosure of Invention
Technical problem to be solved by the invention
In flip chip packages which have been developed for higher functionality, higher integration, and lower cost, it is required to mount chips with a high density while suppressing the resin bleed width at the time of chip mounting for high productivity. If the pressure-bonding load is reduced for this purpose, the resin exudation width can be suppressed, but the corner portions of the chip may become insufficient in resin, and chip peeling may be caused.
The main object of the present disclosure is to provide an adhesive for a semiconductor capable of obtaining a semiconductor device free from resin shortage at the time of mounting by controlling oozing out a resin shape at the time of chip mounting and resin oozing out in a shape along the side surface of a chip, and a method for manufacturing a semiconductor device using the adhesive for a semiconductor.
Means for solving the technical problems
An aspect of the present disclosure is [1] an adhesive for a semiconductor, which is used for sealing at least a part of a connection portion in a semiconductor device, wherein the semiconductor device is a semiconductor device in which electrodes of the connection portion of a semiconductor chip and a wired circuit board are electrically connected to each other, or a semiconductor device in which electrodes of the connection portion of a plurality of semiconductor chips are electrically connected to each other, and a thixotropic value of the adhesive for a semiconductor is 1.0 or more and 3.1 or less, and the thixotropic value is as follows: the thixotropic value is obtained by measuring the viscosity of a sample having a thickness of 400 μm laminated with the adhesive for semiconductor under a constant condition at 120℃with a shear viscosity measuring device, in which the viscosity is continuously changed from 1Hz to 70Hz, and dividing the viscosity value at 7Hz by the viscosity value at 70 Hz.
Further, another aspect of the present disclosure is the adhesive for a semiconductor according to [2] above [1], which contains (a) an epoxy resin, (b) a curing agent, and (c) a high molecular weight component having a weight average molecular weight of 10000 or more.
Another aspect of the present disclosure is the adhesive for a semiconductor according to [3] above, wherein the adhesive further contains (d) a filler.
Another aspect of the present disclosure is the adhesive for a semiconductor according to [4] above [2] or [3], which further contains (e) a flux.
In addition, another aspect of the present disclosure is the adhesive for a semiconductor according to any one of [5] above [2] to [4], wherein the polydispersity Mw/Mn of the high molecular weight component (c) having a weight average molecular weight of 10000 or more is 3 or less.
In addition, another aspect of the present disclosure is the adhesive for a semiconductor according to any one of [2] to [5], wherein a part or all of the material contained in the adhesive for a semiconductor is soluble in cyclohexanone.
Further, another aspect of the present disclosure is the adhesive for a semiconductor according to any one of [1] to [6] above, wherein the adhesive is in a film form.
Further, another aspect of the present disclosure is a method for manufacturing a semiconductor device according to [8], comprising: a step of aligning a semiconductor chip and a wiring circuit board with each other by using the adhesive for a semiconductor of any one of the above [1] to [7], by using a connecting device, and by mutually connecting electrodes of respective connection portions of the semiconductor chip and the wiring circuit board while mutually electrically connecting the electrodes, and sealing at least a part of the connection portions by using the adhesive for a semiconductor; or a step of aligning the plurality of semiconductor chips with the semiconductor adhesive interposed therebetween by a connecting device, electrically connecting electrodes of the respective connection portions of the plurality of semiconductor chips to each other while connecting the semiconductor chips to each other, and sealing at least a part of the connection portions by the semiconductor adhesive.
Effects of the invention
According to the present disclosure, by controlling the thixotropic value of the adhesive for a semiconductor, the shape of the resin oozing out to the outer peripheral portion of the chip at the time of mounting the semiconductor device can be controlled, and by the resin oozing out in a shape along the side surface of the chip, the resin shortage can be suppressed. Further, according to the present disclosure, a semiconductor device using such an adhesive for a semiconductor and a method for manufacturing the same can be provided.
Drawings
Fig. 1 is a schematic cross-sectional view showing an embodiment of a semiconductor device of the present disclosure.
Fig. 2 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present disclosure.
Fig. 3 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present disclosure.
Fig. 4 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present disclosure.
Detailed Description
Hereinafter, preferred embodiments of the present disclosure will be described in detail with reference to the accompanying drawings, as the case may be. In the drawings, the same or corresponding portions are denoted by the same reference numerals, and repetitive description thereof will be omitted. The positional relationship between the upper, lower, left, right, etc. is based on the positional relationship shown in the drawings, unless otherwise specified. Further, the dimensional proportion of the drawings is not limited to the proportion shown in the drawings.
In the present description, a numerical range indicated by "to" is a range including numerical values described before and after "to" as a minimum value and a maximum value, respectively. In the numerical ranges described in stages in the present specification, the upper limit value or the lower limit value of the numerical range in a certain stage may be arbitrarily combined with the upper limit value or the lower limit value of the numerical range in another stage. In the numerical ranges described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. "a or B" may include either one of a and B, or both of them. The materials exemplified in the present specification are not particularly limited, and 1 or 2 or more may be used singly or in combination. In the present specification, "(meth) acrylic" means acrylic acid or methacrylic acid corresponding thereto.
< adhesive for semiconductor >
The adhesive for a semiconductor of the present embodiment is used for sealing at least a part of a connection portion in a semiconductor device in which electrodes of the connection portion of each of a semiconductor chip and a wiring circuit board are electrically connected to each other or in which electrodes of the connection portion of each of a plurality of semiconductor chips are electrically connected to each other.
The thixotropic value of the adhesive for a semiconductor of the present embodiment is 1.0 to 3.1. The thixotropic values are the following values: the thixotropic value is obtained by measuring the viscosity of a sample having a thickness of 400 μm laminated with the adhesive for semiconductor under a constant condition at 120℃with a shear viscosity measuring device, in which the viscosity is continuously changed from 1Hz to 70Hz, and dividing the viscosity value at 7Hz by the viscosity value at 70 Hz. When the thixotropic value is 3.1 or less, the adhesive for semiconductor can sufficiently flow even at the corner of the chip where the shear applied at the time of chip mounting is minimized, and the resin oozes out in a shape along the side surface of the chip. Further, the thixotropic value may be 1.5 or more, 2.0 or more, or 2.5 or more.
The adhesive for a semiconductor of the present embodiment may contain (a) an epoxy resin, (b) a curing agent, and (c) a high molecular weight component having a weight average molecular weight of 10000 or more, and preferably further contains (d) a filler and (e) a flux.
((a) component: epoxy resin)
Examples of the epoxy resin of the component (a) include epoxy resins having 2 or more epoxy groups in the molecule, and bisphenol a type epoxy resins, bisphenol F type epoxy resins, naphthalene type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, phenol aralkyl type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, dicyclopentadiene type epoxy resins, various polyfunctional epoxy resins, and the like can be used. (a) The components may be used singly or in combination of 1 or more than 2.
(a) The content of the component (c) is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and even more preferably 20 to 40% by mass, based on the total amount of the solid components of the adhesive for semiconductor. (a) When the content of the component is 10 mass% or more, it is easy to sufficiently control the flow of the cured resin, and when it is 50 mass% or less, the resin component of the cured product is not excessive, and warpage of the package is easily reduced. In addition, when the content of the component (a) is within the above range, the touch value of the adhesive for a semiconductor can be easily controlled to 1.0 to 3.1. When the resin component is small and the filler content is large, the thixotropic value tends to be reduced, and therefore, when the content of the component (a) is 50 mass% or less, the thixotropic value tends to be reduced.
((b) component: curing agent)
The adhesive for a semiconductor of the present embodiment contains (b) a curing agent. Examples of the curing agent include phenolic resin curing agents, acid anhydride curing agents, amine curing agents, imidazole curing agents, phosphine curing agents, and the like. (b) When the component contains a phenolic hydroxyl group, an acid anhydride, an amine or an imidazole, the flux activity of suppressing the generation of an oxide film at the connection portion is easily exhibited, and the connection reliability and insulation reliability can be easily improved. Hereinafter, each curing agent will be described.
(b-i) phenolic resin curing agent
Examples of the phenolic resin curing agent include curing agents having 2 or more phenolic hydroxyl groups in the molecule, and phenol novolac resins, cresol novolac resins, phenol aralkyl resins, cresol naphthol formaldehyde polycondensates, triphenylmethane type polyfunctional phenolic resins, various polyfunctional phenolic resins, and the like can be used. The phenolic resin curing agent may be used alone or in combination of 1 or more than 2.
The equivalent ratio (molar ratio of phenolic hydroxyl groups/epoxy groups) of the phenolic resin curing agent to the component (a) is preferably 0.3 to 1.5, more preferably 0.4 to 1.0, and even more preferably 0.5 to 1.0, from the viewpoint of excellent curability, adhesion, and storage stability. When the equivalent ratio is 0.3 or more, curability tends to be improved and adhesion tends to be improved, and when it is 1.5 or less, unreacted phenolic hydroxyl groups tend not to remain excessively, water absorption is suppressed to be low, and insulation reliability tends to be further improved.
(b-ii) an acid anhydride-based curing agent
As the acid anhydride-based curing agent, methylcyclohexane tetracarboxylic dianhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, ethylene glycol bis (dehydrated trimellitate) and the like can be used. The acid anhydride-based curing agent may be used alone or in combination of 1 or more than 2.
The equivalent ratio (molar ratio of acid anhydride group/epoxy group) of the acid anhydride-based curing agent to the component (a) is preferably 0.3 to 1.5, more preferably 0.4 to 1.0, and even more preferably 0.5 to 1.0, from the viewpoint of excellent curability, adhesion, and storage stability. When the equivalent ratio is 0.3 or more, curability tends to be improved and adhesion tends to be improved, and when it is 1.5 or less, unreacted acid anhydride groups tend not to remain excessively, water absorption is suppressed to be low, and insulation reliability tends to be further improved.
(b-iii) an amine-based curing agent
Dicyandiamide, various amine compounds, and the like can be used as the amine-based curing agent.
The equivalent ratio (amine/epoxy group, molar ratio) of the amine-based curing agent to the component (a) is preferably 0.3 to 1.5, more preferably 0.4 to 1.0, and even more preferably 0.5 to 1.0, from the viewpoint of excellent curability, adhesion, and storage stability. When the equivalent ratio is 0.3 or more, curability tends to be improved and adhesion tends to be improved, and when it is 1.5 or less, unreacted amine tends not to remain excessively and insulation reliability tends to be further improved.
(b-iv) imidazole curing agent
Examples of the imidazole-based curing agent include 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2' -methylimidazole- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -undecylimidazole- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -ethyl-4 ' -methylimidazole- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -methylimidazole- (1 ') ] -ethyl-s-triazine isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxy-methylimidazole and imidazole adducts. Among them, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -ethyl-4 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2-phenylimidazole isocyanurate adduct, 2-phenyl-4, 5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole are preferable from the viewpoints of more excellent curability, storage stability and connection reliability. The imidazole curing agent may be used alone or in combination of 1 or more than 2. In addition, a latent curing agent obtained by microencapsulating them can be prepared.
The content of the imidazole-based curing agent is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the component (a). When the content of the imidazole-based curing agent is 0.1 part by mass or more, the curability tends to be improved, and when it is 20 parts by mass or less, the adhesive composition is not cured before forming the metal bond, and poor connection tends to be less likely to occur.
(b-v) phosphine-based curing agent
Examples of the phosphine-based curing agent include triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetrakis (4-methylphenyl) borate, and tetraphenylphosphonium (4-fluorophenyl) borate.
The content of the phosphine-based curing agent is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the component (a). When the content of the phosphine-based curing agent is 0.1 part by mass or more, the curability may be improved, and when it is 10 parts by mass or less, the adhesive for semiconductor is not cured before forming the metal bond, and poor connection is less likely to occur.
The phenolic resin curing agent, the acid anhydride curing agent and the amine curing agent may be used singly or in combination of 1 or more than 2 kinds. The imidazole-based curing agent and the phosphine-based curing agent may be used alone, or may be used together with a phenolic resin-based curing agent, an acid anhydride-based curing agent or an amine-based curing agent.
The component (b) is preferably a combination of a phenolic resin curing agent and an imidazole curing agent, a combination of an acid anhydride curing agent and an imidazole curing agent, a combination of an amine curing agent and an imidazole curing agent, or an imidazole curing agent alone, from the viewpoint of excellent curability. Since productivity is improved when the connection is performed in a short period of time, it is more preferable to use an imidazole-based curing agent excellent in quick curability alone. In this case, since volatile components such as low molecular components can be suppressed when curing occurs in a short period of time, the occurrence of voids can be easily suppressed.
( (c) The components are as follows: high molecular weight component having weight average molecular weight of 10000 )
Examples of the high molecular weight component (c) having a weight average molecular weight of 10000 or more (excluding the compound corresponding to the component (a)) include phenoxy resins, polyimide resins, polyamide resins, polycarbodiimide resins, cyanate resins, (meth) acrylic resins, polyester resins, polyethylene resins, polyethersulfone resins, polyetherimide resins, polyvinyl acetal resins, polyurethane resins, and acrylic rubbers, and among these, phenoxy resins, polyimide resins, (meth) acrylic resins, acrylic rubbers, cyanate resins, and polycarbodiimide resins are preferable from the viewpoint of excellent heat resistance and film formability, and phenoxy resins, polyimide resins, (meth) acrylic resins, and acrylic rubbers are more preferable. (c) The components may be used singly or as a mixture or copolymer of 2 or more kinds.
(c) The mass ratio of the component (a) to the component (a) is not particularly limited, but the content of the component (a) is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and still more preferably 0.1 to 3 parts by mass, relative to 1 part by mass of the component (c) in order to maintain the film shape. When the content of the component (a) is 0.01 parts by mass or more, there is no decrease in curability or decrease in adhesion, and when the content is 5 parts by mass or less, there is no decrease in film formability and film formability. The thixotropic value can be adjusted by the combination of the component (c) and the component (a) and the mass ratio thereof.
(c) The weight average molecular weight of the component (a) is 10000 or more in terms of polystyrene, and is preferably 30000 or more, more preferably 40000 or more, and even more preferably 50000 or more, in order to exhibit good film formability alone. When the weight average molecular weight is 10000 or more, there is no concern that the film formability is lowered. In the present specification, the weight average molecular weight refers to a weight average molecular weight measured by polystyrene conversion using high performance liquid chromatography (C-R4A manufactured by shimadzu corporation).
(c) The polydispersity Mw/Mn of the component is preferably 3 or less, more preferably 2.5 or less. When Mw/Mn is 3 or less, the molecular weight tends to be less uneven and the thixotropic value tends to be easily lowered.
((d) component: filler)
Examples of the filler as the component (d) include an insulating inorganic filler. Among them, inorganic fillers having an average particle diameter of 100nm or less are more preferable. Examples of the insulating inorganic filler include glass, silica, alumina, titanium oxide, mica, and boron nitride, and among them, silica, alumina, titanium oxide, and boron nitride are preferable, and silica, alumina, and boron nitride are more preferable. The insulating inorganic filler may be whiskers, and examples of the whiskers include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, magnesium sulfate, boron nitride, and the like. The insulating inorganic filler may be used alone or in combination of 1 or more than 2. (d) The shape, particle size and content of the components are not particularly limited.
The component (d) is preferably insulating from the viewpoint of further excellent insulation reliability. The adhesive for a semiconductor of the present embodiment preferably does not contain a conductive metal filler such as a silver filler or a solder filler.
(d) The component (c) is preferably a filler subjected to surface treatment from the viewpoint of improving dispersibility and adhesion. Examples of the surface treating agent include glycidyl (epoxy) compounds (excluding compounds corresponding to the component (a)), amine compounds, phenyl compounds, phenylamino compounds, (meth) acrylic compounds (for example, compounds having a structure represented by the following general formula (1)), vinyl compounds having a structure represented by the following general formula (2), and the like.
[ chemical formula number 1]
[R 11 Represents a hydrogen atom or an alkyl group, R 12 Represents an alkylene group.]
Examples of the filler surface-treated with the compound having the structure represented by the general formula (1) include R 11 Acrylic surface treatment filler, R, being a hydrogen atom 11 Methacrylic surface treatment filler, R, being methyl 11 In view of reactivity with the resin contained in the adhesive for semiconductor and the surface of the semiconductor substrate, R is preferable from the viewpoint of bond formation, for example, as an ethyl acrylic surface-treated filler for ethyl group 11 A low volume, acrylic surface treatment filler, and methacrylic surface treatment filler. R is R 12 The one having a high weight average molecular weight is also preferable because the volatile component is small.
[ chemical formula number 2]
[R 21 、R 22 R is R 23 Represents a 1-valent organic group, R 24 Represents an alkylene group.]
For example, from the viewpoint of not decreasing the reactivity, R 21 、R 22 R is R 23 Preferably, the group is not bulky, and may be a hydrogen atom or an alkyl group, for example. In addition, R 21 、R 22 R is R 23 It may also be a 1-valent organic group having an improved reactivity of vinyl groups. R is R 24 There is also no particular limitation on the type of the material,from the viewpoint of being easily reduced in voids due to being difficult to volatilize, those having a high weight average molecular weight are preferable. In addition, R 21 、R 22 、R 23 R is R 24 The selection may also be made according to the ease of surface treatment.
As the surface treating agent, a silane treating agent such as an epoxy silane, an amino silane, and a (meth) acrylic silane is preferable from the viewpoint of easiness of surface treatment. The surface treatment agent is preferably a glycidyl group, a phenylamino group, or a (meth) acrylic group compound from the viewpoint of excellent dispersibility, fluidity, and adhesion. The surface treatment agent is more preferably a phenyl group or a (meth) acrylic compound from the viewpoint of excellent storage stability.
(d) The average particle diameter of the component is preferably 100nm or less, more preferably 60nm or less, from the viewpoint of improving visibility. (d) From the viewpoint of improving the adhesion, the component (c) is preferably an inorganic filler having an average particle diameter of 60nm or less, which is surface-treated with (meth) acrylic silane or epoxy silane. On the other hand, the larger the average particle diameter of the component (d), the smaller the thixotropic value tends to be.
(d) The content of the component (a) is preferably 20 to 80% by mass, more preferably 30 to 75% by mass, and still more preferably 50 to 75% by mass, based on the total amount of the semiconductor adhesive. (d) When the content of the component is 20 mass% or more, there is no concern that the adhesion is lowered or the reflow resistance is lowered. When the content of the component (d) is 40 mass% or less, there is no concern that the connection reliability is lowered due to thickening. The thixotropic value tends to be smaller as the content of the component (d) is larger.
((e) component: flux)
The adhesive for a semiconductor may further contain (e) a flux exhibiting flux activity (activity of removing oxides, impurities, and the like). Examples of the flux include nitrogen-containing compounds having an unshared electron pair (such as imidazoles and amines, except for nitrogen-containing compounds having an unshared electron pair contained in the component (b)), carboxylic acids, phenols and alcohols. Further, carboxylic acids exhibit fluxing activity more strongly than alcohols, and are easy to improve connectivity.
(e) The content of the component (c) is preferably 0.2 to 3% by mass, more preferably 0.4 to 1.8% by mass, based on the total amount of the solid components of the adhesive for semiconductor, from the viewpoint of solder wettability.
The adhesive for a semiconductor may further contain an ion scavenger, an antioxidant, a silane coupling agent, a titanium coupling agent, a leveling agent, and the like. These may be used alone in an amount of 1 or in combination of 2 or more. The blending amount of these additives may be appropriately adjusted so that the effects of the respective additives are exhibited.
< method for producing adhesive for semiconductor >
The adhesive for a semiconductor of the present embodiment is preferably in a film form (film-like adhesive) from the viewpoint of improving productivity. The method for producing the film-like adhesive will be described below.
First, the component (a), the component (b), the component (c), and other components as needed are added to an organic solvent, and then they are dissolved or dispersed by stirring, mixing, kneading, or the like, to prepare a resin varnish. Thereafter, after the resin varnish is applied to the release-treated base film using a doctor blade coater, roll coater, applicator, die coater, comma coater, or the like, the organic solvent is reduced by heating, and a film-like adhesive is formed on the base film. In addition, a film-like adhesive may be formed on a wafer by spin-coating a resin varnish on a wafer or the like before reducing an organic solvent by heating, and then drying the solvent.
The organic solvent used for the preparation of the resin varnish is preferably a solvent having a property of uniformly dissolving or dispersing each component, and examples thereof include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, diethylene glycol dimethyl ether, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethylcellosolve acetate, butylcellosolve, dioxane, cyclohexanone, and ethyl acetate. Among them, cyclohexanone is preferably used from the viewpoint of film forming property, and it is preferable that a part or all of the material contained in the adhesive for a semiconductor is soluble in cyclohexanone. That is, it is preferable that a part or all of the material contained in the resin varnish is cyclohexanone dissolved product. These organic solvents may be used alone or in combination of 2 or more. The stirring and mixing in the preparation of the resin varnish may be carried out using, for example, a stirrer, an attritor, a triple roll, a ball mill, a bead mill or a refiner.
The substrate film is not particularly limited as long as it has heat resistance capable of withstanding the heating conditions at the time of volatilizing the organic solvent, and examples thereof include polyester films, polypropylene films, polyethylene terephthalate films, polyimide films, polyetherimide films, polyether naphthalate films, methylpentene films, and the like. The base film is not limited to a single layer formed of 1 of these films, and may be a multilayer film formed of 2 or more films.
As the conditions for volatilizing the organic solvent from the resin varnish after coating, heating at 50 to 200 ℃ for 0.1 to 90 minutes is particularly preferable. The organic solvent is preferably volatilized to 1.5 mass% or less as long as it has no influence on the voids, viscosity adjustment, and the like after the mounting.
The thickness of the film-like adhesive of the present embodiment is preferably 10 to 100 μm, more preferably 20 to 50 μm from the viewpoints of visibility, fluidity, and filling property.
< semiconductor device >
The adhesive for a semiconductor of the present embodiment is preferably used for a semiconductor device, and is particularly preferably used for connection of connection portions in a semiconductor device in which electrodes of connection portions of a semiconductor chip and a wiring circuit board are electrically connected to each other or in a semiconductor device in which electrodes of connection portions of a plurality of semiconductor chips are electrically connected to each other. Hereinafter, a semiconductor device using the adhesive for a semiconductor according to the present embodiment will be described. The electrodes of the connection portion in the semiconductor device may be any of metal bonding of the bump and the wiring, and metal bonding of the bump and the bump. In the semiconductor device, flip chip connection which can obtain electrical connection via an adhesive for a semiconductor can be used, for example.
Fig. 1 is a schematic cross-sectional view showing an embodiment of a semiconductor device (COB type connection mode of a semiconductor chip and a substrate). As shown in fig. 1 a, the first semiconductor device 100 includes a semiconductor chip 10 and a substrate (wiring circuit board) 20 facing each other, wirings 15 disposed on the facing surfaces of the semiconductor chip 10 and the substrate 20, respectively, connection bumps 30 connecting the wirings 15 of the semiconductor chip 10 and the substrate 20 to each other, and an adhesive 40 filling a gap between the semiconductor chip 10 and the substrate 20 without a gap. The semiconductor chip 10 and the substrate 20 are flip-chip connected by the wiring 15 and the connection bump 30. The wiring 15 and the connection bump 30 are sealed with an adhesive 40 for a semiconductor and isolated from the external environment.
As shown in fig. 1 b, the second semiconductor device 200 includes a semiconductor chip 10 and a substrate (wiring circuit board) 20 facing each other, bumps 32 disposed on the facing surfaces of the semiconductor chip 10 and the substrate 20, respectively, and an adhesive 40 for a semiconductor filling a gap between the semiconductor chip 10 and the substrate 20 without a gap. The semiconductor chip 10 and the substrate 20 are flip-chip connected by interconnecting the opposing bumps 32. The bump 32 is sealed from the outside environment by an adhesive 40 for the semiconductor.
Fig. 2 is a schematic cross-sectional view showing another embodiment of the semiconductor device (COC-type connection form of semiconductor chips to each other). As shown in fig. 2 (a), the third semiconductor device 300 is the same as the first semiconductor device 100 except that 2 semiconductor chips 10 are flip-chip connected by the wiring 15 and the connection bumps 30. As shown in fig. 2 (b), the fourth semiconductor device 400 is the same as the second semiconductor device 200 except that 2 semiconductor chips 10 are flip-chip connected by bumps 32.
The semiconductor chip 10 is not particularly limited, and various semiconductors such as an elemental semiconductor composed of one kind of element such as silicon and germanium, and a compound semiconductor such as gallium-arsenic and indium-phosphorus can be used.
The substrate 20 is not particularly limited as long as it is a wired circuit substrate, and a circuit substrate in which a wiring (wiring pattern) is formed by etching and removing unnecessary portions of a metal layer formed on the surface of an insulating substrate containing glass epoxy resin, polyimide resin, polyester resin, ceramic, epoxy resin, bismaleimide triazine resin, or the like as a main component; a circuit board having a wiring (wiring pattern) formed on a surface of the insulating substrate by metal plating or the like; a circuit board in which a conductive material is printed on the surface of the insulating substrate to form a wiring (wiring pattern), and the like.
The connection portions such as the wirings 15 and the bumps 32 contain gold, silver, copper, solder (for example, tin-silver, tin-lead, tin-bismuth, and tin-copper as main components), nickel, tin, lead, and the like as main components, and may contain a plurality of metals.
A metal layer containing gold, silver, copper, solder (main component such as tin-silver, tin-lead, tin-bismuth, tin-copper), tin, nickel, or the like as a main component may be formed on the surface of the wiring (wiring pattern). The metal layer may be composed of only a single component or may be composed of a plurality of components. In addition, a structure in which a plurality of metal layers are stacked may be also employed. Copper and solder are inexpensive and therefore are generally used. Further, copper and solder contain oxides, impurities, and the like, and therefore, it is preferable that the adhesive for a semiconductor have fluxing activity.
As a material of the conductive bump called a bump, gold, silver, copper, solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper), tin, nickel, or the like is used, and may be composed of only a single component or may be composed of a plurality of components. The metal may be laminated to form a structure. The bump may be formed on the semiconductor chip or the substrate. Copper and solder are generally used because they are inexpensive. Further, copper and solder contain oxides, impurities, and the like, and therefore, it is preferable that the adhesive for a semiconductor have fluxing activity.
Further, after the semiconductor device (package) shown in fig. 1 or 2 is stacked, electrical connection may be performed using gold, silver, copper, solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper), tin, nickel, or the like. For example, as is seen in TSV technology, flip-chip bonding or lamination may be performed by providing an adhesive between the semiconductor chips, and forming holes penetrating the semiconductor chips to connect to the electrodes on the pattern surface.
Fig. 3 is a schematic cross-sectional view showing another embodiment of the semiconductor device (a semiconductor chip stacked type configuration (TSV)). As shown in fig. 3, in the fifth semiconductor device 500, the wiring 15 formed on the interposer 50 is connected to the wiring 15 of the semiconductor chip 10 through the connection bump 30, and the semiconductor chip 10 and the interposer 50 are flip-chip connected. The gap between the semiconductor chip 10 and the interposer 50 is filled with the semiconductor adhesive 40 without any gap. The semiconductor chip 10 is repeatedly stacked on the surface of the semiconductor chip 10 opposite to the interposer 50 through the wiring 15, the connection bump 30, and the semiconductor adhesive 40. The wiring 15 on the pattern surface on the front and back of the semiconductor chip 10 is connected to each other by the through electrode 34 filled in the hole penetrating the inside of the semiconductor chip 10. Copper, aluminum, or the like can be used as the material of the through electrode 34.
With such TSV technology, signals can also be acquired from the back side of a semiconductor chip that is not normally used. Further, since the through electrode 34 passes vertically through the semiconductor chip 10, the distance between the semiconductor chips 10 facing each other or between the semiconductor chip 10 and the interposer 50 can be shortened, and flexible connection can be performed. The adhesive for semiconductor of the present embodiment is preferably used as a sealing material between the semiconductor chips 10 facing each other or between the semiconductor chips 10 and the interposer 50 in such TSV technology.
< method for manufacturing semiconductor device >
The method for manufacturing a semiconductor device according to the present embodiment connects a semiconductor chip and a wired circuit board or a plurality of semiconductor chips to each other using the adhesive for a semiconductor according to the present embodiment. The method for manufacturing a semiconductor device according to the present embodiment includes, for example, the steps of: a step of electrically connecting the connection portions of the semiconductor chip and the wired circuit board to each other while connecting the semiconductor chip and the wired circuit board to each other via an adhesive to obtain a semiconductor device; or a step of connecting the plurality of semiconductor chips to each other via an adhesive agent and simultaneously electrically connecting the connection portions of the plurality of semiconductor chips to each other to obtain the semiconductor device.
In the method for manufacturing a semiconductor device according to this embodiment, the connection portions can be connected to each other by metal bonding. That is, the respective connection portions of the semiconductor chip and the wired circuit board are connected to each other by metal bonding, or the respective connection portions of the plurality of semiconductor chips are connected to each other by metal bonding.
As an example of the method for manufacturing the semiconductor device of the present embodiment, a method for manufacturing the sixth semiconductor device 600 shown in fig. 4 will be described. The sixth semiconductor device 600 connects a substrate (for example, a glass epoxy substrate) 60 having a wiring (copper wiring) 15 and the semiconductor chip 10 having the wiring (for example, copper pillar, copper stud) 15 to each other via the adhesive 40 for semiconductor. The wiring 15 of the semiconductor chip 10 is electrically connected to the wiring 15 of the substrate 60 by the connection bump (solder bump) 30. On the surface of the substrate 60 where the wiring 15 is formed, a solder resist 70 is disposed except for the formation position of the connection bump 30.
In the method of manufacturing the sixth semiconductor device 600, first, the adhesive 40 for semiconductor (film-like adhesive or the like) is stuck on the substrate 60 on which the solder resist 70 is formed. The bonding is performed by heat pressing, roll lamination, vacuum lamination, or the like. The supply area and thickness of the adhesive 40 for a semiconductor are appropriately set according to the size of the semiconductor chip 10 or the substrate 60, the bump height, and the like. The semiconductor chip 10 to which the adhesive 40 for semiconductor is attached may be manufactured by attaching the adhesive 40 for semiconductor to the semiconductor chip 10, or by dicing the semiconductor wafer after attaching the adhesive 40 for semiconductor to the semiconductor wafer to manufacture the semiconductor chip 10 as a single piece. In this case, since the adhesive for a semiconductor having high light transmittance can ensure visibility even when the alignment mark is covered, the adhesive is not limited to a semiconductor wafer (semiconductor chip), and the range of adhesion to a substrate is not limited, and the adhesive is excellent in handleability.
After the semiconductor adhesive 40 is adhered to the substrate 60 or the semiconductor chip 10, the connection bumps 30 on the wirings 15 of the semiconductor chip 10 are aligned with the wirings 15 of the substrate 60 by using a connection device such as a flip-chip connector. Then, while heating the semiconductor chip 10 and the substrate 60 at a temperature equal to or higher than the melting point of the connection bump 30, the semiconductor chip 10 and the substrate 60 are connected together by pressing (preferably, when solder is used for the connection portion, a temperature equal to or higher than 240 ℃ is applied to the solder portion), and the space between the semiconductor chip 10 and the substrate 60 is sealed and filled with the semiconductor adhesive 40. The connection load is set in consideration of the uneven absorption of the bump height, the control of the bump deformation amount, and the like, although it depends on the number of bumps. The connection time is preferably a short time from the viewpoint of improving productivity. Preferably, the solder is melted to remove the oxide film, impurities on the surface, and the like, and a metal bond is formed on the connection portion.
The short connection time (press-bonding time) is a time (for example, a time when solder is used) in which a temperature of 240 ℃ or higher is applied to the connection portion during connection formation (main press-bonding) and is 10 seconds or less. The connection time is preferably 5 seconds or less, more preferably 3 seconds or less.
After alignment, the semiconductor chip is temporarily fixed, and heat treatment is performed by a reflow furnace to melt the solder bumps, thereby connecting the semiconductor chip to the substrate, and a semiconductor device can be manufactured. Since the temporary fixation does not require the necessity of forming a metal joint significantly, it is possible to provide advantages such as a low load, a short time, and a low temperature compared to the main pressure welding, an improvement in productivity, and prevention of deterioration of the connecting portion. The adhesive may be cured by heating the semiconductor chip and the substrate by an oven or the like after the semiconductor chip and the substrate are connected. The heating temperature is a temperature at which the curing of the adhesive proceeds, preferably substantially completely. The heating temperature and the heating time are properly set. In this case, the obtained semiconductor device includes a cured product of the adhesive.
Examples
The present disclosure is more specifically described below with reference to examples. The present disclosure is not limited to these embodiments.
The compounds used in each of the examples and comparative examples are as follows.
(a) Epoxy resin
Multifunctional solid epoxy resin containing a triphenolmethane skeleton (trade name "EP1032H60", hereinafter referred to as "EP1032", manufactured by Mitsubishi Chemical Co., ltd.)
Naphthalene skeleton-containing epoxy resin (trade name "HP4032D", manufactured by DIC Co., ltd.)
Bisphenol F type liquid epoxy resin (trade name "YL983U", hereinafter referred to as "YL983". Mitsubishi Chemical Co., ltd.)
Flexible epoxy resin (trade name "YL7175", hereinafter referred to as "YL7175", manufactured by Mitsubishi Chemical Co., ltd.)
(b) Curing agent
2, 4-diamino-6- [2 '-methylimidazole- (1') ] -ethyl-s-triazine isocyanurate adduct (trade name "2MAOK-PW" manufactured by Kagaku Kogyo Co., ltd., "2 MAOK")
(c) High molecular weight component having weight average molecular weight of 10000
Acrylic resin (trade name "kuraritiy LA4285", manufactured by KURARAY corporation, mw/mn=1.28, weight average molecular weight Mw: 80000)
(d) Filling material
Inorganic filler
Epoxy surface-treated nanosilica filler (trade name "50nmSE-AH1", manufactured by Admatechs, co., ltd.; average particle size: about 50nm, hereinafter referred to as "SE nanosilica")
Inorganic silica filler (trade name "SE2050", manufactured by Admatechs, co., ltd.; average particle size: 0.5 μm, hereinafter referred to as "SE 2050")
Inorganic silica filler (trade name "SE2050SEJ", manufactured by Admatechs, co., ltd., "average particle size: 0.5 μm, hereinafter referred to as" SE2050SEJ ")
(e) Fluxing agent
Glutaric acid (Sigma-Aldrich Japan Co., ltd.; melting Point: about 97 ℃ C.)
< preparation of film-like adhesive >
Example 1
11.25g of epoxy resin ("EP 1032"6.8g, "HP4032D"0.75g, "YL983"1.5g, "YL7175"2.2 g), curing agent "2MAOK"0.6g, glutaric acid 0.45g, inorganic filler "SE nano silica" 35.3g, acrylic resin "LA4285"2.0g and cyclohexanone (the amount of the solid content in the resin varnish is 47% by mass) were charged, beads having a diameter of 1.0mm and having a mass equivalent to that of the solid content were added, and stirred for 30 minutes by a bead mill (manufactured by Fritsch Japan Co., ltd., planetary micro-pulverizer P-7). Thereafter, the beads used for stirring were removed by filtration to obtain a resin varnish.
The obtained resin varnish was coated on a base film (trade name "Purex a54" manufactured by Teijin Dupont Film corporation) by a small precision coating apparatus (finisher, kang Jing), and the coated resin varnish was dried (100 ℃/5 minutes) by a dust-free oven (manufactured by Espec corporation) to obtain a film-like adhesive. The thickness of the glass was 0.02 mm.
Example 2
A film-like adhesive was produced in the same manner as in example 1, except that the epoxy resin "HP4032D" was increased to 1.5g and the epoxy resin "YL983" was decreased to 0.75 g.
Comparative example 1
A film-like adhesive was prepared in the same manner as in example 1 except that 2.3g of an inorganic silica filler (trade name: SE2050, average particle diameter: 0.5 μm, manufactured by Admatechs, co., ltd.) was added without adding the epoxy resins "YL7175" and "HP 4032D".
Comparative example 2
A film-like adhesive was prepared in the same manner as in example 1 except that 3.3g of an inorganic silica filler (trade name "SE2050SEJ", manufactured by Admatechs, co., ltd., average particle diameter: 0.5 μm) was added, and the "SE nanosilica" was reduced to 27.9g and the "LA4285" was reduced to 0.5 g.
Table 1 shows the blending of examples 1 and 2 and comparative examples 1 and 2.
< evaluation >
The evaluation methods of the film-like adhesives obtained in examples and comparative examples are shown below.
(1) Preparation of thixotropic value measurement sample
The film-like adhesive thus prepared was laminated (layered) into a plurality of sheets until the total thickness reached 0.4mm (400 μm) by using a bench laminator (trade name "HOTDOG GK-13DX", manufactured by Lami Corporation), and cut into dimensions of 7.3mm in the longitudinal direction and 7.3mm in the transverse direction to obtain measurement samples.
(2) Determination of thixotropic values
For the obtained measurement sample, the viscosity at a frequency of 0.1Hz per second was measured by a shear viscosity measuring device (manufactured by TA Instruments Japan Co., ltd., trade name "ARES") under a constant condition at 120℃and was changed continuously from 1Hz to 70Hz, and the thixotropic value was obtained by dividing the viscosity value at 7Hz by the viscosity value at 70 Hz.
(3) Method for manufacturing semiconductor device
The film-like adhesive (vertical 7.3mm, horizontal 7.3mm, thickness 0.045 mm) thus cut was adhered to a semiconductor chip with solder bumps (chip size: vertical 7.3mm, horizontal 7.3mm, thickness 0.15mm, bump height: total of copper pillars + solder was about 45 μm, bump count was 328, pitch was 80 μm). Then, a semiconductor chip with solder bumps to which a film-like adhesive was attached (mounting conditions: pressure-bonding joint temperature 350 ℃ C./5 seconds/0.5 MPa) was mounted on a glass epoxy substrate (glass epoxy substrate thickness: 420 μm, copper wiring thickness: 9 μm) by using a flip chip connector FCB3 (manufactured by Songshi Co., ltd.) to obtain a semiconductor device similar to that of FIG. 4. The table temperature was 80 ℃.
(4) Method for evaluating spreadability
The semiconductor device obtained by the method for manufacturing a semiconductor device (3) above was observed from above the upper chip using a microscope (manufactured by KEYENCE corporation), and the exudation width of the resin from the chip end was measured. The exudation width was calculated as follows: measuring width W of resin exuded from center of 1 side of chip 1 (unit: μm), and resin from one end (corner of the chip) from the 1 side is 0.2mm center Width W of lateral position exudation 2 (unit: μm), and the ratio (W) of the two was determined 2 /W 1 ). In addition, W 2 The smaller one of the width of the resin oozing from the position 0.2mm from one end of the 1 side of the chip and the width oozing from the position 0.2mm from the other end of the 1 side. The ratio (W) was performed on all 4 sides of the chip 2 /W 1 ) The average value was obtained as "coverage".
The coverage is an indicator indicating whether or not the adhesive resin spreads to the corner of the chip in the semiconductor device. It is preferable that the width of the exudation of the corner portion and the center portion of the side of the semiconductor device is not different, and therefore, the closer to 1, the better the coverage.
The measurement results of the thixotropic values and the evaluation results of the spreadability are shown in table 1.
TABLE 1
As is clear from the evaluation results in Table 1, the coverage of examples 1 and 2, in which the thixotropic value was 3.1 or less, exceeded 0.4, but the coverage of comparative examples 1 and 2, in which the thixotropic value was large and exceeded 3.1, was less than 0.4. This confirmed that the adhesive for film-like semiconductor according to the present disclosure having a low thixotropic value has improved coverage.
Symbol description
10 semiconductor chips, 15 wirings, 20, 60 substrates, 30 connection bumps, 32 bumps, 34 through electrodes, 40 adhesive for semiconductor, 50 interposer, 70 solder resist, 100, 200, 300, 400, 500, 600 semiconductor devices.
Claims (7)
1. An adhesive for a semiconductor, which is used for sealing at least a part of a connection part in a semiconductor device, wherein the semiconductor device is formed by mutually electrically connecting electrodes of the connection parts of a semiconductor chip and a wiring circuit board, or by mutually electrically connecting electrodes of the connection parts of a plurality of semiconductor chips,
the adhesive for semiconductors contains (a) an epoxy resin, (b) a curing agent, and (c) a high molecular weight component having a weight average molecular weight of 40000 or more,
the thixotropic value of the adhesive for semiconductors is 1.0 to 3.1,
the thixotropic values are the following values: the thixotropic value is obtained by measuring the viscosity of a sample having a thickness of 400 μm laminated with the adhesive for semiconductor at a constant temperature of 120 ℃ under a shear viscosity measuring device so as to continuously change the frequency from 1Hz to 70Hz, and dividing the viscosity value at 7Hz by the viscosity value at 70 Hz.
2. The adhesive for semiconductors according to claim 1, further comprising (d) a filler.
3. The adhesive for semiconductors according to claim 1 or 2, further comprising (e) a flux.
4. The adhesive for semiconductors according to claim 1 or 2, wherein the polydispersity Mw/Mn of the high molecular weight component (c) having a weight average molecular weight of 40000 or more is 3 or less.
5. The adhesive for a semiconductor according to claim 1 or 2, wherein a part or all of the material contained in the adhesive for a semiconductor is soluble in cyclohexanone.
6. The adhesive for a semiconductor according to claim 1 or 2, which is film-like.
7. A method for manufacturing a semiconductor device includes the steps of:
a step of aligning a semiconductor chip and a wiring circuit board with each other by using the adhesive for a semiconductor according to any one of claims 1 to 6, using a connecting device, and by mutually connecting electrodes of respective connection portions of the semiconductor chip and the wiring circuit board while mutually connecting the electrodes, and sealing at least a part of the connection portions by the adhesive for a semiconductor; or alternatively
And a step of aligning the plurality of semiconductor chips with the bonding agent for semiconductor interposed therebetween by a connecting device, electrically connecting electrodes of the respective connection portions of the plurality of semiconductor chips to each other while connecting the plurality of semiconductor chips to each other, and sealing at least a part of the connection portions by the bonding agent for semiconductor.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018036450 | 2018-03-01 | ||
| JP2018-036450 | 2018-03-01 | ||
| PCT/JP2019/001342 WO2019167460A1 (en) | 2018-03-01 | 2019-01-17 | Adhesive for semiconductor and method for manufacturing semiconductor device using same |
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| Publication Number | Publication Date |
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| CN111801781A CN111801781A (en) | 2020-10-20 |
| CN111801781B true CN111801781B (en) | 2024-02-20 |
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| Country | Link |
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| JP (1) | JP7248007B2 (en) |
| KR (1) | KR102570823B1 (en) |
| CN (1) | CN111801781B (en) |
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| WO (1) | WO2019167460A1 (en) |
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| JP2001093925A (en) * | 1999-09-27 | 2001-04-06 | Denso Corp | Lsi package assembly method |
| JP2007051184A (en) * | 2005-08-16 | 2007-03-01 | Shin Etsu Chem Co Ltd | Thermosetting epoxy resin composition and semiconductor device produced by using the same |
| JP2013175546A (en) * | 2012-02-24 | 2013-09-05 | Dexerials Corp | Underfill material, and method of manufacturing semiconductor device using the same |
| JP2014175462A (en) * | 2013-03-08 | 2014-09-22 | Mitsubishi Chemicals Corp | Three-dimensional integrated circuit manufacturing method |
| CN104170070A (en) * | 2012-08-06 | 2014-11-26 | 积水化学工业株式会社 | Method for manufacturing semiconductor device and adhesive for mounting flip chip |
| CN106233463A (en) * | 2014-04-22 | 2016-12-14 | 积水化学工业株式会社 | Semiconductor chip adhesive film with through electrode |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6407684B2 (en) | 2014-11-28 | 2018-10-17 | 日東電工株式会社 | Sheet-like resin composition, laminated sheet, and method for manufacturing semiconductor device |
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2019
- 2019-01-17 JP JP2020502852A patent/JP7248007B2/en active Active
- 2019-01-17 CN CN201980016195.XA patent/CN111801781B/en active Active
- 2019-01-17 WO PCT/JP2019/001342 patent/WO2019167460A1/en active Application Filing
- 2019-01-17 KR KR1020207027159A patent/KR102570823B1/en active IP Right Grant
- 2019-01-28 TW TW108103164A patent/TWI782177B/en active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001093925A (en) * | 1999-09-27 | 2001-04-06 | Denso Corp | Lsi package assembly method |
| JP2007051184A (en) * | 2005-08-16 | 2007-03-01 | Shin Etsu Chem Co Ltd | Thermosetting epoxy resin composition and semiconductor device produced by using the same |
| JP2013175546A (en) * | 2012-02-24 | 2013-09-05 | Dexerials Corp | Underfill material, and method of manufacturing semiconductor device using the same |
| CN104170070A (en) * | 2012-08-06 | 2014-11-26 | 积水化学工业株式会社 | Method for manufacturing semiconductor device and adhesive for mounting flip chip |
| JP2014175462A (en) * | 2013-03-08 | 2014-09-22 | Mitsubishi Chemicals Corp | Three-dimensional integrated circuit manufacturing method |
| CN106233463A (en) * | 2014-04-22 | 2016-12-14 | 积水化学工业株式会社 | Semiconductor chip adhesive film with through electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI782177B (en) | 2022-11-01 |
| WO2019167460A1 (en) | 2019-09-06 |
| KR102570823B1 (en) | 2023-08-25 |
| KR20200125956A (en) | 2020-11-05 |
| JPWO2019167460A1 (en) | 2021-02-25 |
| JP7248007B2 (en) | 2023-03-29 |
| CN111801781A (en) | 2020-10-20 |
| TW201936865A (en) | 2019-09-16 |
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