CN111801781A - Adhesive for semiconductor and method for manufacturing semiconductor device using same - Google Patents
Adhesive for semiconductor and method for manufacturing semiconductor device using same Download PDFInfo
- Publication number
- CN111801781A CN111801781A CN201980016195.XA CN201980016195A CN111801781A CN 111801781 A CN111801781 A CN 111801781A CN 201980016195 A CN201980016195 A CN 201980016195A CN 111801781 A CN111801781 A CN 111801781A
- Authority
- CN
- China
- Prior art keywords
- semiconductor
- adhesive
- value
- chip
- semiconductor device
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 230
- 239000000853 adhesive Substances 0.000 title claims abstract description 111
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 230000009974 thixotropic effect Effects 0.000 claims abstract description 21
- 238000007789 sealing Methods 0.000 claims abstract description 8
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 10
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- 239000002184 metal Substances 0.000 description 20
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 235000019692 hotdogs Nutrition 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 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
- 230000000149 penetrating effect Effects 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
- 229920000642 polymer Polymers 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
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 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
- 239000003566 sealing material Substances 0.000 description 1
- 238000000926 separation method Methods 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- 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
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
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)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Wire Bonding (AREA)
- Die Bonding (AREA)
- Adhesive Tapes (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 in which electrodes of the connection portions of a semiconductor chip and a wired circuit board are electrically connected to each other or in which electrodes of the connection portions of a plurality of semiconductor chips are electrically connected to each other, and has a strain value of 1.0 or more and 3.1 or less, the strain value being a value: the viscosity at a frequency of continuously changing from 1Hz to 70Hz was measured by a shear viscosity measuring apparatus under a constant condition at a temperature of 120 ℃ for a sample in which the adhesive for semiconductor was laminated to a thickness of 400 μm, and the value obtained by dividing the value of the viscosity at 7Hz by the value of the viscosity at 70Hz was defined as the above-mentioned thixotropic value.
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, wire bonding methods using a fine metal wire such as a gold wire have been widely used for connecting a semiconductor chip and 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, a flip chip connection method (FC connection method) 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 a flip-chip connection method, 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 a contraction force of a resin, but from the viewpoint of reliability of a connection portion, a method of joining metals using solder, tin, gold, silver, copper, or the like is generally used.
For example, among connections between a semiconductor Chip and a substrate, a Chip On Board (COB) type connection method widely used in BGA (Ball Grid Array), CSP (Chip Size Package), and the like is also a flip Chip connection method. The flip Chip connection method is also widely used for a COC (Chip On Chip) type connection method in which a connection portion (a bump or a wiring) is formed On a semiconductor Chip and connection is performed between semiconductor chips (for example, see patent document 1 below).
As for packages strongly required to be further miniaturized, thinned and highly functional, chip stack packages, POP (Package On Package), TSV (Through-Silicon Via), and the like, which are obtained by stacking and multistage connection methods, have also begun to be widely used. Since the package can be made smaller by arranging the semiconductor wiring substrate not in a planar shape but in a three-dimensional shape, these techniques are widely used, and are effective for improving the performance of the semiconductor, reducing noise, reducing the mounting area, and saving power, and are drawing attention as a next-generation semiconductor wiring technique.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2016-102165
Disclosure of Invention
Technical problem to be solved by the invention
In a flip chip package which has been developed to have higher functions, higher integration, and lower cost, it is required to mount chips with a high density while suppressing the resin bleeding width at the time of mounting chips for high productivity. If the pressure bonding load is reduced for this purpose, the resin bleeding width can be suppressed, but the corner portions of the chip may become deficient in resin, leading to chip separation or the like.
A main object of the present disclosure is to provide an adhesive for a semiconductor, which can obtain a semiconductor device free from resin shortage at the time of mounting a chip by controlling the shape of resin bleeding at the time of mounting a chip and the resin bleeding in a shape along the side surface of the chip, and a method for manufacturing a semiconductor device using the adhesive for a semiconductor.
Means for solving the problems
One 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 in which electrodes of the connection portions of a semiconductor chip and a printed circuit board are electrically connected to each other, or in which electrodes of the connection portions of a plurality of semiconductor chips are electrically connected to each other, wherein a value of a strain of the adhesive for a semiconductor is 1.0 or more and 3.1 or less, and the value of the strain is: the viscosity at a frequency of continuously changing from 1Hz to 70Hz was measured by a shear viscosity measuring apparatus under a constant condition at a temperature of 120 ℃ for a sample in which the adhesive for semiconductor was laminated to a thickness of 400 μm, and the value obtained by dividing the value of the viscosity at 7Hz by the value of the viscosity at 70Hz was defined as the above-mentioned thixotropic value.
Further, another aspect of the present disclosure is [2] the adhesive for a semiconductor according to [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.
Further, another aspect of the present disclosure is [3] the adhesive for a semiconductor according to [2], further comprising (d) a filler.
Further, another aspect of the present disclosure is [4] the adhesive for a semiconductor according to [2] or [3], further comprising (e) a flux.
Further, another aspect of the present disclosure is [5] the adhesive for a semiconductor according to any one of [2] to [4], wherein the polydispersity Mw/Mn of the high molecular weight component having the weight average molecular weight of (c) 10000 or more is 3 or less.
Further, another aspect of the present disclosure is [6] the adhesive for a semiconductor according to any one of [2] to [5], wherein a part or all of materials contained in the adhesive for a semiconductor is soluble in cyclohexanone.
Further, another aspect of the present disclosure is [7] the adhesive for a semiconductor according to any one of [1] to [6], which is in a film form.
Further, another aspect of the present disclosure is [8] a method for manufacturing a semiconductor device, including: a step of aligning the semiconductor chip and the wired circuit board with each other via the adhesive for a semiconductor by a connecting device using the adhesive for a semiconductor according to any one of [1] to [7], electrically connecting electrodes of respective connecting portions of the semiconductor chip and the wired circuit board to each other while connecting each other, and sealing at least a part of the connecting portion with the adhesive for a semiconductor; or aligning the plurality of semiconductor chips with the adhesive for semiconductor therebetween by a connecting device, electrically connecting the electrodes of the respective connecting 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 connecting portions by the adhesive for semiconductor.
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 when the semiconductor device is mounted can be controlled, and the resin oozing out along the side surface of the chip can be suppressed by the resin. 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 one 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 appropriate. In the drawings, the same or corresponding portions are denoted by the same reference numerals, and redundant description is omitted. The positional relationship such as up, down, left, right, and the like is based on the positional relationship shown in the drawings, unless otherwise specified. Further, the dimensional ratios of the drawings are not limited to the ratios shown in the drawings.
In the present description, the numerical range represented by "to" means a range in which the numerical values recited before and after "to" are included as the minimum value and the maximum value, respectively. In the numerical ranges recited in the present specification, the upper limit or the lower limit of the numerical range in one stage may be arbitrarily combined with the upper limit or the lower limit of the numerical range in another stage. In the numerical ranges described in the present specification, the upper limit or the lower limit of the numerical range may be replaced with the values shown in the examples. "a or B" may include either one of a and B, or both. The materials exemplified in the present specification may be used alone in 1 kind or in combination in 2 or more kinds, unless otherwise specified. In the present specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid corresponding thereto.
< adhesive for semiconductor >
The adhesive for a semiconductor according to 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 portions of a semiconductor chip and a wired circuit board are electrically connected to each other, or in a semiconductor device in which electrodes of the connection portions of a plurality of semiconductor chips are electrically connected to each other.
The adhesive for a semiconductor of the present embodiment has a strain value of 1.0 or more and 3.1 or less. The thixotropic values are the following values: the viscosity at a frequency of continuously changing from 1Hz to 70Hz was measured by a shear viscosity measuring apparatus under a constant condition at a temperature of 120 ℃ for a sample in which the adhesive for semiconductor was laminated to a thickness of 400 μm, and the value obtained by dividing the value of the viscosity at 7Hz by the value of the viscosity at 70Hz was defined as the above-mentioned thixotropic value. When the value of the strain is 3.1 or less, the adhesive for a 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 can bleed 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 semiconductors of the present embodiment may contain (a) an epoxy resin, (b) a curing agent, (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.
(component (a): epoxy resin)
Examples of the epoxy resin as 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 can be used singly or in combination of 2 or more.
(a) The content of the component (b) is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and still more preferably 20 to 40% by mass, based on the total solid content of the adhesive for a semiconductor. (a) When the content of the component (b) is 10% by mass or more, it is easy to sufficiently control the flow of the cured resin, and when the content is 50% by mass or less, the resin component of the cured product does not become excessive, and warpage of the package is easily reduced. When the content of the component (a) is within the above range, the thixotropic value of the adhesive for a semiconductor can be easily controlled to be 1.0 or more and 3.1 or less. When the resin component is small and the filler content is large, the thixotropic value tends to be small, and therefore, when the content of the component (a) is 50 mass% or less, the thixotropic value tends to be low.
(component (b): 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, and phosphine curing agents. (b) When the component (a) contains a phenolic hydroxyl group, an acid anhydride, an amine or an imidazole, the fluxing activity for suppressing the formation of an oxide film on the connecting portion is easily exhibited, and the connection reliability and the 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 condensation polymers, triphenylmethane type multifunctional phenolic resins, various multifunctional phenolic resins, and the like can be used. The phenolic resin curing agent may be used alone in 1 kind or in combination of 2 or more kinds.
The equivalent ratio (phenolic hydroxyl group/epoxy group, molar ratio) 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, adhesiveness, 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 to be not left excessively, water absorption tends to be low, and insulation reliability tends to be further improved.
(b-ii) acid anhydride curing agent
Examples of the acid anhydride curing agent include methylcyclohexanetetracarboxylic dianhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, and ethylene glycol bis (anhydrotrimellitate). The acid anhydride curing agent may be used alone in 1 kind or in combination of 2 or more kinds.
The equivalent ratio (acid anhydride group/epoxy group, molar ratio) of the acid anhydride 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, adhesiveness, 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 to be not excessively left, water absorption tends to be low, and insulation reliability tends to be further improved.
(b-iii) amine-based curing agent
As the amine-based curing agent, dicyandiamide, various amine compounds, and the like can be used.
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, adhesiveness, 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 to be not excessively left and insulation reliability tends to be further improved.
(b-iv) imidazole-based 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 '-methylimidazolyl- (1') ] -ethyl-s-triazine, 2, 4-diamino-6- [2 '-undecylimidazolyl- (1') ] -ethyl-s-triazine, and mixtures thereof, 2, 4-diamino-6- [2 ' -ethyl-4 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, adduct of epoxy resin and imidazole, and the like. Among them, from the viewpoint of more excellent curability, storage stability and connection reliability, preferred are 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole 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 isocyanuric acid adduct, and the like, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4, 5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole. The imidazole-based curing agent may be used alone in 1 kind or in combination of 2 or more kinds. Alternatively, a latent curing agent obtained by microencapsulating the above-mentioned materials can be prepared.
The content of the imidazole curing agent is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the component (a). When the content of the imidazole curing agent is 0.1 parts by mass or more, curability tends to be improved, and when it is 20 parts by mass or less, the adhesive composition tends not to be cured before metal bonding is formed, and poor connection tends not to occur.
(b-v) phosphine-based curing agent
The phosphine-based curing agent includes triphenylphosphine, tetraphenylphosphonium tetraphenylboronate, tetraphenylphosphonium tetrakis (4-methylphenyl) borate, tetraphenylphosphonium (4-fluorophenyl) borate, and the like.
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, curability may be improved, and when it is 10 parts by mass or less, the adhesive for a semiconductor is not cured before metal bonding is formed, and poor connection tends to be less likely to occur.
The phenolic resin curing agent, the acid anhydride curing agent and the amine curing agent may be used singly in 1 kind or in combination in 2 or more kinds. The imidazole-based curing agent and the phosphine-based curing agent may be used alone or in combination with a phenol resin-based curing agent, an acid anhydride-based curing agent, or an amine-based curing agent.
From the viewpoint of excellent curability, the component (b) is preferably used in combination with a phenol resin curing agent and an imidazole curing agent, in combination with an acid anhydride curing agent and an imidazole curing agent, in combination with an amine curing agent and an imidazole curing agent, or in combination with an imidazole curing agent alone. Since productivity is improved when the connection is performed in a short time, it is more preferable to use an imidazole-based curing agent having excellent rapid curing properties alone. In this case, since volatile components such as low-molecular components can be suppressed when curing occurs in a short time, generation of voids can be easily suppressed.
(component (c): a high molecular weight component having a weight average molecular weight of 10000 or more)
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 ester resins, (meth) acrylic resins, polyester resins, polyethylene resins, polyethersulfone resins, polyetherimide resins, polyvinyl acetal resins, polyurethane resins, and acrylic rubbers, and among them, phenoxy resins, polyimide resins, (meth) acrylic resins, acrylic rubbers, cyanate ester resins, and polycarbodiimide resins are preferable, and phenoxy resins, polyimide resins, (meth) acrylic resins, and acrylic rubbers are more preferable, from the viewpoint of excellent heat resistance and film formability. (c) The components may be used alone 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, and 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, based on 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, curability is not reduced or adhesion is not reduced, and when the content is 5 parts by mass or less, film formability and film formability are not reduced. Further, the thixotropic value may 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 still 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 possibility that the film forming property is lowered. In the present specification, the weight average molecular weight refers to a weight average molecular weight measured in terms of polystyrene by high performance liquid chromatography (C-R4A, Shimadzu corporation).
(c) The polydispersity Mw/Mn of the component (A) is preferably 3 or less, more preferably 2.5 or less. When Mw/Mn is 3 or less, it is considered that variation in molecular weight is small and thixotropic value tends to be easily lowered.
(component (d): Filler)
Examples of the filler of the component (d) include insulating inorganic fillers. Among these, 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, boron nitride, and the like, 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 a whisker, and examples of the whisker include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, magnesium sulfate, boron nitride, and the like. The insulating inorganic filler may be used alone in 1 kind or in combination of 2 or more kinds. (d) The shape, particle size and content of the component are not particularly limited.
From the viewpoint of further excellent insulation reliability, the component (d) is preferably insulating. 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 treatment agent include glycidyl (epoxy) compounds (excluding compounds corresponding to component (a)), amine compounds, phenyl compounds, phenylamino compounds, (meth) acrylic compounds (for example, compounds having a structure represented by general formula (1)), vinyl compounds having a structure represented by general formula (2), and the like.
[ chemical formula No. 1]
[R11Represents a hydrogen atom or an alkyl group, R12Represents an alkylene group.]
The filler surface-treated with a compound having a structure represented by general formula (1) includes R11Acrylic surface-treated fillers being hydrogen atoms, R11Methacrylic surface-treated Filler being methyl group, R11Ethyl acrylic acid surface-treated fillers and the like which are ethyl groups, from the viewpoint of reactivity with a resin contained in an adhesive for semiconductor and the surface of a semiconductor substrate and bond formationPreferably R11A low bulk, acrylic surface treatment filler, a methacrylic surface treatment filler. R12The weight average molecular weight is also preferably high because the volatile matter is small.
[ chemical formula No. 2]
[R21、R22And R23Represents a 1-valent organic group, R24Represents an alkylene group.]
For example, R is from the viewpoint that reactivity is not lowered21、R22And R23Preferably, the group is not bulky and may be, for example, a hydrogen atom or an alkyl group. In addition, R21、R22And R23Also, the compound may be a 1-valent organic group having an increased reactivity with a vinyl group. R24The weight average molecular weight is preferably high, since it is difficult to volatilize and thus pores can be easily reduced. In addition, R21、R22、R23And R24The selection may also be made in accordance with the ease of surface treatment.
The surface-treating agent is preferably a silane-treating agent such as epoxy silane, amino silane, or (meth) acrylic silane, because of ease of surface treatment. As the surface treatment agent, glycidyl group-based, phenylamino group-based, and (meth) acrylic acid-based compounds are preferable from the viewpoint of excellent dispersibility, fluidity, and adhesive force. As the surface treatment agent, a phenyl-based or (meth) acrylic-based compound is more preferable from the viewpoint of excellent storage stability.
(d) The average particle diameter of the component (C) is preferably 100nm or less, more preferably 60nm or less, from the viewpoint of improving visibility. (d) The component (A) is preferably an inorganic filler having an average particle diameter of 60nm or less which is surface-treated with a (meth) acrylic silane or an epoxy silane, from the viewpoint of improving the adhesive strength. On the other hand, the larger the average particle size of the component (d), the smaller the thixotropic value tends to be.
(d) The content of the component (b) 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 adhesive for a semiconductor. (d) When the content of the component is 20% by mass or more, there is no possibility that the adhesive strength is lowered or the reflow resistance is lowered. When the content of the component (d) is 40% by 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.
(component (e): flux)
The adhesive for semiconductors may further contain (e) a flux exhibiting flux activity (activity for removing oxides, impurities, and the like). Examples of the flux include nitrogen-containing compounds having an unshared electron pair (imidazoles, amines, and the like, except for the nitrogen-containing compounds having an unshared electron pair contained in the component (b)), carboxylic acids, phenols, and alcohols. In addition, carboxylic acids exhibit a stronger fluxing activity than alcohols and tend to improve the 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 solid content of the adhesive for semiconductor, from the viewpoint of solder wettability.
The adhesive for semiconductors may further contain an ion scavenger, an antioxidant, a silane coupling agent, a titanium coupling agent, a leveling agent, and the like. These can be used alone in 1 kind, also can be combined with more than 2 kinds. The amount of the additives may be appropriately adjusted so that the effects of the 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-form adhesive) from the viewpoint of improving productivity. The following describes a method for producing the film adhesive.
First, the component (a), the component (b), the component (c), and if necessary, other components are added to an organic solvent, and then dissolved or dispersed by stirring, mixing, kneading, or the like to prepare a resin varnish. After that, a resin varnish is applied to the base film subjected to the release treatment by using a knife coater, a roll coater, an applicator, a die coater, a comma coater, or the like, and then the organic solvent is reduced by heating, thereby forming a film-like adhesive on the base film. Further, a film-like adhesive may be formed on a wafer by a method in which a resin varnish is spin-coated on a wafer or the like to form a film before the organic solvent is reduced by heating and then the solvent is dried.
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, ethyl cellosolve acetate, butyl cellosolve, dioxane, cyclohexanone, and ethyl acetate. Among these, cyclohexanone is preferably used from the viewpoint of film formability, and a part or all of the materials contained in the adhesive for semiconductor is preferably soluble in cyclohexanone. That is, it is preferable that a part or all of the materials contained in the resin varnish be cyclohexanone dissolved matter. These organic solvents may be used alone or in combination of 2 or more. The stirring, mixing and kneading in the preparation of the resin varnish may be carried out by using, for example, a stirrer, an attritor, a triple roll, a ball mill, a bead mill or a homogenizer.
The substrate film is not particularly limited as long as it has heat resistance capable of withstanding heating conditions when the organic solvent is volatilized, and examples thereof include polyester films, polypropylene films, polyethylene terephthalate films, polyimide films, polyetherimide films, polyether naphthalate films, and methylpentene films. 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.
Specifically, the organic solvent is preferably heated at 50 to 200 ℃ for 0.1 to 90 minutes under conditions for volatilizing the organic solvent from the resin varnish after coating. The organic solvent is preferably volatilized to 1.5 mass% or less as long as it does not affect the voids after mounting, viscosity adjustment, and the like.
The film thickness of the film-like adhesive of the present embodiment is preferably 10 to 100 μm, and more preferably 20 to 50 μm from the viewpoint of visibility, fluidity, and filling property.
< semiconductor device >
The adhesive for a semiconductor of the present embodiment is preferably used for a semiconductor device, is preferably used as an adhesive for a semiconductor, and is particularly preferably used for connection of a connection portion in a semiconductor device in which electrodes of the connection portions of the semiconductor chip and the wired circuit board are electrically connected to each other, or in a semiconductor device in which electrodes of the connection portions of the plurality of semiconductor chips are electrically connected to each other. A semiconductor device using the adhesive for a semiconductor of the present embodiment will be described below. The electrodes of the connection portion in the semiconductor device may be bonded to each other by metal bonding between the bump and the wiring or by metal bonding between the bump and the bump. In the semiconductor device, for example, flip chip connection that can obtain electrical connection via an adhesive for semiconductor can be used.
Fig. 1 is a schematic cross-sectional view showing an embodiment of a semiconductor device (COB type connection form 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 (wired circuit board) 20 facing each other, wirings 15 respectively disposed on mutually facing surfaces of the semiconductor chip 10 and the substrate 20, 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 semiconductor, and are isolated from the external environment.
As shown in fig. 1 b, the second semiconductor device 200 includes a semiconductor chip 10 and a substrate (wired circuit board) 20 facing each other, bumps 32 respectively disposed on the mutually facing surfaces of the semiconductor chip 10 and the substrate 20, and an adhesive 40 for semiconductor filled in the 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 connecting the opposing bumps 32 to each other. The bump 32 is sealed from the external environment by the adhesive 40 for semiconductor.
Fig. 2 is a schematic cross-sectional view showing another embodiment of the semiconductor device (COC type connection form between semiconductor chips). As shown in fig. 2(a), the third semiconductor device 300 is similar to the first semiconductor device 100 except that 2 semiconductor chips 10 are flip-chip connected by the wires 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 or germanium, and a compound semiconductor such as gallium-arsenic or indium-phosphorus can be used.
The substrate 20 is not particularly limited as long as it is a wired circuit board, and a circuit board in which unnecessary portions of a metal layer formed on the surface of an insulating substrate mainly composed of glass epoxy resin, polyimide resin, polyester resin, ceramic, epoxy resin, bismaleimide triazine resin, or the like are etched away to form wiring (wiring pattern); a circuit board having a wiring (wiring pattern) formed on a surface of the insulating substrate by metal plating or the like; and a circuit board or the like in which a conductive material is printed on a surface of the insulating substrate to form a wiring (wiring pattern).
The connection portions such as the wires 15 and the bumps 32 contain gold, silver, copper, solder (mainly containing tin-silver, tin-lead, tin-bismuth, and tin-copper), 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 components such as tin-silver, tin-lead, tin-bismuth, and tin-copper), tin, nickel, and the like as main components 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. Further, a structure in which a plurality of metal layers are stacked may be employed. Copper and solder are generally used because they are inexpensive. Further, since copper and solder contain oxides, impurities, and the like, the adhesive for a semiconductor preferably has fluxing activity.
As a material of the conductive bump called a bump, gold, silver, copper, solder (a main component is, for example, tin-silver, tin-lead, tin-bismuth, tin-copper), tin, nickel, or the like is used as a main component, and may be composed of only a single component or a plurality of components. Further, the metal layer may be formed so as to have a structure in which these metals are stacked. The bump may be formed on a semiconductor chip or a substrate. Copper and solder are generally used because they are inexpensive. Further, since copper and solder contain oxides, impurities, and the like, the adhesive for a semiconductor preferably has fluxing activity.
The semiconductor devices (packages) shown in fig. 1 or 2 may be stacked and then electrically connected to each other by gold, silver, copper, solder (mainly including tin-silver, tin-lead, tin-bismuth, and tin-copper), tin, nickel, or the like. For example, as is seen in the TSV technology, a flip-chip connection or lamination may be performed by having an adhesive present between the semiconductor chips, and holes may be formed through 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 (semiconductor chip stacked Type (TSV)). As shown in fig. 3, in the fifth semiconductor device 500, the wirings 15 formed on the interposer 50 are connected to the wirings 15 of the semiconductor chip 10 via the connection bumps 30, and the semiconductor chip 10 and the interposer 50 are flip-chip connected. The adhesive 40 for a semiconductor is filled in the gap between the semiconductor chip 10 and the interposer 50 without a gap. The semiconductor chip 10 is repeatedly laminated on the surface of the semiconductor chip 10 opposite to the interposer 50 via the wiring 15, the connection bump 30, and the adhesive 40 for semiconductor. The wirings 15 of the pattern surface on the front and back surfaces of the semiconductor chip 10 are connected to each other by the through electrodes 34 filled in the holes penetrating the inside of the semiconductor chip 10. As a material of the through electrode 34, copper, aluminum, or the like can be used.
With such TSV technology, signals can also be acquired from the back side of a semiconductor chip that is not normally used. Furthermore, since the through electrode 34 vertically passes 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 a semiconductor of the present embodiment is preferably used as a sealing material between the semiconductor chips 10 facing each other or between the semiconductor chip 10 and the interposer 50 in the 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 obtaining a semiconductor device by electrically connecting respective connection portions of the semiconductor chip and the printed circuit board to each other while connecting the semiconductor chip and the printed circuit board to each other via an adhesive; or a step of connecting the plurality of semiconductor chips to each other via an adhesive, and electrically connecting the respective connection portions of the plurality of semiconductor chips to each other to obtain a semiconductor device.
In the method of manufacturing a semiconductor device of this embodiment mode, 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.
A method for manufacturing a sixth semiconductor device 600 shown in fig. 4 will be described as an example of a method for manufacturing a semiconductor device according to this embodiment. The sixth semiconductor device 600 connects a substrate (e.g., a glass epoxy substrate) 60 having wirings (copper wirings) 15 and a semiconductor chip 10 having wirings (e.g., copper posts) 15 to each other via an adhesive 40 for a semiconductor. The wiring 15 of the semiconductor chip 10 is electrically connected to the wiring 15 of the substrate 60 by a connection bump (solder bump) 30. On the surface of the substrate 60 on which 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 attached to the substrate 60 on which the solder resist 70 is formed. The adhesion is performed by heat pressing, roll lamination, vacuum lamination, or the like. The supply area and thickness of the adhesive 40 for 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 adhesive 40 may be attached to the semiconductor chip 10, or the semiconductor adhesive 40 may be attached to a semiconductor wafer and then diced to form individual semiconductor chips 10, thereby producing the semiconductor chip 10 to which the semiconductor adhesive 40 is attached. In this case, since the adhesive for a semiconductor having a 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 is not limited to a range in which the adhesive is attached to a substrate, and thus has excellent handleability.
After the adhesive 40 for a semiconductor is attached to the substrate 60 or the semiconductor chip 10, the connection bumps 30 on the wirings 15 of the semiconductor chip 10 and the wirings 15 of the substrate 60 are aligned using a connection device such as a flip-chip connector. Then, the semiconductor chip 10 and the substrate 60 are heated at a temperature not lower than the melting point of the connection bump 30 and pressed (when solder is used for the connection portion, it is preferable to apply a temperature not lower than 240 ℃ to the solder portion), and the semiconductor chip 10 and the substrate 60 are connected and the gap between the semiconductor chip 10 and the substrate 60 is sealed and filled with the adhesive 40 for semiconductor. The connection load depends on the number of bumps, but is set in consideration of absorption of height unevenness of the bumps, control of an amount of deformation of the bumps, and the like. The connection time is preferably short from the viewpoint of improving productivity. It is preferable that the solder is melted to remove an oxide film, impurities on the surface, and the like, and a metal bond is formed on the connection portion.
The short connection time (crimping time) is a time (for example, a time when solder is used) during which a temperature of 240 ℃ or higher is applied to the connection portion during connection formation (main crimping) and is 10 seconds or less. The connection time is preferably 5 seconds or less, more preferably 3 seconds or less.
After the alignment, the solder bumps are temporarily fixed and heat-treated in a reflow furnace, thereby melting the solder bumps and connecting the semiconductor chip to the substrate, whereby a semiconductor device can be manufactured. Since the temporary fixation does not significantly require the necessity of forming a metallic joint, it is possible to achieve advantages such as a low load, a short time, and a low temperature as compared with the above-described main crimping, improvement in productivity, and prevention of deterioration of the connection portion. The adhesive may be cured by heat treatment in an oven or the like after the semiconductor chip and the substrate are connected. The heating temperature is a temperature at which the adhesive is cured, preferably, substantially completely cured. The heating temperature and the heating time may be appropriately set. In this case, the obtained semiconductor device includes a cured product of the adhesive.
Examples
The present disclosure will be described more specifically with reference to examples. The present disclosure is not limited to these embodiments.
The compounds used in the examples and comparative examples are as follows.
(a) Epoxy resin
A multifunctional solid epoxy resin having a trisphenol methane skeleton (product of Mitsubishi Chemical corporation, trade name "EP 1032H 60", hereinafter referred to as "EP 1032")
Naphthalene skeleton-containing epoxy resin (product name "HP 4032D" manufactured by DIC corporation)
Bisphenol F type liquid epoxy resin (product name "YL 983U" manufactured by Mitsubishi Chemical corporation, hereinafter referred to as "YL 983")
Flexible epoxy resin (product name "YL 7175" manufactured by Mitsubishi Chemical corporation, hereinafter referred to as "YL 7175")
(b) Curing agent
2, 4-diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-s-triazine isocyanuric acid adduct (product name "2 MAOK-PW", manufactured by Shikoku Kagaku K., Ltd., hereinafter referred to as "2 MAOK")
(c) High molecular weight component with weight average molecular weight of 10000 or more
Acrylic resin (product name "KURARITY LA 4285" manufactured by KURARAY, K.K.; Mw/Mn: 1.28; weight average molecular weight Mw: 80000)
(d) Filler material
Inorganic filler
Epoxy surface-treated nanosilica fillers (trade name "50 nmSE-AH 1", manufactured by Admatechs corporation, average particle diameter: about 50nm, hereinafter referred to as "SE nanosilica")
An inorganic silica filler (trade name "SE 2050" manufactured by Admatechs, Ltd., average particle diameter: 0.5 μm, hereinafter referred to as "SE 2050")
An inorganic silica filler (trade name "SE 2050 SEJ", manufactured by Admatechs corporation, average particle diameter: 0.5 μm, hereinafter referred to as "SE 2050 SEJ")
(e) Fluxing agent
Glutaric acid (manufactured by Sigma-Aldrich Japan Co., Ltd., melting point: about 97 ℃ C.)
< preparation of film-shaped adhesive >
(example 1)
11.25g of an epoxy resin ("EP 1032" 6.8g, "HP 4032D" 0.75g, "YL 983" 1.5g, "YL 7175" 2.2g), a curing agent "2 MAOK" 0.6g, glutaric acid 0.45g, an inorganic filler "SE nano silica" 35.3g, an acrylic resin "LA 4285" 2.0g, and cyclohexanone (in an amount such that the amount of the solid component in the resin varnish becomes 47 mass%) were charged, microbeads having a diameter of 1.0mm and having the same mass as the solid component were added, and the mixture was stirred for 30 minutes by a bead mill (manufactured by Fritsch Japan K.K., a planetary type pulverizer P-7). Thereafter, the microbeads used for stirring were removed by filtration to obtain a resin varnish.
The obtained resin varnish was coated on a substrate Film (product name "Purex A54" manufactured by Teijin Dupont Film Co., Ltd.) by a small precision coating apparatus (Kanji Seiki Kaisha), and the coated resin varnish was dried (100 ℃ C./5 minutes) by a dust-free oven (manufactured by Espec Co., Ltd.) to obtain a Film-like adhesive. The thickness of the film was 0.02 mm.
(example 2)
A film-like adhesive was prepared in the same manner as in example 1, except that the amount of the epoxy resin "HP 4032D" was increased to 1.5g and the amount of the epoxy resin "YL 983" was decreased to 0.75 g.
Comparative example 1
A film adhesive was prepared in the same manner as in example 1, except that 2.3g of an inorganic silica filler (trade name "SE 2050" manufactured by Admatechs, Ltd., average particle diameter: 0.5 μm) was added in place of the epoxy resin "YL 7175" 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 "SE 2050 SEJ", manufactured by Admatechs Co., Ltd., average particle diameter: 0.5 μm) was added, and that "SE nano-silica" was reduced to 27.9g and "LA 4285" was reduced to 0.5 g.
Table 1 also shows the composition of examples 1 to 2 and comparative examples 1 to 2.
< evaluation >
The evaluation methods of the film-like adhesives obtained in examples and comparative examples are shown below.
(1) Preparation of samples for measuring thixotropic value
The prepared film-like adhesive was laminated (laminated) to a plurality of sheets until the total thickness reached 0.4mm (400 μm) using a desk laminator (product of Lami Corporation, trade name: HOTDOG GK-13 DX), and cut into a size of 7.3mm in the vertical direction and 7.3mm in the horizontal direction to obtain measurement samples.
(2) Determination of the thixotropic value
The viscosity of the obtained measurement sample was measured by a shear viscosity measuring apparatus (TA Instruments Japan, trade name "ARES") under a constant temperature of 120 ℃ at a frequency of 0.1Hz per second continuously changing from 1Hz to 70Hz, and the value obtained by dividing the viscosity value at 7Hz by the viscosity value at 70Hz was defined as the thixotropic value.
(3) Method for manufacturing semiconductor device
The thus prepared film-like adhesive was cut (7.3 mm in length, 7.3mm in width, and 0.045mm in thickness), and adhered to a semiconductor chip with solder bumps (chip size: 7.3mm in length, 7.3mm in width, 0.15mm in thickness, bump height: the total of copper pillars + solder is about 45 μm, the number of bumps is 328, and the pitch is 80 μm). Then, the semiconductor chip with solder bumps to which the film-like adhesive was attached was mounted on a glass epoxy substrate (glass epoxy base material thickness: 420 μm, copper wiring thickness: 9 μm) by using a flip chip connector FCB3 (manufactured by Sonar corporation) (mounting conditions: crimp head temperature 350 ℃/5 sec/0.5 MPa) to obtain the same semiconductor device as that of FIG. 4. The temperature of the table was 80 ℃.
(4) Method for evaluating coverage
The semiconductor device obtained by the method for manufacturing a semiconductor device of (3) above was observed from above the upper chip using a microscope (manufactured by KEYENCE), and the width of resin bleeding from the chip end was measured. The bleed width was calculated as follows: the width W of the resin exuded from the center of 1 side of the chip was measured1(unit: μm) and a width W of the resin oozed from a position on the center side of 0.2mm from one end of the 1 side (chip corner)2(unit: μm), and the ratio (W) of the two is determined2/W1). Further, W2The smaller of the width of the resin oozed from the position on the center side of 0.2mm from one end of the 1 side of the chip and the width of the resin oozed from the position on the center side of 0.2mm from the other end. This ratio (W) is performed for all 4 sides of the chip2/W1) The average value of (2) was determined as "coverage".
The coverage is an index indicating whether or not the adhesive resin spreads to the chip corner portion in the semiconductor device. Preferably, since there is no difference in the width of the corner portion and the center portion of the side of the semiconductor device, the closer the coverage is to 1, the better.
The measurement results of the strain value and the evaluation results of the coverage are shown in table 1.
[ Table 1]
As is clear from the evaluation results in table 1, the coverage of examples 1 and 2 having a thixotropic value of 3.1 or less exceeds 0.4, but the coverage of comparative examples 1 and 2 having a thixotropic value of 3.1 or less is less than 0.4. From this, it was confirmed that the film-like adhesive for semiconductor of the present disclosure having a low thixotropic value has improved coverage.
Description of the symbols
10 semiconductor chips, 15 wiring, 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 device.
Claims (8)
1. An adhesive for a semiconductor, which is used for sealing at least a part of a connection portion in a semiconductor device in which electrodes of the connection portions of a semiconductor chip and a wired circuit board are electrically connected to each other or in which electrodes of the connection portions of a plurality of semiconductor chips are electrically connected to each other,
the adhesive for semiconductor has a strain value of 1.0 to 3.1 inclusive,
the thixotropic values are the following values: the viscosity at a frequency of continuously changing from 1Hz to 70Hz was measured by a shear viscosity measuring apparatus under a constant condition at a temperature of 120 ℃ for a sample in which the adhesive for a semiconductor was laminated to a thickness of 400 μm, and the value obtained by dividing the value of the viscosity at 7Hz by the value of the viscosity at 70Hz was defined as the thixotropic value.
2. The adhesive for semiconductors according to claim 1, which comprises (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.
3. The adhesive for semiconductors according to claim 2, further comprising (d) a filler.
4. The adhesive for semiconductors according to claim 2 or 3, further comprising (e) a flux.
5. The adhesive for semiconductors according to any one of claims 2 to 4, wherein the polydispersity Mw/Mn of the high molecular weight component having a weight average molecular weight of 10000 or more (c) is 3 or less.
6. The adhesive for semiconductors according to any one of claims 2 to 5, wherein a part or all of a material contained in the adhesive for semiconductors is soluble in cyclohexanone.
7. The adhesive for semiconductors according to any one of claims 1 to 6, which is in the form of a film.
8. A method for manufacturing a semiconductor device includes the steps of:
a step of aligning the semiconductor chip and the printed circuit board with each other via the adhesive for a semiconductor by using the adhesive for a semiconductor according to any one of claims 1 to 7, electrically connecting the electrodes of the respective connection portions of the semiconductor chip and the printed circuit board to each other while connecting them to each other, and sealing at least a part of the connection portion with the adhesive for a semiconductor; or
And aligning the plurality of semiconductor chips with the adhesive for semiconductor interposed therebetween by a connecting device, electrically connecting the electrodes of the respective connecting 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 connecting portions by the adhesive for semiconductor.
Applications Claiming Priority (3)
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| JP2018-036450 | 2018-03-01 | ||
| JP2018036450 | 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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| CN111801781A true CN111801781A (en) | 2020-10-20 |
| CN111801781B CN111801781B (en) | 2024-02-20 |
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| JP (1) | JP7248007B2 (en) |
| KR (1) | KR102570823B1 (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 |
Family Cites Families (1)
| 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 |
-
2019
- 2019-01-17 WO PCT/JP2019/001342 patent/WO2019167460A1/en active Application Filing
- 2019-01-17 JP JP2020502852A patent/JP7248007B2/en active Active
- 2019-01-17 CN CN201980016195.XA patent/CN111801781B/en active Active
- 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 |
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| Publication number | Publication date |
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| KR102570823B1 (en) | 2023-08-25 |
| JP7248007B2 (en) | 2023-03-29 |
| CN111801781B (en) | 2024-02-20 |
| KR20200125956A (en) | 2020-11-05 |
| TWI782177B (en) | 2022-11-01 |
| TW201936865A (en) | 2019-09-16 |
| WO2019167460A1 (en) | 2019-09-06 |
| JPWO2019167460A1 (en) | 2021-02-25 |
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