SE543901C2 - Semiconductor device and method for producing same - Google Patents
Semiconductor device and method for producing sameInfo
- Publication number
- SE543901C2 SE543901C2 SE2050185A SE2050185A SE543901C2 SE 543901 C2 SE543901 C2 SE 543901C2 SE 2050185 A SE2050185 A SE 2050185A SE 2050185 A SE2050185 A SE 2050185A SE 543901 C2 SE543901 C2 SE 543901C2
- Authority
- SE
- Sweden
- Prior art keywords
- resin
- semiconductor device
- insulating
- wire
- sealing layer
- Prior art date
Links
- 239000004065 semiconductor Substances 0.000 title claims abstract description 138
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 229920005989 resin Polymers 0.000 claims abstract description 185
- 239000011347 resin Substances 0.000 claims abstract description 185
- 239000007788 liquid Substances 0.000 claims abstract description 131
- 239000000463 material Substances 0.000 claims abstract description 124
- 239000003566 sealing material Substances 0.000 claims abstract description 109
- 238000007789 sealing Methods 0.000 claims abstract description 106
- 239000011248 coating agent Substances 0.000 claims abstract description 97
- 238000000576 coating method Methods 0.000 claims abstract description 97
- 239000000758 substrate Substances 0.000 claims abstract description 62
- 239000002798 polar solvent Substances 0.000 claims description 67
- 229920006015 heat resistant resin Polymers 0.000 claims description 61
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- 239000003822 epoxy resin Substances 0.000 claims description 46
- 229920000647 polyepoxide Polymers 0.000 claims description 46
- 239000011256 inorganic filler Substances 0.000 claims description 38
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 38
- 229920001721 polyimide Polymers 0.000 claims description 26
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- 125000003118 aryl group Chemical group 0.000 claims description 13
- 230000015556 catabolic process Effects 0.000 claims description 13
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 10
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
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- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
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- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- 239000004332 silver Substances 0.000 description 1
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- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
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- 150000003609 titanium compounds Chemical class 0.000 description 1
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- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
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- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J7/04—Coating
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
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Abstract
A semiconductor device having a substrate, a semiconductor element disposed on the substrate, a wire that electrically connects the substrate and the semiconductor element, a first sealing layer that seals the space below the apex of the wire, and a second sealing layer that is provided on top of the first sealing layer with the bonding wire interposed therebetween, wherein the first sealing layer is formed from a cured film of a liquid sealing material, and the second sealing layer is formed from a dried coating film of an insulating resin coating material.
Description
DESCRIPTION SEMICONDUCTOR DEVICE AND METHOD FOR PRODUCING SAME TECHNICAL FIELD 1. 1. 1. id="p-1"
id="p-1"
[0001] Embodiments of the present invention relate to a semiconductor device and a method for producing that semiconductor device, and more specifically, relate to a semiconductor device in which a thinner structure is achieved by sealing the regions above and below the wires with different materials, and a method for producing that semiconductor device.
BACKGROUND ART 2. 2. 2. id="p-2"
id="p-2"
[0002] In recent years, as typified by mobile phones, electrical equipment that uses semiconductor devices continue to become thinner. Further, from the viewpoint of security protection, in addition to security management that relies on passwords, biometric authentication is gamering much attention. For example, in the case of mobile phones, models equipped with a fingerprint authentication sensor, which represents one example of biometric authentication, tend to be becoming more prevalent. Although these types of new electrical devices continue to be developed one after another, specific portions of semiconductor devices have been confirmed as being vulnerable to electrostatic discharge (ESD). 3. 3. 3. id="p-3"
id="p-3"
[0003] Electrostatic discharge (hereafter abbreviated as ESD) is one cause of damage or malfunction of semiconductor devices. Similarly, in the case of fingerprint authentication sensors, the effects of ESD cannot be ignored. Accordingly, those portions of semiconductor devices that exhibit weak resistance to ESD require the formation of an insulating protective layer.
Further, as technology progresses, reductions in the thickness of electrical equipment and semiconductor devices are increasingly required, and therefore the thickness of the insulating protective layer itself must also be reduced.
PRIOR ART DOCUMENTS PATENT DOCUMENT 4. 4. 4. id="p-4"
id="p-4"
[0004] Patent Document 1: JP 2013-166925 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION In general, portions of semiconductor devices prone to ESD concentration are conductive protrusions in which electric charge can readily accumulate. For example, the upper portion of a wire that electrically connects a substrate and a semiconductor element, and the area between tapers of metal wall portions on a circuit board tend to exhibit weak ESD resistance. When an insulating protective layer is formed on the upper portion of a wire to improve the ESD resistance, various problems arise due to the complex shape of the wire.
Firstly, it is preferable that the material used for forming the insulating protective layer on the upper portion of the wire (hereafter also referred to as the insulating protective material) does not flow beneath the wire following application, but is rather retained on the top of the wire. In other words, the insulating protective material preferably has appropriate thixotropy.
Further, in order to meet the requirement for reduced thickness of the insulating protective layer, the insulating protective material preferably has excellent insulation properties. In particular, from the viewpoint of obtaining satisfactory ESD resistance, the insulating protective material is preferably a material which, following film formation, yields a dielectric breakdown voltage of at least 150 kV/mm. 6. 6. 6. id="p-6"
id="p-6"
[0006] In response to these requirements, materials having, for example, a polyimide resin as a base are already known as insulating protective materials, and the fluidity is controlled in accordance with the usage environment. For example, in order to impart thixotropy, paste -like insulating protective materials in which an inorganic filler such as a fine silica filler or some other form of organic filler has been dispersed in the base resin can be used. In those cases where a liquid insulating protective material having no thixotropic properties is used to form an insulating protective layer, flow of the liquid after application means the film thickness on the upper portion of the wire, which requires the most electrostatic protection, tends to become thinner. In those cases where a liquid insulating protective material containing a polyimide resin as the base resin but having no thixotropic properties is actually applied to a curved wire, the insulating protective material flows from the applied surface, and ensuring satisfactory thickness as an insulating protective layer becomes difficult. Accordingly, imparting the insulating protective material with suitable thixotropy may be considered as a method for retaining the insulating protective material on the applied surface. 7. 7. 7. id="p-7"
id="p-7"
[0007] However, paste-like insulating protective materials in which a fine inorganic filler or the like has been dispersed in the base resin tend to develop an interface between the insulating component such as the base resin and the inorganic filler following film formation. As a result of the existence of this interface in the film, even if a highly insulating resin such as a polyimide resin is used, the dielectric breakdown voltage of the film tends to decrease significantly, and achieving satisfactory insulation properties is difficult. Accordingly, in order to ensure favorable insulation properties for the semiconductor device, the insulating protective material must be applied so as to obtain an insulating protective layer with greater thickness, meaning achieving a reduction in thickness becomes problematic. 8. 8. 8. id="p-8"
id="p-8"
[0008] One method that has been disclosed to improve the deterioration in film insulation performance caused by the aforementioned development of an interface between the insulating component and the inorganic filler provides a resin paste containing an organic filler (a resin filler) that dissolves upon heating to exhibit excellent compatibility with the insulating component (Patent Document 1). By using this resin paste, excellent shape stability can be obtained when printing to flat substrates, and excellent insulation properties can be achieved.
However, in investigations conducted by the inventors of the present invention, when the above resin paste was applied to a wire as an insulating protective material, it became clear that the resin paste did not spread satisfactorily into the space below the wire, meaning voids tended to develop in the portion beneath the wire. If voids exist in a semiconductor device, then the device becomes prone to the effects of humidity, and the reliability of the semiconductor device tends to deteriorate. 9. 9. 9. id="p-9"
id="p-9"
[0009] In light of the above circumstances, achieving a thin semiconductor device having excellent ESD resistance requires technology that enables formation of a thin insulating protective layer on the upper portion of a wire using a highly insulating material, and also enables sealing of the space beneath the wire without any void formation. Accordingly, in order to address these issues, an object of the present invention relates to the provision of a thin semiconductor device having superior ESD resistance and excellent reliability using a material that is capable of forming the aforementioned insulating protective layer on the upper portion of a wire and also sealing the space beneath the wire, as well as a method for producing such a semiconductor device.
MEANS TO SOLVE THE PROBLEMS . . . id="p-10"
id="p-10"
[0010] Embodiments of the present invention relate to the following aspects. However, the present invention is not limited to the following, and includes a variety of embodiments.
One embodiment relates to a semiconductor device having a substrate, a semiconductor element disposed on the substrate, a wire that electrically connects the substrate and the semiconductor element, a first sealing layer that seals the space below the apex of the wire, and a second sealing layer that is provided on top of the first sealing layer with the wire interposed therebetween, wherein the first sealing layer is formed from a cured film of a liquid sealing material, and the second sealing layer is formed from a dried coating film of an insulating resin coating material.
In the above embodiment, the semiconductor device preferably also has a resin sealing member provided so as to cover at least the second sealing layer.
The dielectric breakdown voltage of the dried coating film of the above insulating resin coating material is preferably at least 150 kV/mm.
The insulating resin coating material preferably contains a resin filler having an average particle size of 0.1 to 5.0 μm.
The viscosity at 25°C of the insulating resin coating material is preferably within a range from 30 to 500 Pa.s.
The thixotropic index at 25°C of the insulating resin coating material is preferably within a range from 2.0 to 10.0. 12. 12. 12. id="p-12"
id="p-12"
[0012] The insulating resin coating material preferably contains at least one insulating resin selected from the group consisting of a polyamide, a polyamideimide and a polyimide.
The thickness of the second sealing layer is preferably not more than 100 μm. The thickness of the second sealing layer is more preferably 50 μm or less.
The Tg value (glass transition temperature) of the above insulating resin is preferably at least 150°C. 13. 13. 13. id="p-13"
id="p-13"
[0013] In the embodiment described above, the liquid sealing material contains a thermosetting resin component and an inorganic filler, and the thixotropic index at 75°C of the liquid sealing material, obtained as the value of viscosity A / viscosity B, is preferably within a range from 0.1 to 2.5, wherein the viscosity A is the viscosity (Pa.s) measured under conditions of 75°C and a shear velocity of 5 s<-1>, and the viscosity B is the viscosity (Pa.s) measured under conditions of 75°C and a shear velocity of 50 s<-1>.
The chlorine ion content in the liquid sealing material is preferably not more than 100 ppm. The maximum particle size of the above inorganic filler in the liquid sealing material is preferably not more than 75 μm. 14. 14. 14. id="p-14"
id="p-14"
[0014] The viscosity of the liquid sealing material measured under conditions of 75°C and a shear velocity of 5 s<-1>is preferably not more than 3.0 Pa.s.
The viscosity of the liquid sealing material measured under conditions of 25°C and a shear velocity of 10 s<-1>is preferably not more than 30 Pa.s.
The amount of the inorganic filler, based on the total mass of the liquid sealing material, is preferably at least 50% by mass. . . . id="p-15"
id="p-15"
[0015] The above thermosetting resin component in the liquid sealing material preferably contains an aromatic epoxy resin and an aliphatic epoxy resin.
The aromatic epoxy resin preferably contains at least one resin selected from the group consisting of a liquid bisphenol epoxy resin and a liquid glycidylamine epoxy resin, and the aliphatic epoxy resin preferably contains a linear aliphatic epoxy resin.
The semiconductor of the embodiment described above can be used favorably in a fingerprint authentication sensor. However, the device is not limited to fingerprint authentication sensors, and applications as an insulating resin coating material for the upper portions of wires in thin devices can be anticipated. Further, it is surmised that the combination of an insulating resin coating material and a liquid sealing material according to the present invention, and productions methods that utilize this combination of materials, will enable the production of novel thin devices. 16. 16. 16. id="p-16"
id="p-16"
[0016] Another embodiment relates to a method for producing a semiconductor device having a substrate, a semiconductor element disposed on the substrate, a wire that electrically connects the substrate and the semiconductor element, a first sealing layer that seals the space below the apex of the wire, and a second sealing layer that is provided on top of the first sealing layer with the wire interposed therebetween, the method including: a step of electrically connecting the substrate and the semiconductor element disposed on the substrate using the wire, a step of forming the first sealing layer by supplying a liquid sealing material to the space below the apex of the wire, and a step of forming the second sealing layer by supplying an insulating resin coating material to the top of the first sealing layer with the wire interposed therebetween.
The present invention is related to the subject matter disclosed in prior Japanese Application 2017-155891 filed on August 10, 2017, the entire contents of which are incorporated by reference herein.
EFFECTS OF THE INVENTION 17. 17. 17. id="p-17"
id="p-17"
[0017] Embodiments of the present invention are able to provide a thin semiconductor device having superior ESD resistance and excellent reliability, and a method for producing such a semiconductor device.
BRIEF DESCRIPTION OF THE DRAWINGS 18. 18. 18. id="p-18"
id="p-18"
[0018] FIG. 1 is a side sectional view of a semiconductor device according to one embodiment. FIG. 2 is a partial plan view of a semiconductor device according to one embodiment.
FIG. 3 is a series of schematic cross-sectional views describing a method for producing a semiconductor device according to one embodiment, wherein (a) to (d) correspond to each of the steps.
EMBODIMENTS FOR CARRYING OUT THE INVENTION 19. 19. 19. id="p-19"
id="p-19"
[0019] Embodiments of the present invention are described below in further detail.
Semiconductor Device> The semiconductor device is described using the drawings. In the following description, terms that indicate direction such as "above", "below", "upper portion" and "lower portion" are used to specify direction within the drawings as appropriate, but in no way limit the direction of installation when the device is used. . . . id="p-20"
id="p-20"
[0020] FIG. 1 is a side sectional view of a semiconductor device according to one embodiment. FIG. 2 is a partial plan view of the semiconductor device according to one embodiment. As illustrated in FIG. 1 and FIG. 2, the semiconductor device has a substrate 1, a semiconductor element 2 disposed on top of the substrate 1, a wire 3 that electrically connects the substrate 1 and the semiconductor element 2, a first sealing layer 4a that seals the space below the apex 3a of the wire 3, and a second sealing layer 4b that is provided on top of the first sealing layer 4a with the wire 3 interposed therebetween. As illustrated in FIG. 1, the semiconductor device preferably also has a resin sealing member 5 provided so as to cover at least the second sealing layer 4b. 21. 21. 21. id="p-21"
id="p-21"
[0021] The apex 3 a of the wire means the location at which the height of the wire from the substrate surface, indicated by the reference sign "h" in FIG. 1, reaches a maximum. The first sealing layer 4a is formed from the cured film of a liquid sealing material, and is formed by injecting the liquid sealing material into a space beneath the wire compartmentalized by the substrate 1, a portion of the semiconductor element 2, and the arc-shaped wire 3 having the apex 3a. Further, the second sealing layer 4b is formed from a dried coating film of an insulating resin coating material, and is formed by applying the insulating resin coating material following formation of the first sealing layer 4a.
In this manner, by adopting the embodiment described above and forming sealing layers using different materials in the space below the wire apex 3a and the space above the wire, a thin semiconductor device having superior ESD resistance and excellent reliability can be provided. The structure of the semiconductor device is described below in further detail. 22. 22. 22. id="p-22"
id="p-22"
[0022] 1. Substrate There are no particular limitations on the substrate, and any substrate composed of a material that is capable of mounting a semiconductor element and capable of being subjected to wire bonding may be used. The material for the substrate may be selected from among known materials within the technical field, in accordance with the intended application for the semiconductor device.
For example, when the semiconductor device is used in a fingerprint authentication application, typically, a thin rigid substrate such as a glass epoxy substrate may be used. 23. 23. 23. id="p-23"
id="p-23"
[0023] In another example, when the semiconductor device is used in a power module application, typically, DCB (Direct Copper Bond) substrates and ceramic substrates such as an alumina-based substrates may be used. In those cases where a copper circuit or the like is bonded directly to a ceramic substrate, installation of a heat-resistant bonding layer is unnecessary, and therefore superior heat dissipation and superior insulation properties can be more easily achieved. Accordingly, these types of ceramic substrates having directly bonded copper circuits or the like can be used favorably in high-voltage and high-current applications such as vehicle-mounted semiconductors, semiconductors for railways and semiconductors for industrial machinery. 24. 24. 24. id="p-24"
id="p-24"
[0024] 2. Semiconductor Element The semiconductor element is connected electrically to the substrate via the wire.
For example, the semiconductor element may be a semiconductor element for a fingerprint authentication sensor, or a Si-IGBT (insulated-gate bipolar transistor), a SiC (silicon carbide) or a MOSFET (metal oxide semiconductor field effect transistor) for a power module application. The semiconductor element is not limited to these semiconductor elements, and in any case where a semiconductor element is used that requires ESD resistance, or requires superior insulation properties for use under high-voltage and high-current conditions, the effects provided by the above embodiment can be easily realized. . . . id="p-25"
id="p-25"
[0025] The semiconductor element and the substrate are typically conductively bonded together by solder balls or the like. When a semiconductor element for a power module application is used, the conductive bonding between the semiconductor element and the substrate may also use other materials besides solder balls such as sintered silver and sintered copper. 26. 26. 26. id="p-26"
id="p-26"
[0026] 3. Wire The wire is used for electrically connecting the semiconductor element and the substrate. The material for the wire may be selected from among known materials within the technical field, in accordance with the intended application for the semiconductor device. For example, in those cases where the semiconductor device is to be used in a fingerprint authentication sensor application, a gold wire, silver alloy wire or copper wire or the like may be used. Gold wires are typically the most widely used. In another example, in those cases where the semiconductor device is to be used in a power module application, an aluminum wire is typically used. 4a. First Sealing Layer The first sealing layer is formed from the cured film of a liquid sealing material. As can be seen in FIG. 1, the first sealing layer is formed by injecting the liquid sealing material into a space beneath the wire compartmentalized by the substrate 1, a portion of the semiconductor element 2 and the arc-shaped wire 3 having the apex 3a, and then curing the liquid sealing material. 28. 28. 28. id="p-28"
id="p-28"
[0028] In one embodiment, the liquid sealing material contains a resin component and an inorganic filler. When the viscosity ( Pa.s) of the liquid sealing material measured under conditions of 75°C and a shear velocity of 5 s<1>is deemed as viscosity A, and the viscosity (Pa.s) measured under conditions of 75°C and a shear velocity of 50 s<-1>is deemed as viscosity B, the thixotropic index at 75°C of the liquid sealing material, obtained as the value of viscosity A / viscosity B, is preferably within a range from 0.1 to 2.5. The liquid sealing material may, if necessary, also contain other components besides the resin component and the inorganic filler. 29. 29. 29. id="p-29"
id="p-29"
[0029] In this description, the term "liquid sealing material" means a resin material that is liquid at room temperature, can be cured by heating or the like, and can be used favorably as an underfill material for filling the space between the semiconductor element and the substrate. Using the liquid sealing material to seal the space beneath the wire with no voids means that when the space above the wire is subsequently sealed with an insulating resin coating material, problems such as wire flow or the like caused by the coating material can be avoided. Further, other problems such as liquid flow of the insulating resin coating material during application can also be prevented, facilitating retention of the coating material on the wire application surface. . . . id="p-30"
id="p-30"
[0030] When a thixotropic index at 75°C of the liquid sealing material is within a range from 0.1 to 2.5, it makes easier to seal the space beneath the wire without voids by the liquid sealing material. 31. 31. 31. id="p-31"
id="p-31"
[0031] Although not a particular limitation, in one embodiment, the thixotropic index of the liquid sealing material at 75°C is more preferably within a range from 0.5 to 2.0, and even more preferably from 1.0 to 2.0. 32. 32. 32. id="p-32"
id="p-32"
[0032] The viscosity ( Pa.s) of the liquid sealing material measured under conditions of 75°C and a shear velocity of 5 s<-1>is preferably not more than 3.0 Pa.s, and more preferably 2.0 Pa.s or less. Provided the viscosity (Pa.s) of the liquid sealing material at 75°C and a shear velocity of 5 s<-1>is not more than 3.0 Pa.s, the occurrence of wire flow tend to be more effectively suppressed when the liquid sealing material is applied around the wire.
Although there are no particular limitations on the lower limit for the above viscosity, from the viewpoint of retaining the material in the applied state around the periphery of the wire, the viscosity is preferably at least 0.01 Pa.s. 33. 33. 33. id="p-33"
id="p-33"
[0033] The liquid sealing material has a viscosity measured at 25°C and a shear velocity of 10 s<-1>that is preferably not more than 30 Pa.s, and more preferably 20 Pa.s or less. Although there are no particular limitations on the lower limit for this viscosity, from the viewpoint of retaining the material in the applied state around the periphery of the wire, the viscosity is preferably at least 0.1 Pa.s. 34. 34. 34. id="p-34"
id="p-34"
[0034] The viscosity of the liquid sealing material at 25°C is a value measured using an E-type viscometer (for example, a VISCONIC EHD manufactured by Tokyo Keiki Inc.), whereas the viscosity at 75 °C is a value measured using a rheometer (for example, a product AR2000 manufactured by TA Instruments, Inc.). . . . id="p-35"
id="p-35"
[0035] The thixotropic index at 75°C for the liquid sealing material is obtained as the value of viscosity A / viscosity B, where the viscosity measured under conditions of 75°C and a shear velocity of 5 s<-1>is deemed as viscosity A, and the viscosity measured under conditions of 75°C and a shear velocity of 50 s<-1>is deemed as viscosity B. 36. 36. 36. id="p-36"
id="p-36"
[0036] There are no particular limitations on the method used to ensure that the liquid sealing material satisfies the viscosity condition described above. For example, examples of methods for reducing the viscosity of the liquid sealing material include methods that use a low-viscosity resin component and methods in which a solvent is added, and any one of these methods or a combination of methods may be used. 37. 37. 37. id="p-37"
id="p-37"
[0037] Resin Component There are no particular limitations on the resin component contained in the liquid sealing material, provided the liquid sealing material is able to satisfy the condition described above. From the viewpoints of the compatibility with existing facilities, and the stability of the characteristics of the liquid sealing material, the use of a thermosetting resin component is preferred, and the use of an epoxy resin is more preferred. Furthermore, the use of a resin component that is liquid at normal temperature (25°C) (hereafter also simply described as "liquid") is preferable, and the use of a liquid epoxy resin is particularly preferred. The resin component may also be a combination of an epoxy resin and a curing agent. 38. 38. 38. id="p-38"
id="p-38"
[0038] (Epoxy Resin) Examples of an epoxy resin that may be used as the liquid sealing material include a diglycidyl ether epoxy resins of bisphenol A, bisphenol F, bisphenol AD, bisphenol S and hydrogenated bisphenol A, a resin (novolac epoxy resin) typified by ortho-cresol novolac epoxy resin obtained by epoxidation of a novolac resin of a phenol and an aldehyde, a glycidyl ester epoxy resin obtained by the reaction of an epichlorohydrin and a polybasic acid such as phthalic acid or dimer acid, a glycidylamine epoxy resin obtained by the reaction of an epichlorohydrin and an amine compound such as p-aminophenol, diaminodiphenylmethane and isocyanuric acid, a linear aliphatic epoxy resin obtained by oxidation of an olefin bond with a peracid such as a peracetic acid, and an alicyclic epoxy resin. A single epoxy resin may be used alone, or a combination of two or more resins may be used. 39. 39. 39. id="p-39"
id="p-39"
[0039] Among the above epoxy resins, from the viewpoints of the viscosity, actual usage experience and material cost, at least one resin selected from the group consisting of a diglycidyl ether epoxy resin and a glycidylamine epoxy resin is preferred. Among such resins, from the viewpoint of fluidity, a liquid bisphenol epoxy resin is preferred, whereas from the viewpoints of heat resistance, adhesiveness and fluidity, a liquid glycidylamine epoxy resin is preferred. 40. 40. 40. id="p-40"
id="p-40"
[0040] In one embodiment, the liquid sealing material uses an epoxy resin having an aromatic ring (an aromatic epoxy resin) and an aliphatic epoxy resin as resin components. For example, a liquid bisphenol F epoxy resin and a liquid glycidylamine epoxy resin may be used as the aromatic epoxy resin, and a linear aliphatic epoxy resin may be used as the aliphatic epoxy resin. 41. 41. 41. id="p-41"
id="p-41"
[0041] Examples of the glycidylamine epoxy resin include p-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline, diglycidylaniline, diglycidyltoluidine, diglycidylmethoxyaniline, diglycidyldimethylaniline and diglycidyltrifluoromethylaniline.
Examples of the linear aliphatic epoxy resin include 1,6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, propylene glycol diglycidyl ether, l,3-bis(3-glycidoxypropyl)tetramethyldisiloxane and cyclohexanedimethanol diglycidyl ether. 42. 42. 42. id="p-42"
id="p-42"
[0042] In those cases where a combination of a liquid bisphenol F epoxy resin, a liquid glycidylamine epoxy resin and a linear aliphatic epoxy resin is used as the epoxy resin, there are no particular limitations on the blend ratio between these compounds. The blend ratio may be such that, for example, the liquid glycidylamine epoxy resin represents 40% by mass to 70% by mass of the total mass, and the combination of the liquid bisphenol F epoxy resin and the linear aliphatic epoxy resin represents 30% by mass to 60% by mass of the total mass. 43. 43. 43. id="p-43"
id="p-43"
[0043] From the viewpoint of ensuring satisfactory manifestation of their properties, the amount of the epoxy resin described above (or the combined mass in the case of a combination of two or more of the above epoxy resins) within the total mass of all epoxy resins is preferably at least 20% by mass, more preferably at least 30% by mass, and even more preferably 50% by mass or greater. There are no particular limitations on the upper limit for this amount, and the amount may be determined so as to achieve the desired properties and characteristics for the liquid sealing material. 44. 44. 44. id="p-44"
id="p-44"
[0044] A liquid epoxy resin is preferably used as the epoxy resin, but an epoxy resin that is solid at normal temperature (25°C) may also be used in combination. In those cases where an epoxy resin that is solid at normal temperature is used in combination with the liquid epoxy resin, the proportion of the solid epoxy resin is preferably not more than 20% by mass of the total mass of all the epoxy resin. 45. 45. 45. id="p-45"
id="p-45"
[0045] From the viewpoint of suppressing wire corrosion, the chlorine ion content in the liquid sealing material is preferably as low as possible. Specifically, the chlorine ion content is preferably not more than 100 ppm.
In this description, the chlorine ion content in the liquid sealing material is obtained by treating the material by ion chromatography using a sodium carbonate solution as the eluent under conditions including a temperature of 121 °C and a time of 20 hours, and represents the value (ppm) equivalent to 2.5g/50cc. 46. 46. 46. id="p-46"
id="p-46"
[0046] (Curing Agent) The types of compounds typically used as curing agents for epoxy resin such as amine -based curing agents, phenol-based curing agents and acid anhydride-based curing agents may be used as the curing agent without any particular limitations. From the viewpoint of suppressing wire flow, the use of a liquid curing agent is preferred. From the viewpoints of exhibiting excellent resistance to temperature cycling and excellent moisture resistance and the like, and being capable of improving the reliability of semiconductor packages, the curing agent is preferably an aromatic amine compound, and is more preferably a liquid aromatic amine compound. A single curing agent may be used alone, or a combination of two or more curing agents may be used. 47. 47. 47. id="p-47"
id="p-47"
[0047] Examples of the liquid aromatic amine compound include diethyltoluenediamine, 1-methyl-3, 5-diethyl-2,4-diaminobenzene, 1-methyl-3, 5 -diethyl-2, 6-diaminobenzene, l,3,5-triethyl-2,6-diaminobenzene, 3, 3'-diethyl-4, 4'-diaminodiphenylmethane, 3,5,3',5'-tetramethyl-4,4'-diaminodiphenylmethane, and dimethylthiotoluenediamine. 48. 48. 48. id="p-48"
id="p-48"
[0048] The liquid aromatic amine compound may also be obtained in the form of a commercially available product. Examples of products that can be obtained include jER Cure W (product name, manufactured by Mitsubishi Chemical Corporation), KAYAHARD A-A, KAYAHARD A-B and KAYAHARD A-S (product names, manufactured by Nippon Kayaku Co., Ltd.), TOHTO AMINE HM-205 (product name, manufactured by NIPPON STEEL Chemical & Material Co., Ltd.), ADEKA HARDENER EH-101 (product name, manufactured by ADEKA Corporation), EPOMIK Q-640 and EPOMIK Q-643 (product names, manufactured by Mitsui Chemicals, Inc.), and DETDA80 (product name, manufactured by Lonza Group AG). 49. 49. 49. id="p-49"
id="p-49"
[0049] Among the various liquid aromatic amine compounds, from the viewpoint of the storage stability of the liquid sealing material, 3, 3 '-diethyl-4, 4'-diaminodiphenylmethane, diethyltoluenediamine and dimethylthiotoluenediamine are preferred. Any of these compounds or a mixture thereof is preferably used as the main component of the curing agent. Examples of the diethyltoluenediamine include 3, 5-diethyltoluene -2, 4-diamine and 3, 5-diethyltoluene -2, 6-diamine, and either of these compounds may be used alone or a combination of both compounds may be used, although the proportion of 3, 5-diethyltoluene-2, 4-diamine is preferably at least 60% by mass of the total mass of diethyltoluenediamine. 50. 50. 50. id="p-50"
id="p-50"
[0050] There are no particular limitations on the amount of the curing agent in the liquid sealing material, which may be selected with due consideration of factors such as the equivalence ratio relative to the epoxy resin. From the viewpoint of suppressing the amounts of unreacted epoxy resin or curing agent, the amount of the curing agent is preferably an amount that ensures that the ratio of the number of equivalents of functional groups in the curing agent (for example, the number of equivalents of active hydrogens in the case of an amine -based curing agent) relative to the number of equivalents of epoxy groups in the epoxy resin is within a range from 0.7 to 1.6 is preferred, an amount that yields a ratio within a range from 0.8 to 1.4 is more preferred, and a ratio that yields a ratio within a range from 0.9 to 1.2 is even more preferred. 51. 51. 51. id="p-51"
id="p-51"
[0051] There are no particular limitations on the type of inorganic filler included in the liquid sealing material. Examples include powders of silica, calcium carbonate, clay, alumina, silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate, aluminum nitride, beryllia, zirconia, zircon, forsterite, steatite, spinel, mullite and titania, as well as beads obtained by spheroidization of these powders and glass fiber and the like. Moreover, an inorganic filler having a flame retardant effect may also be used, and examples of such inorganic fillers include aluminum hydroxide, magnesium hydroxide, zinc borate, and zinc molybdate. A single inorganic filler may be used alone, or a combination of two or more inorganic fillers may be used. 52. 52. 52. id="p-52"
id="p-52"
[0052] Among the various inorganic fillers, from the viewpoints of ease of availability, chemical stability and material costs, silica is preferred. Examples of the silica include spherical silica and crystalline silica, but from the viewpoint of enhancing the fluidity and permeability of the liquid sealing material into narrow spaces, a spherical silica is preferred. Examples of the spherical silica include silica obtained by the vaporized metal combustion method and fused silica and the like. 53. 53. 53. id="p-53"
id="p-53"
[0053] The inorganic filler may have a surface that has been subjected to a surface treatment. For example, the inorganic filler may have been surface-treated with a coupling agent described below. 54. 54. 54. id="p-54"
id="p-54"
[0054] The volume average particle size of the inorganic filler is preferably within a range from 0.1 μm to 30 μm, more preferably from 0.3 μm to 5 μm, and even more preferably from 0.5 μm to 3 μm. Particularly in the case of a spherical silica, the volume average particle size preferably falls within the above range. Provided the volume average particle size is at least 0.1 μm, the dispersibility within the liquid sealing material is excellent, and the fluidity tends to be excellent. Provided the volume average particle size is not more than 30 μm, precipitation of the inorganic filler within the liquid sealing material is reduced, and the permeability and fluidity of the liquid sealing material into narrow spaces improve, meaning the occurrence of voids and unfilled portions tends to be better suppressed. 55. 55. 55. id="p-55"
id="p-55"
[0055] The volume average particle size of the inorganic filler means the particle size in the volumebased particle size distribution obtained using a laser diffraction particle size distribution analyzer where the accumulated value from the small particle side reaches 50% (namely, D50%). 56. 56. 56. id="p-56"
id="p-56"
[0056] The maximum particle size of the inorganic filler is preferably not more than 75 μm, moreover preferably not more than 50 μm, and even more preferably 20 μm or less. 57. 57. 57. id="p-57"
id="p-57"
[0057] In this description, the maximum particle size of the inorganic filler means the particle size in the volume-based particle size distribution where the accumulated value from the small particle side reaches 99% (namely, D99%). 58. 58. 58. id="p-58"
id="p-58"
[0058] The amount of the inorganic filler is preferably at least 50% by mass based on the total mass of the liquid sealing material. Provided the amount of the inorganic filler is at least 50% by mass based on the total mass of the liquid sealing material, the heat dissipation properties and strength in the vicinity of the wire tend to be satisfactorily maintained. The amount of the inorganic filler based on the total mass of the liquid sealing material is more preferably at least 60% by mass, and even more preferably 70% by mass or greater.
From the viewpoint of suppressing any increase in the viscosity of the liquid sealing material, the amount of the inorganic filler is preferably not more than 80% by mass based on the total mass of the liquid sealing material. 59. 59. 59. id="p-59"
id="p-59"
[0059] The liquid sealing material may contain a solvent. By including a solvent, the viscosity of the liquid sealing material can be easily adjusted to a value within the desired range. A single solvent may be used alone, or a combination of two or more solvents may be used. 60. 60. 60. id="p-60"
id="p-60"
[0060] There are no particular limitations on the type of solvent used, and the solvent may be selected from among those solvents typically used in the resin compositions used in mounting techniques for semiconductor devices. Specific examples include: alcohol-based solvents such as butyl carbitol acetate, methyl alcohol, ethyl alcohol, propyl alcohol and butyl alcohol, ketone-based solvents such as acetone and methyl ethyl ketone, glycol ether-based solvents such as ethylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol ethyl ether, and propylene glycol methyl ether acetate, lactone-based solvents such as γ-butyrolactone, δ-valerolactone, and ε-caprolactone, amide-based solvents such as dimethylacetamide and dimethylformamide, and aromatic-based solvents such as toluene and xylene.
From the viewpoint of preventing bubble formation caused by overly rapid volatilization during curing of the liquid sealing material, the use of a high-boiling point solvent (for example, a boiling point of at least 170°C at normal pressure) is preferred. 61. 61. 61. id="p-61"
id="p-61"
[0061] In those cases where the liquid sealing material contains a solvent, although there are no particular limitations on the amount of the solvent, the amount is preferably within a range from 1% by mass to 70% by mass of the total mass of the liquid sealing material. 62. 62. 62. id="p-62"
id="p-62"
[0062] The liquid sealing material may, if necessary, also contain a curing accelerator that accelerates the reaction between the epoxy resin and the curing agent.
There are no particular limitations on the curing accelerator, and conventionally known compounds may be used. Examples include: cycloamidine compounds such as l,8-diaza-bicyclo[5.4.0]undecene-7, 1,5-diazabicyclo[4.3.0]nonene, and 5,6-dibutylamino-l,8-diaza-bicyclo[5.4.0]undecene-7, tertiary amine compounds such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris(dimethylaminomethyl)phenol, imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2 -phenylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2'-methylimidazolyl-(1'))-ethyl-s-triazine, and 2-heptadecylimidazole, organophosphine compounds such as trialkylphosphines (such as tributylphosphine), dialkylarylphosphines (such as dimethylphenylphosphine), alkyldiarylphosphines (such as methyldiphenylphosphine), triphenylphosphine, and alkyl-substituted triphenylphosphines, and compounds having intramolecular polarization obtained by adding, to any of the above organophosphines, a compound having a π bond such as maleic anhydride, a quinone compound such as 1,4-benzoquinone, 2,5-toluquinone, 1, 4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2, 3-dimethoxy-5-methyl-1 ,4-benzoquinone, 2, 3-dimethoxy-1 ,4-benzoquinone or phenyl- 1,4-benzoquinone, diazophenylmethane, or a phenol resin, as well as derivatives of these compounds.
Additional examples include phenyl boron salts such as 2-ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate. Furthermore, examples of curing accelerators having latency include core-shell particles having a core composed of a compound having an amino group that is solid at normal temperature coated with a shell composed of an epoxy compound that is solid at normal temperature. A single curing accelerator may be used alone, or a combination of two or more curing accelerators may be used. 63. 63. 63. id="p-63"
id="p-63"
[0063] In those cases where the liquid sealing material contains a curing accelerator, although there are no particular limitations on the amount of the curing accelerator, the amount is preferably within a range from 0.1 parts by mass to 40 parts by mass, and more preferably from 1 part by mass to 20 parts by mass, per 100 parts by mass of the epoxy resin. 64. 64. 64. id="p-64"
id="p-64"
[0064] From the viewpoints of improving the thermal shock resistance and reducing stress on the semiconductor element, the liquid sealing material may, if necessary, also contain a flexibility agent.
There are no particular limitations on the flexibility agent, which may be selected from among flexibility agents typically used in resin compositions. Among these typical flexibility agents, rubber particles are preferred. Examples of the rubber particles include particles of styrene -butadiene rubber (SBR), nitrile-butadiene rubber (NBR), butadiene rubber (BR), urethane rubber (UR) and acrylic rubber (AR). Among these rubbers, from the viewpoints of the heat resistance and moisture resistance, acrylic rubber particles are preferred, and acrylic-based polymer particles having a coreshell structure (namely, core-shell acrylic rubber particles) are more preferred. 65. 65. 65. id="p-65"
id="p-65"
[0065] Further, silicone rubber particles can also be used favorably. Examples of the silicone rubber particles include silicone rubber particles obtained by crosslinking a polyorganosiloxane such as a linear polydimethylsiloxane, polymethylphenylsiloxane or polydiphenylsiloxane, particles obtained by coating the surfaces of silicone rubber particles with a silicone resin, and core-shell polymer particles composed of a core of a solid silicone particle obtained by emulsion polymerization or the like and a shell of an organic polymer such as an acrylic resin. The shape of these silicone rubber particles may be either amorphous or spherical, but in order to lower the viscosity of the liquid sealing material, a spherical shape is preferred. These silicone rubber particles can be obtained as commercially available products from companies such as Dow Coming Toray Silicone Co., Ltd., and Shin-Etsu Chemical Co., Ltd. 66. 66. 66. id="p-66"
id="p-66"
[0066] The liquid sealing material may also contain a coupling agent for the purpose of improving the adhesion at the interface between the resin component and the inorganic filler, or at the interface between the resin component and the wire. The coupling agent may be used for surface treatment of the inorganic filler, or may be added separately from the inorganic filler. 67. 67. 67. id="p-67"
id="p-67"
[0067] There are no particular limitations on the coupling agent, and conventional materials may be used. Examples include a silane compound having an amino group (primary, secondary or tertiary), various other silane compounds such as an epoxysilane, a mercaptosilane, an alkylsilane, an ureidosilanes and a vinylsilane, as well as a titanium compound, an aluminum chelate, and aluminum/zirconium-based compounds. A single coupling agent may be used alone, or a combination of two or more coupling agents may be used. 68. 68. 68. id="p-68"
id="p-68"
[0068] Specific examples of a silane coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(P-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, β-(3, 4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γglycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γaminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γaminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ-(N,N-dimethyl)aminopropyltrimethoxysilane, γ-(N,N-diethyl)aminopropyltrimethoxysilane, γ-(Ν,Ν-dibutyl)aminopropyltrimethoxysilane, γ-(N-methyl)anilinopropyltrimethoxysilane, γ-(Ν-ethyl)anilinopropyltrimethoxysilane, γ-(N,N-dimethyl)aminopropyltriethoxysilane, γ-(Ν,Ν-diethyl) aminopropyltriethoxysilane, γ-(Ν,Ν -dibutyl)aminopropyltriethoxysilane, γ-(Νmethyl)anilinopropyltriethoxysilane, γ-(N-cthyl)anilinopropyltricthoxysilγa-nc, (N,N-dimethyl)aminopropylmethyldimethoxysilane, γ-(N,N-dicthyl)aminopropylmcthyldimcthoxysilanc, γ-(N,N-dibutyl)aminopropylmethyldimethoxysilane, γ-(N-methyl)anilinopropylmethyldimethoxysilane, γ-(N-ethyl)anilinopropylmethyldimethoxysilane, N-(trimethoxysilylpropyl)ethylenediamine, N-(dimethoxymethylsilylisopropyl)ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, andγ- mercaptopropylmethyldimethoxysilane. 69. 69. 69. id="p-69"
id="p-69"
[0069] Specific examples of a titanium coupling agent include isopropyl triisostearoyl titanate, isopropyl tris(dioctylpyrophosphate) titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, tetraoctylbis(ditridecylphosphite) titanate, tetra(2,2-diallyloxymethyl-l -butyl) bis(ditridecyl) phosphite titanate, bis(dioctylpyrophosphate) oxyacetate titanate, bis(dioctylpyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri(dioctylphosphate) titanate, isopropyl tricumylphenyl titanate, and tetraisopropyl bis(dioctylphosphite) titanate. 70. 70. 70. id="p-70"
id="p-70"
[0070] In those cases where the liquid sealing material contains a coupling agent, the amount of the coupling agent is not particularly limited, but is preferably within a range from 1 part by mass to 30 parts by mass per 100 parts by mass of the inorganic filler. 71. 71. 71. id="p-71"
id="p-71"
[0071] From the viewpoints of improving the anti-migration properties, moisture resistance and hightemperature storage properties and the like of the semiconductor package, the liquid sealing material may also contain an ion trapping agent. A single ion trapping agent may be used alone, or a combination of two or more ion trapping agents may be use. 72. 72. 72. id="p-72"
id="p-72"
[0072] Examples of the ion trapping agent include anion exchangers represented by compositional formulas (V) and (VI) shown below.
Mg1_aAla(OH)2(CO3)a/2.mH20 (V) (wherein 0 < a ≤ 0.5, and m is a positive number) BiOa(OH)b(NO3)c(VI) (wherein 0.9 ≤ a ≤ 1.1, 0.6 ≤ b ≤ 0.8, and 0.2 ≤ c ≤ 0.4) 73. 73. 73. id="p-73"
id="p-73"
[0073] A compound of the above formula (V) can be obtained as a commercially available product (product name: DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.). Further, a compound of the above formula (VI) can also be obtained as a commercially available product (product name: IXE500, manufactured by Toagosei Co., Ltd.). Other anion exchangers besides the compounds mentioned above may also be used as ion trapping agents. Examples include oxide hydrates of elements selected from among magnesium, aluminum, titanium, zirconium, and antimony and the like. 74. 74. 74. id="p-74"
id="p-74"
[0074] In those cases where the liquid sealing material contains an ion trapping agent, there are no particular limitations on the amount of the ion trapping agent. For example, the amount is preferably within a range from 0.1% by mass to 3.0% by mass, and more preferably from 0.3% by mass to 1.5% by mass, of the total mass of the liquid sealing material. 75. 75. 75. id="p-75"
id="p-75"
[0075] In those cases where the ion trapping agent is particulate, the volume average particle size (D50%) of the particles is preferably within a range from 0.1 μm to 3.0 μm. Further, the maximum particle size is preferably not more than 10 μm. 76. 76. 76. id="p-76"
id="p-76"
[0076] The liquid sealing material may, if necessary, also contain other components besides those described above. For example, a colorant such as a dye and carbon black, a diluent, a leveling agent and an antifoaming agent may be added according to need. 77. 77. 77. id="p-77"
id="p-77"
[0077] 4b. Second Sealing Layer The second sealing layer 4b is formed from a dried coating film of an insulating resin coating material, and is formed by applying the insulating resin coating material following formation of the first sealing layer 4a. The second sealing layer 4b functions as an insulating protective layer for the wire. 78. 78. 78. id="p-78"
id="p-78"
[0078] The insulating resin coating material has one or more of the following characteristics. (i) The dielectric breakdown voltage, at least following film formation, is at least 150 kV/mm (ii) The insulating resin coating material contains a resin filler having an average particle size of 0.1 to 5.0 pm. (iii) The viscosity at 25°C is within a range from 30 to 500 Pa.s. (iv) The thixotropic index at 25°C is within a range from 2.0 to 10.0. (v) Following film formation under heat, the insulating resin component and the resin filler are dispersed uniformly, and no interface develops between the insulating resin component and the resin filler. Accordingly, superior insulation properties can be maintained even in the case of a thin film. 79. 79. 79. id="p-79"
id="p-79"
[0079] With the insulating resin coating material, there is a possibility that voids may form during application, depending on the shape of the semiconductor device that represents the application target.
For example, in the case of protection of the portion above a wire in a semiconductor device, because the ends of the wire are secured, a space is formed beneath the wire, and therefore in the subsequent sealing step, there is a possibility that the sealing material may not satisfactorily penetrate into that space. When a void exists in a semiconductor device, the effects of humidity and the like can have a significant effect in lowering the reliability of the semiconductor device, and therefore the formation of voids within a semiconductor device is usually not permitted. 80. 80. 80. id="p-80"
id="p-80"
[0080] In order to avoid the formation of this type of void in the semiconductor device or the wire portion, by first sealing the portion beneath the wire with the liquid sealing material described above, void formation in the semiconductor device can be suppressed, and the reliability of the semiconductor device can be improved. The liquid sealing material fills the space beneath the wire, and not only contributes to maintaining the reliability of the semiconductor, but also has an effect in protecting the wire itself. The wire can sometimes collapse under the pressure applied during the device sealing step. However, by first performing sealing with the liquid sealing material, collapse of the wire can also be avoided. 81. 81. 81. id="p-81"
id="p-81"
[0081] In one embodiment, the insulating resin coating material preferably has a dielectric breakdown voltage following film formation that is at least 150 kV/mm, contains a resin filler having an average particle size of 0.1 to 5.0 μm, has a viscosity at 25°C of 30 to 500 Pa.s, and has a thixotropic index of 2.0 to 10.0. 82. 82. 82. id="p-82"
id="p-82"
[0082] The dielectric breakdown voltage following film formation is preferably at least 150 kV/mm, and is more preferably 200 kV/mm or greater. In one embodiment, the insulating resin coating material enables a dielectric breakdown voltage of at least 200 kV/mm to be obtained, and can contribute to reduced thickness of the semiconductor device. 83. 83. 83. id="p-83"
id="p-83"
[0083] The insulating resin may be selected from among highly heat-resistant resins such as a polyamide, a polyamideimide and a polyimide. In one embodiment, the insulating resin coating material preferably contains at least one insulating resin selected from the group consisting of a polyamide, a polyamideimide and a polyimide. In particular, in terms of not requiring a hightemperature imidization treatment during formation of the semiconductor device, a polyamide or polyamideimide is preferred, and in terms of achieving superior heat resistance, a polyamideimide resin is particularly desirable. Any highly heat-resistant resin that exhibits excellent adhesion to resin sealing members may be used. If a polyimide has a resin structure that remains soluble in solvents even following imide group formation, then from the viewpoint of heat resistance, a polyamide is sometimes the most preferred. 84. 84. 84. id="p-84"
id="p-84"
[0084] The components that constitute the insulating resin coating material are described below. The insulating resin coating material contains a mixed solvent that includes a first polar solvent (A1) and a second polar solvent (A2) having a boiling point lower than that of the first polar solvent (A1) in a mass ratio (A1 :A2) within a range from 6:4 to 9:1, an insulating heat-resistant resin (B) that is soluble in the mixed solvent of the first polar solvent (A1) and the second polar solvent (A2) at room temperature, and an insulating heat-resistant resin (C) which, at room temperature, is soluble in the first polar solvent (A1), insoluble in the second polar solvent (A2), and insoluble in the mixed solvent of the first polar solvent (A1) and the second polar solvent (A2).
In this description, "room temperature" means 25°C. 85. 85. 85. id="p-85"
id="p-85"
[0085] The insulating heat-resistant resin (B) is soluble in the mixed solvent of the first polar solvent (A1) and the second polar solvent (A2) at room temperature, whereas the insulating heat-resistant resin (C) is insoluble in the mixed solvent of the first polar solvent (A1) and the second polar solvent (A2) at room temperature. As a result, in the insulating resin coating material, the insulating heatresistant resin (C) is dispersed within a mixed solvent containing the first polar solvent (A1), the second polar solvent (A2) and the insulating heat-resistant resin (B), and functions as a filler.
Accordingly, the thixotropic index can be easily adjusted to a value that is suitable for supplying the insulating resin coating material with a dispensing technique to form the second sealing layer on the upper portion of the wire. Moreover, by heating the insulating resin coating material to a temperature at which the insulating heat-resistant resin (C) also dissolves, thereby eliminating the filler. As a result, an accurate resolution can be achieved, and the flatness of the surface of the resin film can be improved. 86. 86. 86. id="p-86"
id="p-86"
[0086] Examples of the first polar solvent (A1) and the second polar solvent (A2) include: polyether alcohol-based solvents such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether and tetraethylene glycol monoethyl ether, ether-based solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, triethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dipropyl ether and tetraethylene glycol dibutyl ether, sulfur-containing solvents such as dimethylsulfoxide, diethylsulfoxide, dimethylsulfone and sulfolane, ester-based solvents such as ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate and butyl cellosolve acetate, ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetophenone, nitrogen-containing solvents such as N-methylpyrrolidone, dimethylacetamide, dimethylformamide, 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone and 1,3 -dimethyl-2 -imidazolidinone, aromatic hydrocarbon-based solvents such as toluene and xylene, lactone-based solvents such as γ-butyrolactone, γ-valerolactone, γ-caprolactone, γheptalactone, α-acetyl-γ-butyrolactone and ε-caprolactone, alcohol-based solvents such as butanol, octyl alcohol, ethylene glycol and glycerol, and phenol-based solvents such as phenol, cresol and xylenol. 87. 87. 87. id="p-87"
id="p-87"
[0087] The combination of the first polar solvent (A1) and the second polar solvent (A2) may be selected appropriately from among these solvents in accordance with the varieties of the insulating heat-resistant resin (B) and the insulating heat-resistant resin (C). 88. 88. 88. id="p-88"
id="p-88"
[0088] Examples of preferred solvents for the first polar solvent (A1) include: nitrogen-containing solvents such as N-methylpyrrolidone, dimethylacetamide, dimethylformamide, 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone and 1,3-dimethyl-2-imidazolidinone, sulfur-containing solvents such as dimethylsulfoxide, diethylsulfoxide, dimethylsulfone and sulfolane, lactone-based solvents such as γ-butyrolactone, γ-valerolactone, γ-caprolactone, γheptalactone, α-acetyl- γ-butyrolactone and ε-caprolactone, ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetophenone, and alcohol-based solvents such as butanol, octyl alcohol, ethylene glycol and glycerol.
In those cases where each of the insulating heat-resistant resin (B) and the insulating heatresistant resin (C) described below is independently at least one resin selected from among a polyamide resin, a polyimide resin, a polyamideimide resin, and precursors to a polyimide resin and a polyamideimide resin, γ-butyrolactone is particularly desirable as the first polar solvent (A1). 89. 89. 89. id="p-89"
id="p-89"
[0089] Examples of preferred solvents for the second polar solvent (A2) include: ether-based solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, triethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dipropyl ether and tetraethylene glycol dibutyl ether, polyether alcohol-based solvents such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether and tetraethylene glycol monoethyl ether, and ester-based solvents such as ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate and butyl cellosolve acetate.
In those cases where each of the insulating heat-resistant resin (B) and the insulating heatresistant resin (C) described below is independently at least one resin selected from among a polyamide resin, a polyimide resin, a polyamideimide resin, and precursors to a polyimide resin and a polyamideimide resin, a polyether alcohol-based solvent or an ester-based solvent is preferred as the second polar solvent (A2). 90. 90. 90. id="p-90"
id="p-90"
[0090] From the viewpoint of improving the handling properties of the insulating resin coating material, the difference between the boiling point of the first polar solvent (A1) and the boiling point of the second polar solvent (A2) in the insulating resin coating material is preferably within a range from 10 to 100°C, more preferably from 10°C to 50°C, and even more preferably from 10°C to 30°C. Further, from the viewpoint of lengthening the usable lifetime of the insulating resin coating material during application, the boiling points of both the first polar solvent (A1) and the second polar solvent (A2) are preferably at least 100°C, and more preferably 150°C or higher. 91. 91. 91. id="p-91"
id="p-91"
[0091] The insulating heat-resistant resin (B) and the insulating heat-resistant resin (C) are each, independently, preferably at least one resin selected from among a polyamide resin, a polyimide resin, a polyamideimide resin, and precursors to a polyimide resin and a polyamideimide resin. Examples of these polyamide resin, polyimide resin, polyamideimide resin, and precursors to polyimide resin and polyamideimide resin include resins obtained by reaction between an aromatic, aliphatic or alicyclic diamine compound, and a polyvalent carboxylic acid having 2 to 4 carboxyl groups. The expression "a precursors to polyimide resin and polyamideimide resin" mean a polyamic acid which is a substance prior to a dehydration cyclization that form a polyimide resin or polyamideimide resin upon dehydration cyclization. The insulating heat-resistant resin (C) is, for example, preferably soluble in the mixed solvent described above upon heating to at least 60°C (and preferably 60 to 200°C, and more preferably 100 to 180°C). 92. 92. 92. id="p-92"
id="p-92"
[0092] Examples of the aromatic, aliphatic or alicyclic diamine compound include diamine compounds having an arylene group, an alkylene group which may have an unsaturated bond, a cycloalkylene group which may have an unsaturated bond, or a group having a combination of these groups. These groups may be bonded via a carbon atom, an oxygen atom, a sulfur atom, a silicon atom, or a group containing a combination of these atoms. Further, the hydrogen atom bonded to the carbon skeleton of the alkylene group may each be substituted with a fluorine atom. From the viewpoints of the heat resistance and mechanical strength, an aromatic diamine is preferred. 93. 93. 93. id="p-93"
id="p-93"
[0093] Examples of the polyvalent carboxylic acid having 2 to 4 carboxyl groups include a dicarboxylic acid or a reactive acid derivative thereof, a tricarboxylic acid or a reactive acid derivative thereof, and a tetracarboxylic dianhydride. These compounds may be a dicarboxylic acid, a tricarboxylic acid or a reactive acid derivative thereof in which the carboxyl groups are bonded to an aryl group or a cycloalkyl group that may include a crosslinked structure or unsaturated bond within the ring, or a tetracarboxylic dianhydride in which the carboxyl groups are bonded to an aryl group or a cycloalkyl group that may include a crosslinked structure or unsaturated bond within the ring, and the dicarboxylic acid, tricarboxylic acid or reactive acid derivative thereof, and the tetracarboxylic dianhydride may be bonded via a single bond, or a carbon atom, an oxygen atom, a sulfur atom, a silicon atom, or a group containing a combination of these atoms. Furthermore, the hydrogen atom bonded to the carbon skeleton of the alkylene group may each be substituted with a fluorine atom. Among these compounds, from the viewpoints of the heat resistance and mechanical strength, tetracarboxylic dianhydrides are preferred. The combination of the aromatic, aliphatic or alicyclic diamine compound and the polyvalent carboxylic acid having 2 to 4 carboxyl groups may be selected as appropriate in accordance with the reactivity and the like. 94. 94. 94. id="p-94"
id="p-94"
[0094] The reaction may be conducted without using a solvent, or may be conducted in the presence of an organic solvent. The reaction temperature is preferably from 25°C to 250°C, and the reaction time may be selected appropriately in accordance with the batch scale and the reaction conditions employed. 95. 95. 95. id="p-95"
id="p-95"
[0095] There are also no particular limitations on the method used for subjecting the polyimide resin precursor or polyamideimide resin precursor to dehydration cyclization to form a polyimide resin or polyamideimide resin, and typical methods may be used. For example, thermal cyclization methods in which the dehydration cyclization is conducted by heating under normal pressure or reduced pressure, or chemical cyclization methods that use a dehydration agent such as acetic anhydride, either in the presence or absence of a catalyst, may be used. 96. 96. 96. id="p-96"
id="p-96"
[0096] In the case of a heat cyclization method, the cyclization is preferably performed while the water produced by the dehydration reaction is removed from the system. At this time, the reaction liquid may be heated to a temperature within a range from 80 to 400°C, and preferably from 100 to 250°C. Further, the water may also be removed by azeotropic distillation by using a solvent capable of forming an azeotrope with water, such as benzene, toluene or xylene.
In the case of a chemical cyclization method, the reaction is performed in the presence of a chemical dehydration agent at a temperature of 0 to 120°C, and preferably 10 to 80°C. Examples of chemical dehydration agents that can be used favorably include acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride and benzoic anhydride, and carbodiimide compounds such as dicyclohexylcarbodiimide. During the reaction, a material that accelerates the cyclization reaction such as pyridine, isoquinoline, trimethylamine, triethylamine, aminopyridine or imidazole is also preferably used in combination with the chemical dehydration agent. The chemical dehydration agent is used in a ratio of 90 to 600 mol% relative to the total amount of the diamine compound, and the material that accelerates the cyclization reaction is used in a ratio of 40 to 300 mol% relative to the total amount of the diamine compound. Further, a dehydration catalyst, including phosphorus compounds such as triphenyl phosphite, tricyclohexyl phosphite, triphenyl phosphate, phosphoric acid and phosphorus pentoxide, and boron compounds such as boric acid and boric anhydride, may also be used. 98. 98. 98. id="p-98"
id="p-98"
[0098] By pouring the reaction liquid obtained following completion of the imidization by dehydration into a large excess of a solvent that exhibits compatibility with the aforementioned first polar solvent (A1) and the second polar solvent (A2) and also acts as a poor solvent relative to the insulating heat-resistant resins (B) and (C), such as a lower alcohol like methanol, water, or a mixture thereof, thus obtaining a precipitate of the resin, and then filtering the precipitate and drying the solvent. From the viewpoint of reducing residual ionic impurities, a thermal cyclization method is preferred. 99. 99. 99. id="p-99"
id="p-99"
[0099] The types of preferred first polar solvents (A1) and second polar solvents (A2) may be determined in accordance with the types of the insulating heat-resistant resin (B) and insulating heatresistant resin (C). Examples of preferred combinations (mixed solvents) of the first polar solvent (A1) and the second polar solvent (A2) include the two types (a) and (b) described below. 100. 100. 100. id="p-100"
id="p-100"
[0100] (a) A combination of the first polar solvent (A1): an aforementioned nitrogen-containing solvent such as N-methylpyrrolidone or dimethylacetamide; an aforementioned sulfur-containing solvent such as dimethylsulfoxide; an aforementioned lactone-based solvent such as γ-butyrolactone; or an aforementioned phenol-based solvent such as xylenol, and the second polar solvent (A2): an aforementioned ether-based solvent such as diethylene glycol dimethyl ether; an aforementioned ketone -based solvent such as cyclohexanone; an aforementioned ester-based solvent such as butyl cellosolve acetate; an aforementioned alcohol-based solvent such as butanol; or an aforementioned aromatic hydrocarbon-based solvent such as xylene. (b) A combination of the first polar solvent (A1): an aforementioned ether-based solvent such as tetraethylene glycol dimethyl ether; or an aforementioned ketone-based solvent such as cyclohexanone, and the second polar solvent (A2): an aforementioned ester-based solvent such as butyl cellosolve acetate or ethyl acetate; an aforementioned alcohol-based solvent such as butanol; an aforementioned polyether alcohol-based solvent such as diethylene glycol monoethyl ether; or an aforementioned aromatic hydrocarbon-based solvent such as xylene. 101. 101. 101. id="p-101"
id="p-101"
[0101] Examples of the insulating heat-resistant resin (B) and the insulating heat-resistant resin (C) that may be used with the type (a) mixed solvent include the resins described below. Examples of the insulating heat-resistant resin (B) include resins having structural units represented by formulas (1) to (10) shown below. 102. 102. 102. id="p-102"
id="p-102"
[0102] Image available on "Original document" In formula (1), X represents -CH2-, -O-, -CO-, -SO2-, or a group represented by any of formulas (a) to (i) shown below, and in formula (i), p represents an integer of 1 to 100. 103. 103. 103. id="p-103"
id="p-103"
[0103] Image available on "Original document" In formula (2), R<1>and R<2>each represent a hydrogen atom or a hydrocarbon group of 1 to 6 carbon atoms, and may be the same or different. X has the same meaning as X in formula (1). 105. 105. 105. id="p-105"
id="p-105"
[0105] Image available on "Original document" In formula (3), M is a group represented by formula (c), (h), (i) or (j) shown below, and in formula (i), p represents an integer of 1 to 100. 106. 106. 106. id="p-106"
id="p-106"
[0106] Image available on "Original document" 107. 107. 107. id="p-107"
id="p-107"
[0107] Image available on "Original document" In formula (4), X has the same meaning as X in formula (1). 108. 108. 108. id="p-108"
id="p-108"
[0108] Image available on "Original document" In formula (5), X has the same meaning as X in formula (1). 109. 109. 109. id="p-109"
id="p-109"
[0109] Image available on "Original document" In formula (6), R<3>and R<4>each represent a methyl group, ethyl group, propyl group or phenyl group, and may be the same or different. X has the same meaning as X in formula (1). 110. 110. 110. id="p-110"
id="p-110"
[0110] Image available on "Original document" In formula (8), x1represents 0 or 2, and X has the same meaning as X in formula (1). 112. 112. 112. id="p-112"
id="p-112"
[0112] Image available on "Original document" Examples of the insulating heat-resistant resin (C) include resins having structural units represented by formulas (11) to (20) shown below. 115. 115. 115. id="p-115"
id="p-115"
[0115] Image available on "Original document" In formula (11), Y is a group represented by formula (a), (c) or (h) shown below. 116. 116. 116. id="p-116"
id="p-116"
[0116] Image available on "Original document" 117. 117. 117. id="p-117"
id="p-117"
[0117] Image available on "Original document" In formula (12), Y has the same meaning as Y in formula (11). The portions indicated by * are bonded together (this convention also applies below). 118. 118. 118. id="p-118"
id="p-118"
[0118] Image available on "Original document" Image available on "Original document" In formula (14), Z represents -CH2-, -O-, -CO-, -SO2-, or a group represented by formula (a) or (d) shown below. 120. 120. 120. id="p-120"
id="p-120"
[0120] Image available on "Original document" In formula (16), Z has the same meaning as Z in formula (14). 123. 123. 123. id="p-123"
id="p-123"
[0123] Image available on "Original document" In formula (20), X has the same meaning as X in formula (1), and each of n and m independently represents an integer of 1 or greater. The ratio (n/m) between n and m is preferably within a range from 80/20 to 30/70, and more preferably from 70/30 to 50/50. 127. 127. 127. id="p-127"
id="p-127"
[0127] Among the various combinations described above, using a lactone-based solvent or nitrogencontaining solvent as the first polar solvent (A1), and an ether-based solvent or ester-based solvent as the second polar solvent (A2), and using a resin represented by formula (1) as the insulating heatresistant resin (B), and a resin having a structural unit represented by formula (20) or formula (16) as the insulating heat-resistant resin (C) is preferred. 128. 128. 128. id="p-128"
id="p-128"
[0128] Examples of the insulating heat-resistant resin (B) and the insulating heat-resistant resin (C) that may be used with the type (b) mixed solvent include the resins described below.
Examples of the insulating heat-resistant resin (B) include resins having structural units represented by formulas (21) and (22) shown below, and polysiloxaneimides having structural units represented by formula (6) shown above. 129. 129. 129. id="p-129"
id="p-129"
[0129] Image available on "Original document" In formula (22), Z<1>represents -O-, -CO-, or a group represented by any of formulas (d), (e), (k) and (1) shown below. R<5>and R<6>each represent a group represented by formula (m) or (n) shown below, and may be the same or different. Further, p represents an integer of 1 to 100. 131. 131. 131. id="p-131"
id="p-131"
[0131] Image available on "Original document" Image available on "Original document" Image available on "Original document" Examples of the insulating heat-resistant resin (C) include polyetheramideimides having a structural unit in which X in the above formula (1) is a group represented by formula (a), (b) or (i) shown below, and the polyimides represented by formulas (5) to (9) shown above (but excluding those cases where X in formulas (5), (6) and (8) is a group represented by formula (a) shown below). 134. 134. 134. id="p-134"
id="p-134"
[0134] Image available on "Original document" 135. 135. 135. id="p-135"
id="p-135"
[0135] Image available on "Original document" In formula (i), p represents an integer of 1 to 100. 136. 136. 136. id="p-136"
id="p-136"
[0136] There are no particular limitations on the order of addition of the raw materials when preparing the insulating resin coating material. For example, the above raw materials for the insulating resin coating material may all be mixed together simultaneously, or the first polar solvent (A1) and the second polar solvent (A2) may first be mixed, the insulating heat-resistant resin (B) then mixed with the mixed solvent, and the insulating heat-resistant resin (C) then added to the mixed solution of the first polar solvent (A1), the second polar solvent (A2) and the insulating heat-resistant resin (B).
It is preferable that the raw material mixture for the insulating resin coating material is heated to a temperature at which the insulating heat-resistant resin (C) dissolves satisfactorily in the mixed solution of the first polar solvent (A1), the second polar solvent (A2) and the insulating heat-resistant resin (B), and is mixed thoroughly under stirring or the like. 138. 138. 138. id="p-138"
id="p-138"
[0138] At room temperature, the insulating resin coating material obtained in the manner described above has the insulating heat-resistant resin (C) dispersed in a solution containing the first polar solvent (A1), the second polar solvent (A2) and the insulating heat-resistant resin (B). In other words, the insulating heat-resistant resin (C) exists as a filler in the insulating resin coating material, and can impart a suitable level of thixotropy to the insulating resin coating material during supply of the coating material to the upper portion of the wire. 139. 139. 139. id="p-139"
id="p-139"
[0139] The insulating heat-resistant resin (C) dispersed within the insulating resin coating material may exist in particulate form with an average particle size of not more than 50 pm, preferably from 0.01 to 10 μm, and more preferably from 0.1 to 5 μm. Further, the maximum particle size is preferably 10 μm, and more preferably 5 μm. The average particle size and maximum particle size of the insulating heat-resistant resin (C) can be measured using a particle size distribution analyze SALD-2200 manufactured by Shimadzu Corporation. 140. 140. 140. id="p-140"
id="p-140"
[0140] The mixing ratio between the first polar solvent (A1) and the second polar solvent (A2) varies depending on the types of insulating heat-resistant resin (B) and insulating heat-resistant resin (C) used, the solubility of these resins in the first polar solvent (A1) and the second polar solvent (A2), and the amounts used of the resins, but from the viewpoint of maintaining a superior balance between the fluidity of the insulating resin coating material, the resolution of the resin film, the shape retention and the flatness of the surface, the mixing ratio (A1 : A2) is typically within a range from 6:4 to 9: 1, and is preferably from 6.5:3.5 to 8.5:1.5, and particularly preferably from 7:3 to 8:2. 141. 141. 141. id="p-141"
id="p-141"
[0141] In the insulating resin coating material, the mixed solvent of the first polar solvent (A1) and the second polar solvent (A2) is added in an amount that is preferably within a range from 100 to 3,500 parts by mass, and more preferably from 150 to 1,000 parts by mass, per 100 parts by mass of the total resin mass of the insulating heat-resistant resin (B) and the insulating heat-resistant resin (C). 142. 142. 142. id="p-142"
id="p-142"
[0142] The mixing ratio between the insulating heat-resistant resin (B) and the insulating heatresistant resin (C) is not particularly limited, and the blend amounts may be set as desired, but the insulating heat-resistant resin (C) is preferably added in an amount of 10 to 300 parts by mass, and more preferably an amount of 10 to 200 parts by mass, per 100 parts by mass of the total amount of the insulating heat-resistant resin (B). If the amount used of the insulating heat-resistant resin (C) is less than 10 parts by mass, then the thixotropy properties of the obtained heat-resistant insulating resin coating material tend to deteriorate, whereas if the amount exceeds 300 parts by mass, then the physical properties of the obtained resin film tend to deteriorate. 143. 143. 143. id="p-143"
id="p-143"
[0143] From the viewpoint of shape retention, the insulating resin coating material has a viscosity at 25°C that is within a range from 30 to 500 Pa.s, preferably from 50 to 400 Pa.s, and more preferably from 70 to 300 Pa.s. If the viscosity at 25°C is 30 Pa.s or less, then shape retention during printing tends to become problematic. Further, if the viscosity is 500 Pa.s or greater, then the workability tends to be more likely to deteriorate. The viscosity can be controlled by adjusting the non-volatile fraction concentration (hereafter abbreviated as NV) of the insulating resin coating material, or adjusting the molecular weight of the first polar solvent (A1), the insulating heat-resistant resin (B) or the insulating heat-resistant resin (C). For example, the molecular weights of the insulating heatresistant resin (B) and the insulating heat-resistant resin (C), measured as a standard polystyreneequivalent weight average molecular weight using gel permeation chromatography, are typically adjusted to values within a range from 10,000 to 100,000, preferably from 20,000 to 80,000, and particularly preferably from 30,000 to 60,000. 144. 144. 144. id="p-144"
id="p-144"
[0144] The insulating resin coating material has a thixotropic index that is typically within a range from 2.0 to 10.0, preferably from 2.0 to 6.0, more preferably from 2.5 to 5.5, and even more preferably from 3.0 to 5.0. If the thixotropic index is less than 2.0, then the printability deteriorates, whereas if the thixotropic index exceeds 6.0, then the workability deteriorates and producing the insulating resin coating material becomes difficult. 145. 145. 145. id="p-145"
id="p-145"
[0145] . Resin Sealing Member The resin sealing member is provided so as to cover at least the aforementioned second sealing layer. The resin sealing member is preferably provided across the entire surface of the substrate so as to cover the semiconductor element and the upper surface of the second sealing layer. Because the wire has already been sealed, the occurrence of problems such as wire flow need not be considered during formation of the resin sealing member. The resin sealing member is not particularly limited, and may be formed using the types of materials known in the technical field. 146. 146. 146. id="p-146"
id="p-146"
[0146] Examples of the material used for forming the resin sealing member include a curable composition containing an epoxy resin and a phenol resin. The phenol resin is used as a curing agent for the epoxy resin.
Specific examples of the epoxy resin include a biphenyl epoxy resin, a bisphenol (such as bisphenol F and bisphenol A) epoxy resin, a triphenylmethane epoxy resin, an ortho-cresol novolac epoxy resin, and a naphthalene epoxy resin. Further, specific examples of the phenol resin include a triphenylmethane phenol resin, a phenol aralkyl phenol resin, a xyloc phenol resin, a copolymer phenol aralkyl phenol resin, a naphthol aralkyl phenol resin, and a biphenylene aralkyl phenol resin. For both types of resin, a single resin may be used alone, or a combination of two or more resins may be used. 147. 147. 147. id="p-147"
id="p-147"
[0147] FIG. 3 is a series of schematic cross-sectional views describing a method for producing a semiconductor device, wherein (a) to (d) correspond to each of the steps. In one embodiment, the production method includes at least steps (a) to (c) described below, and preferably also includes step (d). 148. 148. 148. id="p-148"
id="p-148"
[0148] Step (a): As illustrated in FIG. 3(a), the substrate 1 and the semiconductor element 2 disposed on top of the substrate 1 are electrically connected by the wire 3. The term "electrically connected" usually means that an electrode (not shown in the drawings) is provided on each of the substrate 1 and the semiconductor element 2, and these electrodes are connected using a wire. Connection of the wire can be achieved using a wire bonding device. In one embodiment, the height from the surface of the substrate to the apex 3a of the wire (indicated by the reference sign "h" in the drawing) may be from 0.5 to 1.5 mm. For example, the height is preferably about 1 mm. Further, the wire diameter, in the case of a gold wire, may be within a range from 10 μm to 30 μm. In those cases where an aluminum wire is used in a power semiconductor application, the wire diameter of the aluminum wire may be within a range from 80 to 600 μm, and the height h also tends to increase compared with the case of a gold wire. 149. 149. 149. id="p-149"
id="p-149"
[0149] Step (b): As illustrated in FIG. 3(b), a liquid sealing material is supplied to the space beneath the apex 3a of the wire. There are no particular limitations on the method used for supplying the liquid sealing material, and a dispenser method, injection method, or printing method or the like may be used. In one embodiment, a dispenser method is preferably employed. Among the various possibilities, a method in which a jet dispenser device is used to inject the liquid sealing material from the side of the wire is preferred. By using a jet dispenser device to inject the liquid sealing material into the space beneath the wire, the space can easily be filled without voids. By subsequently curing the liquid sealing material supplied to the space, the first sealing layer 4a can be formed. Curing of the liquid sealing material may be conducted prior to supply of the insulating resin coating material described in the subsequent step (c), or may be conducted after supply of the insulating resin coating material. For example, in those cases where the liquid sealing material is a thermosetting resin, the liquid sealing material is preferably cured by heating following injection of the liquid sealing material into the space. The temperature during this heated curing may be adjusted appropriately depending on the type of liquid sealing material being used, but a typical temperature is preferably within a range from 100 to 200°C. 150. 150. 150. id="p-150"
id="p-150"
[0150] Step (c): As illustrated in FIG. 3(c), an insulating resin coating material is supplied onto the top of the first sealing layer 4a with the wire 3 interposed therebetween. In those cases where curing of the liquid sealing material is not conducted during step (b), the insulating resin coating material is supplied onto the top of the liquid sealing material that has been supplied into the aforementioned space. There are no particular limitations on the method used for supplying the insulating resin coating material, and a dispenser method or an injection method or the like may be used. In one embodiment, a dispenser method is preferably employed. The insulating resin coating material is preferably supplied on top of the first sealing layer formed from the cured product of the liquid sealing material. By performing step (c) following step (b), the insulating resin coating material can be retained on top of the wire without the occurrence of problems such as liquid flow, and subsequent drying enables the second sealing layer to be formed easily.
In one embodiment, from the viewpoint of ensuring satisfactory insulation properties, the thickness of the second sealing layer is preferably at least 5 pm, more preferably at least 8 pm, and even more preferably 10 pm or greater. On the other hand, from the viewpoint of reducing thickness, the above thickness is preferably not more than 100 μm, more preferably not more than 50 pm, and even more preferably 30 pm or less. In one embodiment, the above thickness is preferably within a range from 10 to 30 μm. Accordingly, the amount of the insulating resin coating material supplied is preferably adjusted so that the thickness following drying falls within the above range. 151. 151. 151. id="p-151"
id="p-151"
[0151] Step (d): As illustrated in FIG. 3(d), a resin sealing member is formed so as to cover at least the second sealing layer 4b. The resin sealing member is preferably formed so as to cover the entire surface of the semiconductor element and the substrate, including the second sealing layer 4b. In the production method of this embodiment, because the wire is sealed prior to the formation of the resin sealing member, problems such as wire flow do not occur. There are no particular limitations on the technique used for forming the resin sealing member, and techniques known in the technical field may be used.
In one embodiment, formation of the resin sealing member can be conducted by performing transfer molding in a mold having the desired shape using a curable composition containing the epoxy resin and phenol resin described above. Further, there are no particular limitations on the thickness of the resin sealing member, and because the insulation properties can be ensured by the second sealing layer, the resin sealing member may have a thin design. In one embodiment, the thickness of the semiconductor device obtained following formation of the resin sealing member is preferably not more than 1.5 mm, and more preferably 1.1 mm or less. 152. 152. 152. id="p-152"
id="p-152"
[0152] In one embodiment, the method for producing a semiconductor device has a step of electrically connecting a substrate and a semiconductor element disposed on the substrate using a wire, a step of forming a first sealing layer by supplying a liquid sealing material to the space below the apex of the wire and then curing the liquid sealing material, and a step of forming a second sealing layer by supplying an insulating resin coating material to the top of the first sealing layer through the wire and then performing drying. In another embodiment, the method for producing a semiconductor device also includes, following the step of forming the second sealing layer in the production method of the above embodiment, a step of forming a resin sealing member that covers at least the second sealing layer.
EXAMPLES 153. 153. 153. id="p-153"
id="p-153"
[0153] Embodiments of the present invention are described below using a series of examples, but the present invention is in no way limited by the following examples, and of course also includes embodiments having various modifications. 154. 154. 154. id="p-154"
id="p-154"
[0154] 1. Preparation of Liquid Sealing Material (Preparation Example 1) The materials shown below were blended together, and then kneaded and dispersed using a triple roll mill and a vacuum Raikai mixer to prepare a liquid sealing material.
Epoxy resin 1: p-(2,3-epoxypropoxy)-N,N-bis(2,3-expoxypropyl)aniline (product name: EP-3950S, manufactured by ADEKA Corporation, total chlorine content: not more than 1,500 ppm) 60 parts Epoxy resin 2: a bisphenol F epoxy resin (product name: YDF-8170C, manufactured by NIPPON STEEL Chemical & Material Co., Ltd.) 20 parts Epoxy resin 3: 1,6-hexanediol diglycidyl ether (product name: SR-16HL, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) 20 parts Curing agent: diethyltoluenediamine (product name: jER Cure W, manufactured by Mitsubishi Chemical Corporation) 42 parts Ion trapping agent: a bismuth-based ion trapping agent (product name: IXE-500, manufactured by Toagosei Co., Ltd.) 3 parts Solvent: butyl carbitol acetate 57 parts Inorganic filler 1 : a spherical fused silica surface-treated with a silane coupling agent (product name: SE5050-SEJ, manufactured by Admatechs Co., Ltd., volume average particle size: 1.5 μm) 707 parts Inorganic filler 2: a spherical fused silica surface-treated with a silane coupling agent (product name: SE2050-SEJ, manufactured by Admatechs Co., Ltd., volume average particle size: 0.5 μm) 235 parts 155. 155. 155. id="p-155"
id="p-155"
[0155] For the liquid sealing material prepared in the manner described above, the viscosity at 25°C and a shear velocity of 10 s<-1>and the viscosity at 75°C and a shear velocity of 5 s<-1>were measured. Further, the viscosity at 75°C and a shear velocity of 50 s<-1>was also measured, and the thixotropic index at 75°C was determined. The results of these measurements are shown below.
°C viscosity: 20 (Pa.s) (shear velocity: 10 s<-1>) 75°C viscosity: 2.0 (Pa.s) (shear velocity: 5 s<-1>) Thixotropic index at 75°C: 1.7 (ratio of viscosities at shear velocities 5 s<-1>/50 s<-1>) Measurement of the viscosity at 25°C was performed using an E-type viscometer (VISCONIC EHD, manufactured by Tokyo Keiki Inc.). Further, measurement of the viscosity at 75°C was performed using a rheometer (product name: AR2000, manufactured by TA Instruments, Inc.). 156. 156. 156. id="p-156"
id="p-156"
[0156] Further, the chlorine ion content (ppm) of the prepared liquid sealing material was measured. The measurement was performed by conducting a treatment by ion chromatography at 121 °C for 20 hours using sodium carbonate as the eluent. The result of the measurement revealed a chlorine ion content in the liquid sealing material of 10 ppm. 157. 157. 157. id="p-157"
id="p-157"
[0157] 2. Preparation of Insulating Resin Coating Material (Preparation 2) Preparation of Insulating Resin Coating Material (P-l)> (1) Synthesis Example for Heat-Resistant Resin (B) A 5-liter four-neck flask fitted with a thermometer, a stirrer, a nitrogen inlet tube and a condenser fitted with an oil-water separator was charged, under a stream of nitrogen, with 650.90 g (1.59 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (hereafter abbreviated as BAPP) and 43.80 g (0.18 mol) of l,3-bis(3-aminopropyl)-tetramethyldisiloxane (hereafter abbreviated as BY16-871 (manufactured by Dow Coming Toray Co., Ltd.)), and these components were then dissolved by adding 3,609.86 g of N-methyl-2-pyrrolidone (hereafter abbreviated as NMP). Subsequently, 384.36 g (1.83 mol) of trimellitic anhydride chloride (TAC) was added while the flask was cooled to ensure that the temperature of the solution did not exceed 20°C.
After stirring for one hour at room temperature, 215.90 g (2.14 mol) of triethylamine (hereafter abbreviated as TEA) was added while the flask was cooled to ensure that the temperature did not exceed 20°C, and the reaction was then allowed to proceed for one hour at room temperature, thus producing a polyamic acid varnish. The obtained polyamic acid varnish was then subjected to a dehydration reaction at 180°C over a period of 6 hours, thus producing a varnish of a polyamideimide resin. This polyamideimide resin varnish was poured into water, and the resulting precipitate was separated, ground, and dried to obtain a polyamideimide resin powder (PAI-1). The Mw value of the thus obtained polyamideimide resin (PAI-1) was 77,000. 158. 158. 158. id="p-158"
id="p-158"
[0158] (2) Synthesis Example for Heat-Resistant Resin (C) A 1-liter four-neck flask fitted with a thermometer, a stirrer, a nitrogen inlet tube and a condenser fitted with an oil-water separator was charged, under a stream of nitrogen, with 69.72 g (170.1 mmol) of BAPP and 4.69 g (18.9 mmol) of BY16-871, and these components were then dissolved by adding 693.52 g of NMP. Subsequently, 25.05 g (119.0 mmol) of TAC and 25.47 g (79.1 mmol) of 3,4,3', 4'-benzophenonetetracarboxylic dianhydride (hereafter abbreviated as BTDA) were added while the flask was cooled to ensure that the temperature did not exceed 20°C.
After stirring for one hour at room temperature, 14.42 g (142.8 mmol) of TEA was added while the flask was cooled to ensure that the temperature did not exceed 20°C, and the reaction was then allowed to proceed for one hour at room temperature, thus producing a polyamic acid varnish. The obtained polyamic acid varnish was then subjected to a dehydration reaction at 180°C over a period of 6 hours, thus producing a varnish of a polyimide resin. This polyimide resin varnish was poured into water, and the resulting precipitate was separated, ground, and dried to obtain a polyimide resin powder (PAIF-1). The Mw value of the thus obtained polyimide resin (PAIF-1) was 42,000. 159. 159. 159. id="p-159"
id="p-159"
[0159] (3) Preparation of Insulating Resin Coating Material A 0.5 -liter four-neck flask fitted with a thermometer, a stirrer, a nitrogen inlet tube and a condenser was charged, under a stream of nitrogen, with 92.4 g of γ-butyrolactone (hereafter abbreviated as γ-BL) as the first polar solvent (A1), 39.6 g of triethylene glycol dimethyl ether (hereafter abbreviated as DMTG) as the second polar solvent (A2), 30.8 g of the previously synthesized polyamideimide resin powder (PAI-1) as the heat-resistant resin (B) and 13.2 g of the previously synthesized polyimide resin powder (PAIF-1) as the heat-resistant resin (C), and the temperature was raised to 180°C while the mixture was stirred. After stirring at 180°C for two hours, the heating was stopped, the reaction mixture was allowed to cool under stirring, when the temperature reached 60°C, 16.8 g of γ-BL and 7.2 g of DMTG were added, stirring was continued for a further one hour, and the reaction mixture was then cooled, yielding a yellow composition. The composition was placed in a filtration device KST-47 (manufactured by Admatechs Co., Ltd), and a silicone rubber piston was inserted to perform pressurized filtration under a pressure of 3.0 kg/cm<2>, thus obtaining an insulating resin coating material (P-1). 160. 160. 160. id="p-160"
id="p-160"
[0160] (Preparation Example 3) Preparation of Inorganic Filler-Containing Insulating Resin Coating Material (P-2)> Following preparation of PAI-1 in the same manner as Preparation Example 2(1), 5 wt% of AEROSIL 200 manufactured by Nippon Aerosil Co., Ltd. was added to prepare an insulating resin coating material of a comparative example.
Specifically, a 0.5 -liter four-neck flask fitted with a thermometer, a stirrer, a nitrogen inlet tube and a condenser was charged, under a stream of nitrogen, with 92.4 g of γ-BL as the first polar solvent (A1), 39.6 g of triethylene glycol dimethyl ether (hereafter abbreviated as DMTG) as the second polar solvent (A2), 30.8 g of the previously synthesized polyamideimide resin powder (PAI-1) as the heat-resistant resin (B) and 9.8 g of AEROSIL 200, and the temperature was raised to 180°C while the mixture was stirred. After stirring at 180°C for two hours, the heating was stopped, the reaction mixture was allowed to cool under stirring, when the temperature reached 60°C, 16.8 g of γ-BL and 7.2 g of DMTG were added, stirring was continued for a further one hour, and the reaction mixture was then cooled, yielding a yellow composition. The composition was placed in a filtration device KST-47 (manufactured by Admatechs Co., Ltd), and a silicone rubber piston was inserted to perform pressurized filtration under a pressure of 3.0 kg/cm<2>, thus obtaining an insulating resin coating material (P-2) of a comparative example. 161. 161. 161. id="p-161"
id="p-161"
[0161] 3 . Production of Semiconductor Devices (Example 1) A semiconductor element was mounted on a glass epoxy substrate using solder, and a structure was prepared in which the semiconductor element mounted on the substrate and the substrate were electrically connected by gold wires. Twenty gold bonding wires were formed on each of the four sides of the semiconductor element (giving a total of 80 wires). The height from the substrate to the wire apexes was 0.9 mm.
Subsequently, a jet dispenser device (device name: S2-910, manufactured by Nordson Advanced Technology K.K.) was used to supply the liquid sealing material obtained in Preparation Example 1 to the space beneath the apexes of the wires in the structure described above. The supplied liquid sealing material was then cured by heating at 175°C for two hours, thus forming a first sealing layer (wire sealing layer).
A dispenser device (device name: SDP500, manufactured by Saneitec Co., Ltd.) was then used to supply the insulating resin coating material obtained in Preparation Example 2 onto the top of the first sealing layer with the wires interposed therebetween. Subsequently, the coating film of the coating material was dried by heating under temperature conditions of 100°C for 30 minutes and then 200°C for one hour, thus forming a second sealing layer (insulating protective layer) with a thickness of 12 pm. 162. 162. 162. id="p-162"
id="p-162"
[0162] (Comparative Example 1) A structure having a semiconductor element mounted on a substrate wherein the semiconductor element and the substrate were electrically connected by wires was prepared, in the same manner as Example 1. Subsequently, a dispenser device (device name: SDP500, manufactured by Saneitec Co., Ltd.) was used to supply the insulating resin coating material obtained in Preparation Example 2 onto only the top of the wires in the structure. The space beneath the wires was obstructed by the wires, and was unable to be satisfactorily filled with the insulating resin coating material. The coating film was then dried by heating under temperature conditions of 100°C for 30 minutes and then 200°C for one hour, thus forming a sealing layer (insulating protective layer). The amount supplied of the insulating resin coating material was adjusted so as to achieve a dried film thickness of the sealing layer above the wires of 12 μm, the same as Example 1. 163. 163. 163. id="p-163"
id="p-163"
[0163] (Comparative Example 2) A structure having a semiconductor element mounted on a substrate wherein the semiconductor element and the substrate were electrically connected by wires was prepared, in the same manner as Example 1. Subsequently, a jet dispenser device (device name: S2-910, manufactured by Nordson Advanced Technology K.K.) was used to supply the liquid sealing material obtained in Preparation Example 1 to both the space beneath the wires and the region above the wires in the structure. The coating film was then cured by heating under temperature conditions of 175°C for two hours, thus forming a sealing layer (wire sealing layer). The amount supplied of the liquid sealing material was adjusted so as to achieve a film thickness of the sealing layer positioned above the wires of 12 μm, the same as Example 1. 164. 164. 164. id="p-164"
id="p-164"
[0164] (Comparative Example 3) A structure having a semiconductor element mounted on a substrate wherein the semiconductor element and the substrate were electrically connected by wires was prepared, in the same manner as Example 1. Subsequently, a first sealing layer was formed beneath the wires in the structure in the same manner as Example 1, and the inorganic filler-containing insulating resin coating material obtained in Preparation Example 3 was then supplied onto the top of the first sealing layer with the wires interposed therebetween. The amount supplied of the inorganic filler-containing insulating resin coating material was adjusted so as to achieve a dried film thickness of the sealing layer above the wires of 12 μm, the same as Example 1. 165. 165. 165. id="p-165"
id="p-165"
[0165] 4. Evaluation of Semiconductor Devices Semiconductor Device Reliability> For each of the semiconductor devices obtained in Example 1 and Comparative Examples 1 to 3, the reliability of the device was evaluated by ascertaining the presence or absence of voids in the sealing layers on the wires using ultrasonic microscope measurements.
The ultrasonic microscope measurements were conducted using an apparatus D9000 manufactured by SONOSCAN, Inc. In those cases where the existence of voids in the semiconductor device could not be detected by the ultrasonic microscope measurements, the reliability was judged to be good. In contrast, when the ultrasonic microscope measurements confirmed the existence of voids, the reliability was judged to be poor. The results are shown in Table 1. 166. 166. 166. id="p-166"
id="p-166"
[0166] For each of the semiconductor devices obtained in Example 1 and Comparative Examples 1 to 3, a measurement sample was prepared in the manner described below to enable evaluation of the dielectric breakdown voltage of the sealing layer formed on the upper portion of the wires.
A measurement sample 1 corresponding with Example 1 (Comparative Example 1) was prepared by first using an applicator to apply the insulating resin coating material P-1 obtained in Preparation Example 2 to an aluminum substrate. Heating was then conducted in an oven at 100°C for 30 minutes and then at 200°C for one hour, thus obtaining a dried coating film with a thickness of 10 pm.
A measurement sample 2 corresponding with Comparative Example 2 was prepared by first using an applicator to apply the liquid sealing material obtained in Preparation Example 1 to an aluminum substrate. The coating film was then cured by heating at 175°C for two hours, thus obtaining a cured film with a thickness of 10 μm.
A measurement sample 3 corresponding with Comparative Example 3 was prepared by first using an applicator to apply the inorganic filler-containing insulating resin coating material P-2 obtained in Preparation Example 3 to an aluminum substrate. Heating was then conducted in an oven at 100°C for 30 minutes and then at 200°C for one hour, thus obtaining a dried coating film with a thickness of 10 μm.
The measurement samples 1 to 3 produced in the manner described above were each sandwiched between a pair of electrodes, and the dielectric breakdown voltage was measured. The measurement was performed in oil, with reference to JIS C2110, under conditions including a rate of voltage increase of 0.5 kV/second, a measurement temperature of room temperature, and an electrode shape composed of 020 mm spheres. The results are shown in Table 1. 167. 167. 167. id="p-167"
id="p-167"
[0167] For each of the semiconductor devices obtained in Example 1 and Comparative Examples 1 to 3, rather than actually measuring the ESD resistance, the ESD resistance was evaluated from the value of the dielectric breakdown voltage for a separately measured dried coating film (cured film). For example, the dielectric breakdown voltage of the measurement sample 1 prepared above was 230 kV/mm, which is the same as 230 V/μm. Accordingly, if the film thickness of the sealing layer (film) obtained upon film formation is 10 μm, this is equivalent to the sealing layer (film) having an insulation of 2,300 V (2.3 kV). Usually, if a sealing layer (film) is able to maintain insulation relative to a voltage exceeding 2 kV, then sufficient ESD resistance can be obtained for the semiconductor device.
Generally, increasing the film thickness enhances the insulation properties, enabling the ESD resistance to be improved. For example, in those cases where a material is applied in sufficient amount to obtain a film thickness of at least 100 pm, ensuring favorable insulation properties is easy. However, achieving uniform application of a sufficient amount of the insulating resin coating material to obtain a film thickness of at least 100 μm is difficult. Further, this is also undesirable in terms of going against the current market trend demanding thinner semiconductor devices. Accordingly, as described below, 2 kV was used as a benchmark value, and the insulation of each of the measurement samples 1 to 3 with a thickness of 10 μm, calculated from the measured value for the dielectric breakdown voltage in each case, was used to evaluate the ESD resistance. The results are shown in Table 1.
Claims (20)
1. A semiconductor device having a substrate, a semiconductor element disposed on thesubstrate, a Wire that electrically connects the substrate and the semiconductor element, a first sealinglayer that seals a space below an apex of the Wire,Wherein the first sealing layer is formed from a cured film of a liquid sealing material,characterized by a second sealing layer that is provided on top of the first sealing layer Withthe Wire interposed therebetvveen,Wherein the second sealing layer is formed from a dried coating film of an insulating resincoating material, Wherein the insulating resin coating material comprises a resin f1ller having an average particle size of 0.1 to 5.0 um.
2. The semiconductor device according to Claim 1, also having a resin sealing member provided so as to cover at least the second sealing layer.
3. The semiconductor device according to Claim 1 or 2, Wherein a dielectric breakdoWn voltage of the dried coating film of the insulating resin coating material is at least 150 kV/mm.
4. The semiconductor device according to any one of Claims 1 to 3, Wherein the insulating resincoating material comprises a mixed solvent that includes a first polar solvent (Al) and a second polarsolvent (A2) having a boiling point lower than that of the first polar solvent (Al) in a mass ratio(A1:A2) Within a range from 6:4 to 9:1, an insulating heat-resistant resin (B) that is soluble in the mixed solvent of the first polarsolvent (A1) and the second polar solvent (A2) at room temperature, and an insulating heat-resistant resin (C) Which, at room temperature, is soluble in the first polarsolvent (A1), insoluble in the second polar solvent (A2), and insoluble in the mixed solvent of the first polar solvent (A1) and the second polar solvent (A2).
5. The semiconductor device according to any one of Claims 1 to 4, Wherein a viscosity at 25°C of the insulating resin coating material is Within a range from 30 to 500 Pa-s.
6. The semiconductor device according to any one of Claims 1 to 5, Wherein a thixotropic index at 25°C of the insulating resin coating material is Within a range from 2.0 to 10.0.
7. The semiconductor device according to any one of Claims 1 to 6, Wherein the insulating resin coating material comprises at least one insulating resin selected from the group consisting of a polyamide, a polyamideimide and a polyimide.
8. The semiconductor device according to any one of Claims 1 to 7, Wherein a thickness of the second sealing layer is not more than 100 um.
9. The semiconductor device according to Claim 8, Wherein the thickness of the second sealing layer is not more than 50 um.
10. The semiconductor device according to any one of Claims 7 to 9, Wherein a Tg value of the insulating resin is at least 150°C.
11. The semiconductor device according to any one of Claims 1 to 10, Wherein the liquid sealingmaterial comprises a therrnosetting resin component and an inorganic filler, and a thixotropic index at75°C of the liquid sealing material, obtained as a value of viscosity A/ viscosity B, is Within a rangefrom 0.1 to 2.5, Wherein the viscosity A is a viscosity (Pa-s) measured under conditions of 75°C and ashear velocity of 5 s* and the viscosity B is a viscosity (Pa-s) measured under conditions of 75°C and a shear velocity of 50 s*.
12. The semiconductor device according to any one of Claims 1 to 11, Wherein a chlorine ion content in the liquid sealing material is not more than 100 ppm.
13. The semiconductor device according to Claim 11 or 12, Wherein a maximum particle size of the inorganic filler in the liquid sealing material is not more than 75 um.
14. The semiconductor device according to any one of Claims 1 to 13, Wherein a viscosity of theliquid sealing material measured under conditions of 75°C and a shear velocity of 5 s* is not more than 3.0 Pa-s.
15. The semiconductor device according to any one of Claims 1 to 14, Wherein a viscosity of theliquid sealing material measured under conditions of 25°C and a shear velocity of 10 s* is not more than 30 Pa-s.
16. The semiconductor device according to any one of Claims 11 to 15, Wherein an amount of the inorganic filler, based on a total mass of the liquid sealing material, is at least 50% by mass.
17. The semiconductor device according to any one of Claims 11 to 16, Wherein the therrnosetting resin component in the liquid sealing material comprises an aromatic epoxy resin and an aliphatic epoxy resin.
18. The semiconductor device according to Claim 17, Wherein the aromatic epoxy resin comprisesat least one resin selected from the group consisting of a liquid bisphenol epoxy resin and a liquid glycidylamine epoxy resin, and the aliphatic epoxy resin comprises a linear aliphatic epoxy resin.
19. The semiconductor device according to any one of Claims 1 to 18, Which is used in a fingerprint authentication sensor.
20. A method for producing a semiconductor device having a substrate, a semiconductor elementdisposed on the substrate, a Wire that electrically connects the substrate and the semiconductorelement, a first sealing layer that seals a space below an apex of the Wire, and a second sealing layerthat is provided on top of the first sealing layer With the Wire interposed therebetWeen, the methodcomprising: a step of electrically connecting the substrate and the semiconductor element disposed on thesubstrate using the Wire, a step of forrning the first sealing layer by supplying a liquid sealing material to the spacebelow the apex of the Wire and performing curing to obtain a cured film of the liquid sealing material,and a step of forrning the second sealing layer by supplying an insulating resin coating material ontop of the first sealing layer With the Wire interposed therebetWeen and performing drying to obtain adried coating film of the insulating resin coating material, Wherein the insulating resin coating material comprises a resin filler having an average particle size of 0.1 to 5.0 um.
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JPWO2019031513A1 (en) | 2020-10-01 |
SE2050185A1 (en) | 2020-02-20 |
WO2019031513A1 (en) | 2019-02-14 |
TWI763902B (en) | 2022-05-11 |
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