JP6106389B2 - Pre-installed semiconductor sealing film - Google Patents

Description

  The present invention relates to a pre-installed semiconductor sealing film, and more particularly to a pre-installed semiconductor sealing film used in flip chip bonding.

  In recent years, flip chip bonding has been used as a semiconductor chip mounting method that can cope with higher density and higher frequency of wiring and the like of semiconductor devices. Generally, in flip chip bonding, a gap between a semiconductor chip and a substrate is sealed with a material called underfill.

  Conventionally, in flip chip bonding, after bonding a semiconductor chip and a substrate by soldering or the like, a gap between the semiconductor chip and the substrate is filled with an underfill agent, which is a thermosetting liquid sealing resin composition, and a semiconductor device is manufactured. The manufacturing method was performed. In recent years, first, after applying an underfill agent to a substrate and mounting a semiconductor chip, the underfill agent is cured and the semiconductor chip and the substrate are connected at the same time, thereby shortening the process and shortening the curing time. As a result, a pre-supplied flip chip bonding process that can manufacture a semiconductor device at low cost and low energy has attracted attention. A liquid encapsulant resin composition for this process (hereinafter referred to as a pre-supplied liquid encapsulating resin) Called composition).

  However, in the flip chip bonding process using the pre-supplied liquid sealing resin composition, bleeding on the upper surface of the semiconductor chip is a problem. FIG. 1 is a schematic cross-sectional view for explaining a bleed phenomenon in a flip chip bonding process using a pre-supplied liquid sealing resin composition. FIG. 1 is a diagram in which a semiconductor chip 24 on which bumps 23 are formed is placed on a substrate 21 on which wirings 22 are formed after applying a pre-feed type liquid sealing resin composition 20. At this time, if the supply amount of the pre-feed type liquid sealing resin composition 20 is increased, a bleed 20B is generated on the side surface of the semiconductor chip 24, and the pre-feed type liquid sealing resin composition 20 rises. There is a problem that a bleed 20 </ b> C in which the pre-feed type liquid sealing resin composition 20 rises up to the upper surface of the semiconductor chip 24 is generated.

  In order to solve this problem, a mounting method using a pre-installed semiconductor sealing film (hereinafter referred to as pre-installed flip chip mounting) is being considered instead of the pre-supplied liquid sealing resin composition. . In the pre-installation type flip chip mounting, the supply amount of the pre-installation type semiconductor encapsulation film can be controlled by the thickness and area of the pre-installation type semiconductor encapsulation film. This is because the supply amount can be easily controlled. In addition to the properties as a general sealing material, this pre-installed semiconductor sealing film may be flexible and not harden during preheating at, for example, 60 to 80 ° C. for flip chip mounting. Required. As in the case of the pre-feed type, the pre-installed flip chip mounting can produce a semiconductor device that is flip-chip mounted at low cost and low energy.

  As a component of the pre-installed semiconductor sealing film, an epoxy resin is used to satisfy the requirements as a general sealing material, and a latent curing agent may be used to cure after forming a film. Conceivable. The epoxy resin composition using a latent curing agent includes (a) an epoxy resin, (b) a thermoplastic resin that can be dissolved in the epoxy resin, and (c) a latent heat curing type that is activated at 70 to 90 ° C. An epoxy resin composition comprising a curing agent is disclosed (Patent Document 1). However, in this epoxy resin composition, since the latent curing agent is activated at 70 to 90 ° C., the epoxy resin composition is cured and cannot be used as a pre-installed semiconductor sealing film. .

  On the other hand, the latent curing agent includes an amine-based curing agent (A) -containing core, and a capsule film covering the core, and the capsule film has an amine-based curing agent (A) as a curing agent. A capsule-type curing agent containing a cured product of a resin is disclosed (Patent Document 2). However, this capsule-type curing agent is intended to obtain high connection reliability, adhesive strength, and high sealing performance even under low temperature or short-time curing conditions (see “Invention of Patent Document 2”). Therefore, it cannot be used as a latent curing agent for a pre-installed semiconductor sealing film as it is.

JP-A-6-9758 International Publication No. 2004/037885

  SUMMARY OF THE INVENTION An object of the present invention is to provide a pre-installed semiconductor sealing film that can be used in pre-installation type flip chip mounting because it does not harden during pre-heating for flip chip mounting but cures during flip chip mounting. .

The present invention relates to a pre-installed semiconductor sealing film that has solved the above problems by having the following configuration.
[1] It contains (A) a liquid epoxy resin, (B) a thermoplastic resin, (C) a curing agent, (D) a latent curing accelerator heat-treated at 50 to 100 ° C., and (E) an inorganic filler. A pre-installed film for semiconductor encapsulation, which is characterized.
[2] The pre-installed semiconductor sealing film according to [1], wherein the component (B) is 10 to 30 parts by mass with respect to 100 parts by mass of the pre-installed semiconductor sealing film.
[3] The preinstalled semiconductor according to [1] or [2], wherein the component (B) is 15 to 65 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B). Film for sealing.
[4] The preinstalled semiconductor according to any one of [1] to [3], wherein the component (D) is 2 to 5 parts by mass with respect to 100 parts by mass of the preinstalled semiconductor sealing film. Film for sealing.
[5] The preinstalled semiconductor according to any one of [1] to [4], wherein the component (E) is 40 to 70 parts by mass with respect to 100 parts by mass of the preinstalled semiconductor sealing film. Film for sealing.
[6] A semiconductor device manufactured using the pre-installed semiconductor sealing film according to any one of [1] to [5].

  According to the present invention [1], there is provided a pre-installed semiconductor sealing film that is not cured during preheating for flip chip mounting but is cured during flip chip mounting. be able to.

  According to the present invention [6], it is possible to obtain a semiconductor device that can be manufactured by low-cost, low-energy pre-installed flip chip mounting at low cost.

It is a schematic diagram of the cross section for demonstrating the bleed phenomenon in the flip chip bonding process using the pre-feed type liquid sealing resin composition. It is a schematic diagram of the cross section for demonstrating the flip chip mounting using the film for semiconductor sealing. It is a figure which shows the measurement result in DSC of (D) component used in Example 1. FIG. 10 is a scanning electron micrograph of the cross section of Example 7. 2 is a scanning electron micrograph of the cross section of Example 1. FIG. 2 is a scanning electron micrograph of the cross section of Comparative Example 1. It is a schematic diagram explaining the evaluation method of the adhesive strength of a board | substrate and a semiconductor chip.

  The pre-installed semiconductor sealing film of the present invention (hereinafter referred to as a semiconductor sealing film) includes (A) a liquid epoxy resin, (B) a thermoplastic resin, (C) a curing agent, and (D) 50 to 100 ° C. And a latent curing accelerator heat-treated with (E) and an inorganic filler.

  (A) A component provides sclerosis | hardenability, heat resistance, and adhesiveness to the film for semiconductor sealing, and provides durability to the film for semiconductor sealing after hardening. As component (A), liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, liquid naphthalene type epoxy resin, liquid aminophenol type epoxy resin, liquid biphenyl type epoxy resin, liquid hydrogenated bisphenol type epoxy resin, liquid fat Cyclic epoxy resin, liquid alcohol ether type epoxy resin, liquid cyclic aliphatic type epoxy resin, liquid fluorene type epoxy resin, etc., liquid naphthalene type epoxy resin, liquid bisphenol F type epoxy resin, liquid bisphenol A type epoxy resin, A liquid aminophenol type epoxy resin and a liquid biphenyl type epoxy resin are preferred from the viewpoints of curability, heat resistance, adhesiveness, and durability. The epoxy equivalent of the component (A) is preferably 80 to 250 g / eq from the viewpoints of reactivity and curing density. Commercially available products include Nippon Steel Chemical's bisphenol A type epoxy resin (product name: YD-128), Nippon Steel Chemical's bisphenol F type epoxy resin (product name: YDF870GS), Mitsubishi Chemical's aminophenol type epoxy resin (grade: JER630, JER630LSD), DIC naphthalene type epoxy resin (product name: HP4032D), Momentive Performance Materials Japan (product name: TSL9906), and the like. (A) A component may be individual or may use 2 or more types together.

  The component (B) imparts flexibility to the semiconductor sealing film. Examples of the component (B) include phenoxy resins, polyimide resins, polyethylene resins, polystyrene resins, polyesters, polyethers, polyamides, and polyether ester amides. From the viewpoint of alleviating internal stress of the cured semiconductor sealing film. A phenoxy resin is preferred. Here, the phenoxy resin is a polymer polyhydroxy polyether (thermoplastic resin) synthesized by a direct reaction of a dihydric phenol and epichlorohydrin or an addition polymerization reaction of a diglycidyl ether of a dihydric phenol and a dihydric phenol. Yes, a polymer having a weight average molecular weight of 10,000 or more. The weight average molecular weight is preferably 10,000 to 100,000, more preferably 40,000 to 80,000. Here, the weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.

  Dihydric phenols include bisphenol A, bisphenol F, bisphenol S, dihydroxynaphthalene, bisphenol D, bisphenol E, bisphenol Z, bisphenol fluorene, biscresol fluorene, biphenol, catechol, resorcin, hydroquinone, 2,5-di-t. -Halogenated bisphenols such as butyl hydroquinone or brominated bisphenol A, 10- (2,5-dihydroxyphenyl) -10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 7-dihydroxynaphthyl) -10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinylhydroquinone, diphenylphosphinylnaphthoxy Phosphine-containing phenols such as cyclooctylene phosphinyl-1,4-benzenediol or cyclooctylene phosphinyl-1,4-naphthalenediol, and the like. Examples include those produced by direct reaction of phenols and epichlorohydrin, or those synthesized by addition polymerization reaction of the above dihydric phenols and their diglycidyl ether compounds. As the component (B), bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, bisphenol A-bisphenol F copolymer type phenoxy resin, and the like are more preferable. When the component (B) is a phenoxy resin, the stress between the semiconductor chip and the substrate is relieved to relieve the internal stress of the pre-installed semiconductor sealing film after curing, and between the semiconductor chip and the substrate ( It is considered that the adhesion is improved by the presence of the component B). (B) As a commercial item of a component, Nippon Steel Chemical phenoxy resin (product name: YP-50S) etc. are mentioned. (B) A component may be individual or may use 2 or more types together.

  The component (C) only needs to have the curing ability of the component (A). Examples of the component (C) include phenolic curing agents, amine-based curing agents, and acid anhydride-based curing agents, and are reactive. From the viewpoint of stability, a phenolic curing agent is preferred. Examples of the phenolic curing agent include phenol novolak and cresol novolak, and phenol novolak is preferable. Examples of amine-based curing agents include chain aliphatic amines, cycloaliphatic amines, aliphatic aromatic amines, aromatic amines, and the like, and aromatic amines are preferred. Examples of acid anhydride curing agents include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, hydrogenated methylnadic acid anhydride, and trialkyltetrahydroanhydride. Phthalic acid, methylcyclohexene tetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, ethylene glycol bisanhydro trimellitate, glycerin bis (anhydro trimelli Tate) Monoacetate, dodecenyl succinic anhydride, aliphatic dibasic acid polyanhydride, chlorendic anhydride, methylbutenyl tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, methyl hymic anhydride, alkenyl In succinic anhydride substituted, glutaric anhydride and the like, methyl butenyl tetrahydrophthalic acid anhydride are preferred. Commercially available products include DIC phenol resin curing agents (product name: KA-1160), Meiwa Kasei phenol curing agents (product names: MEH8000, MEH8005), Nippon Kayaku amine curing agents (product name: Kayahard A-A), Mitsubishi. Examples thereof include chemical acid anhydrides (grade: YH306, YH307), 3 or 4-methyl-hexahydrophthalic anhydride (product name: HN-5500) manufactured by Hitachi Chemical. (C) A component may be individual or may use 2 or more types together.

  The component (D) does not cure the semiconductor sealing film during preheating for flip chip mounting, but allows the semiconductor sealing film to be cured during flip chip mounting. Here, the latent curing accelerator is microencapsulated with urethane resin as the shell and curing accelerator as the core, and the epoxy resin and masterbatch are the workability and curing speed. From the viewpoint of storage stability, it is preferable. It is considered that the urethane resin in the shell is appropriately polymerized by heat-treating the epoxy resin and the masterbatch latent curing accelerator at 50 to 100 ° C. If the heat treatment temperature of the latent curing accelerator is less than 50 ° C., the stability during preheating and the connectivity of flip chip mounting are not sufficient, and if the heat treatment temperature of the latent curing accelerator exceeds 100 ° C., epoxy The master batch of the resin and the latent curing accelerator is semi-cured or cured. (D) The heat processing temperature of a component is preferable in it being 60-100 degreeC, it is more preferable in it being 70-100 degreeC, and it is further more preferable in it being 70-90 degreeC.

  (D) It is preferable that the heat processing time of a component is 6 to 72 hours. In addition, when the heat processing temperature of (D) component is 50 degreeC, it is preferable that it is 48 hours or more, and when the heat processing temperature of (D) component is 100 degreeC, it is preferable that it is 48 hours or less, It is more preferable that it is 12 hours or less.

  Moreover, (D) component has preferable reaction start temperature in 110-150 degreeC, and it is more preferable in it being 120-142 degreeC. Here, the reaction start temperature is measured by DSC (differential scanning calorimetry). Here, the reaction start temperature is a temperature at which the latent curing agent starts a curing reaction in the film for semiconductor encapsulation (D), and is observed as a temperature at which the exotherm of the (D) component starts in DSC. Is done.

  As the latent curing accelerator, an imidazole compound curing accelerator microencapsulated with a urethane resin or the like is preferable from the viewpoint of storage stability, and is dispersed in a liquid epoxy resin such as liquid bisphenol A to be masterbatched. Further, a microencapsulated imidazole compound curing accelerator is more preferable from the viewpoints of workability, curing speed, and storage stability. Examples of imidazole curing agents include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2,4- Diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a] benzimidazole can be mentioned, and 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine, 2 , 4-Diamino-6- [2'-undecylimidazolyl- (1) -ethyl-s-triazine, 2, - diamino-6- [2'-ethyl-4'-methylimidazolyl- - (1 ')] - ethyl -s- triazine, and curing rate, workability, preferable from the viewpoint of moisture resistance.

  As a commercial product of the epoxy resin and the masterbatch latent latent accelerator, a microencapsulated imidazole compound curing agent manufactured by Asahi Kasei E-materials (product name: NovaCure 4982 (very thick type), NovaCure 3932 (medium thickness type), NovaCure 4921 (thin type), HX3722, HXA3932HP), and the like, and a microencapsulated imidazole compound curing agent (product name: NovaCure 4982 (extra-thick type)) manufactured by Asahi Kasei E-Materials is preferred. Here, the very thick type is a latent curing accelerator having a gelation temperature of 140 to 150 ° C., the middle thickness type is a latent curing accelerator having a gelation temperature of 100 to 110 ° C., and the thin type is It is a latent curing accelerator having a gelation temperature of 70 to 80 ° C. The gelation temperature is measured at a gel time of less than 5 minutes according to JIS K5600-9-1. (D) A component may be individual or may use 2 or more types together.

  (E) The elasticity modulus and thermal expansion coefficient of the film for semiconductor sealing after hardening are adjusted with a component. Examples of the component (E) include silica fillers such as colloidal silica, hydrophobic silica, fine silica, and nano silica, aluminum nitride, alumina, silicon nitride, and boron nitride. Silica filler is preferable from the viewpoint of versatility and electrical characteristics. . Moreover, the average particle diameter of the component (E) (if it is not granular, the average maximum diameter) is not particularly limited, but is 0.05 to 50 μm, and the filler is uniformly dispersed in the film for semiconductor encapsulation It is preferable to make it. When the thickness is less than 0.05 μm, the viscosity of the semiconductor sealing film increases during mounting, and the fluidity may be deteriorated. If it exceeds 50 μm, it may be difficult to make the filler uniformly present in the semiconductor sealing film, and the connection between the semiconductor and the substrate may be difficult. (E) As for the average particle diameter of a component, it is more preferable that it is 0.1-30 micrometers, and it is further more preferable that it is 0.1-5 micrometers. Commercially available products include silica manufactured by Admatex (product name: SO-E2, average particle size: 0.5 μm), silica made by DENKA (product name: FB-5D, average particle size: 5 μm), manufactured by Fuso Chemical Industries (product name) : SP03B, average particle diameter: 300 nm) and the like. Here, the average particle diameter of the component (E) is measured by a dynamic light scattering nanotrack particle size analyzer. (E) A component may be individual or may use 2 or more types together.

  The film for semiconductor encapsulation preferably contains the component (B) in an amount of 7 to 30 parts by mass, more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the semiconductor encapsulation film. This is because if the amount is 7 parts by mass or more, the semiconductor sealing film has sufficient flexibility, and if it is 30 parts by mass or less, the semiconductor sealing film has sufficient flexibility. If it is 30 parts by weight or more, the semiconductor sealing film tends to be brittle and it is difficult to maintain a flexible film shape.

  Moreover, as for the film for semiconductor sealing, as for (B) component, it is preferable in it being 15-65 mass parts with respect to the sum total: 100 mass parts of (A) component and (B) component. More preferably. This is because if the amount is 15 parts by mass or more, the flexibility of the semiconductor sealing film is sufficient, and if it is 65 parts by mass or less, the semiconductor sealing film is sufficiently flexible.

  The curing agent equivalent of the component (C) is preferably 0.1 to 1.1 times the epoxy equivalent of the component (A), and if it is less than 0.1 times, the curing with the component (A) tends to be insufficient. Adhesion tends to be insufficient. On the other hand, when the curing agent equivalent of the component (C) exceeds 1.1 times, curing with the component (A) tends to be insufficient, and voids are likely to occur. Further, the curing agent equivalent of the component (C) is preferably 0.1 to 0.5 times the functional group equivalent of the component (B), and if it is less than 0.1 times, curing tends to be insufficient. If it exceeds 0.5 times, it tends to be hard and brittle after curing. From the above, the curing agent equivalent of the component (C) is preferably 0.2 to 1.6 times the total of the epoxy equivalent of the component (A) and the functional group equivalent of the component (B). Here, the curing agent equivalent of the component (C) is, for example, a phenol equivalent when the component (C) is a phenolic curing agent, an amine equivalent when the component is an amine curing agent, and an acid anhydride equivalent when the component is an acid anhydride curing agent. is there.

  The component (D) does not cure the semiconductor sealing film during preheating for flip chip mounting, but cures the semiconductor sealing film during flip chip mounting. 2-5 parts by mass is preferable. In addition, when the latent hardening | curing agent is masterbatched with the epoxy resin, naturally the preferable amount of (D) component calculates with the quantity of the latent hardening | curing agent in a masterbatch.

  (E) From a viewpoint of the elasticity modulus and thermal expansion coefficient of the film for semiconductor sealing after hardening, it is preferable in it being 30-80 mass parts with respect to 100 mass parts of pre-installed type semiconductor sealing films. 40-70 parts by mass is more preferable.

  In the film for semiconductor encapsulation, an ion trap agent for preventing migration of wiring and bumps, rosin flux agent, acid anhydride, hydrazide, carbon, and the like, as long as the object of the present invention is not impaired. Acid-based fluxing agents, coupling agents such as silane coupling agents, pigments such as carbon black, dyes, antifoaming agents, antioxidants, leveling agents, thixotropic agents, stress relaxation agents, other additives, etc. Can be blended. In particular, carbon black is preferably added from the viewpoint of concealment. From the viewpoint of suppressing voids during flip chip mounting, it is preferable not to include an organic solvent, particularly a low boiling point organic solvent.

  The thickness of the semiconductor sealing film is preferably 10 to 100 μm from the viewpoint of the gap between the flip chip and the substrate, and the height of the bump of the semiconductor chip and the height of the wiring on the substrate.

  The melt viscosity of the semiconductor sealing film is preferably 10,000 to 40,000 Pa · s from the viewpoint of suppressing voids at the time of bonding and suppressing voids at the time of flip chip mounting.

  The film for semiconductor encapsulation can be formed by applying a film-forming composition for semiconductor encapsulation on a support and then drying it. Examples of the support include a polyethylene terephthalate (PET) film.

  The composition for forming a film for semiconductor encapsulation, for example, stirs, melts, mixes, and disperses components (A) to (E) and other additives simultaneously or separately, with heat treatment as necessary. Can be obtained. The mixing, stirring, dispersing and the like devices are not particularly limited, and a raikai machine equipped with a stirring and heating device, a three-roll mill, a ball mill, a planetary mixer, a bead mill and the like can be used. . Moreover, you may use combining these apparatuses suitably.

  The method for applying the semiconductor sealing film-forming composition on the support is not particularly limited, but the microgravure method, the slot die method, and the doctor blade method are preferable from the viewpoint of thinning and film thickness control.

  The drying conditions of the film forming composition for encapsulating a semiconductor applied on a support can be appropriately set according to the thickness of the application, for example, at 60 to 120 ° C. for about 1 to 30 minutes. It can be. The semiconductor sealing film thus obtained is in an uncured state.

  In FIG. 2, the schematic diagram of the cross section for demonstrating the front-installation type flip chip mounting using the film for semiconductor sealing is shown. As shown in FIG. 2A, first, a substrate 11 on which wirings 12 are formed is prepared. Next, as shown in FIG. 2B, the semiconductor sealing film 10 is placed on the substrate 11 on which the wiring 12 is formed, and preheated. Thereafter, as shown in FIG. 2C, the bumps 13 formed on the semiconductor chip 14 are aligned so as to correspond to the wirings 12 on the substrate 11. Here, both the wiring 12 and the bump 13 have a solder layer formed on the surface thereof. Finally, as shown in FIG. 2D, after the wiring 12 on the substrate 11 and the bump 13 on the semiconductor chip 14 are brought into contact with each other, the wiring 12 on the substrate 11 and the bump on the semiconductor chip 14 are heated. 13 and the semiconductor sealing film are simultaneously cured. The semiconductor sealing film becomes the cured first-installation type semiconductor sealing film 10A.

  Curing at the time of flip-chip mounting of the semiconductor sealing film is preferably performed at 180 to 300 ° C. for 5 to 30 seconds, and particularly preferably within 15 seconds from the viewpoint of improving productivity.

  Thus, the pre-installed semiconductor sealing film of the present invention is not cured at the time of preheating for flip chip mounting, but is cured at the time of flip chip mounting, so that it can be used for the pre-installed flip chip mounting. Moreover, a heating process can be put after mounting and the hardening of a semiconductor sealing film can also be accelerated | stimulated.

  The present invention will be described with reference to examples, but the present invention is not limited thereto. In the following examples, parts and% indicate parts by mass and mass% unless otherwise specified.

[Examples 1 to 20, Comparative Examples 1 to 5, Reference Examples 1 to 3]
The composition for film formation for semiconductor sealing was adjusted with the composition shown in Tables 1-3. The components (A) to (D) were mixed with methyl ethyl ketone, and then the component (E) was mixed to obtain a film forming composition for semiconductor encapsulation. The obtained semiconductor sealing film-forming composition was applied using a doctor blade and then dried to obtain a semiconductor sealing film having a thickness of 50 μm. In addition, Tables 1 to 3 show the reaction start temperatures of the component (D) measured by a NETZSCH DSC (model number: DSC204 F1 Phoenix). In Table 3, in Comparative Examples 4 and 5 using imidazole instead of the component (D), the activity start temperature of imidazole is shown in the column of reaction start temperature or activity start temperature. Here, the activation start temperature refers to the temperature at which imidazole is activated alone, and was measured from the temperature at which DSC started to generate heat. In FIG. 3, the measurement result in DSC of (D) component used in Example 1 is shown. A broken line in FIG. 3 indicates a baseline. As can be seen from FIG. 3, the heat generation start temperature of the component (D) used in Example 1 was 110 ° C.

[Evaluation of stability during installation]
In order to evaluate the stability at the time of pre-installation in the pre-installation type flip chip mounting, the minimum melt viscosity (initial minimum melt viscosity) of the semiconductor sealing film was measured by VAR100 manufactured by Viscoanalyzer. Next, the minimum melt viscosity after being held at 70 ° C. for 3 hours was similarly measured. The stability at the time of installation (unit:%) is expressed by the following formula:
(Stability at installation) = (Minimum melt viscosity after 3 hours) / (Initial minimum melt viscosity)
× 100
Determined by The stability at the time of installation is good if it is 160% or less. Tables 1 to 3 show the evaluation results of stability at the time of installation.

[Evaluation of connectivity between wiring on substrate and bump on semiconductor chip]
A Si chip having a width of 7 mm, a length of 7 mm, and a thickness of 125 μm in which 544 bumps of 30 μm were formed at a pitch of 50 μm was prepared. The bumps are bumps that are solder-capped with Cu pillars. Further, a glass epoxy substrate having a substrate thickness: 350 μm having wiring corresponding to the bump pattern of the silicon chip was prepared. A film for sealing a semiconductor was placed on the substrate having the wiring and preheated at 70 ° C. Using a flip chip bonder, the bump on the Si chip and the wiring on the substrate were brought into contact with each other at a load of 30 N and 200 ° C. for 1.2 seconds on the preheated wiring on the substrate, and then the temperature was raised. After maintaining at 280 ° C. for 10 seconds, the sample was cooled to 200 ° C. and taken out from the flip chip bonder to prepare an evaluation sample. When the resistance value between the bump on the Si chip and the wiring on the substrate is measured with a multimeter (model number: HP34001A) manufactured by Agilent Technologies, the resistance value is less than 1.1 times the design value. The case where it was 1.1 times or more of the design value but was within the measurement range of the measuring device was “◯”, and the case where it was not possible to measure because it was outside the measuring range of the measuring device was “×”. Here, the design value of the resistance value was 29Ω. Tables 1 to 3 show the evaluation results of the connectivity between the wiring on the substrate and the bumps on the semiconductor chip (shown as connectivity in the table).

  In FIG. 4, the scanning electron micrograph of the cross section of Example 7 is shown. In FIG. 5, the scanning electron micrograph of the cross section of Example 1 is shown. In FIG. 6, the scanning electron micrograph of the cross section of the comparative example 1 is shown. FIG. 4 shows a case where the connectivity evaluation result is “◎”, FIG. 5 shows a case where “◯”, and FIG. 6 shows a case where “×”. In FIG. 6, the semiconductor sealing film remains between the wiring on the substrate and the bump on the semiconductor chip.

[Evaluation of void generation rate]
An evaluation sample prepared for evaluating the connectivity between the wiring on the substrate and the bump on the semiconductor chip was measured with an ultrasonic microscope, and the void generation rate was evaluated. The void generation rate (unit:%) is expressed by the following formula:
(Void occurrence rate) = (Void area) / (Chip area) × 100
I asked for it. Tables 1 to 3 show the evaluation results of the void generation rate.

[Evaluation of bonding strength between substrate and semiconductor chip]
An evaluation sample prepared for evaluating the connectivity between the wiring on the substrate and the bump on the semiconductor chip was used. FIG. 7 is a schematic diagram illustrating a method for evaluating the adhesive strength between the substrate and the semiconductor chip. An FR-4 substrate dried at 150 ° C. for 20 minutes as a substrate 31 and a 2 mm square SiN film-attached Si chip as a semiconductor chip 34 were prepared. A 1 mm square semiconductor sealing film was placed on the substrate 31, and the semiconductor chip 34 was mounted on the semiconductor sealing film. Thereafter, the semiconductor sealing film was cured at 160 ° C. for 60 minutes to form a cured semiconductor sealing film 30A. Shear strength (unit: N / mm ² ) was measured using an Aiko-Engineering tabletop strength tester (model number: 1605HTP). The shear strength is preferably 3.0 N / mm ² or more. Tables 1 to 3 show the evaluation results of the shear strength (described as adhesive strength in the table) between the substrate and the semiconductor chip.

  To summarize the test results, in all of Examples 1 to 21, the stability of the previous installation, the connectivity between the wiring on the substrate and the bump on the semiconductor chip, the void generation rate, the adhesive strength between the substrate and the semiconductor chip. The evaluation result was good. In particular, in Examples 2 to 18 and 20, the evaluation results of the connectivity between the wiring on the substrate and the bump on the semiconductor chip were very good. In contrast, Comparative Example 1 in which the latent curing accelerator was heat-treated at 40 ° C. had poor stability and connectivity at the time of installation, and Comparative Example 2 in which the latent curing accelerator was heat-treated at 110 ° C. When the master batch of the epoxy resin and the latent curing agent was heat-treated, the master batch was semi-cured, and the film forming composition for semiconductor encapsulation could not be mixed. Comparative Example 3 using a latent curing accelerator that was not heat-treated had poor stability and connectivity at the time of installation. In Reference Example 1, when the master batch of the epoxy resin and the latent curing agent was heat-treated, the master batch was cured, and the composition for forming a film for semiconductor encapsulation could not be mixed. In Comparative Example 4 using imidazole 1 instead of the component (D), the void generation rate was high. In Comparative Example 5 using imidazole 2 instead of the component (D), the connectivity between the wiring on the substrate and the bump on the semiconductor chip was poor, and it was semi-cured in the stability evaluation test at the time of installation. . Reference Example 2 using a latent curing agent that was heat-treated at 50 ° C. for 12 hours as the component (D) had poor stability and connectivity at the time of previous installation.

  The pre-installed semiconductor sealing film of the present invention is not cured during preheating for flip chip mounting, but is cured during flip chip mounting, and thus can be used for pre-installed flip chip mounting. For this reason, by using the pre-installed semiconductor sealing film of the present invention, a semiconductor device manufactured by low-cost, low-energy pre-installed flip chip mounting can be obtained.

DESCRIPTION OF SYMBOLS 1, 2 Semiconductor device 10 Pre-installation type semiconductor sealing film 10A, 30A Cured pre-installation type semiconductor sealing film 11, 21, 31 Substrate 12, 22 Wiring 13, 23 Bump 14, 24, 34 Semiconductor chip 20 Supply type liquid sealing resin composition 20B, 20C Bleed 35 Share tool

Claims (5)

(A) Liquid naphthalene type epoxy resin, liquid bisphenol F type epoxy resin, and liquid epoxy resin containing liquid bisphenol A type epoxy resin, (B) thermoplastic resin which is phenoxy resin, (C) phenolic curing agent, (D ) was heated at 50 to 100 ° C., latent curing accelerator reaction starting temperature heat generation of DSC starts is 110 to 150 ° C., and unrealized, and the component (D) to (E) an inorganic filler, previously stationary semiconductor sealing film with respect to 100 parts by weight, and wherein 2 to 5 parts by weight including Mukoto, film for previously installed semiconductor encapsulation.   (B) The pre-installed type semiconductor sealing film according to claim 1, wherein the component is 10 to 30 parts by mass with respect to 100 parts by mass of the pre-installed semiconductor sealing film.   The pre-installed semiconductor sealing film according to claim 1 or 2, wherein the component (B) is 15 to 65 parts by mass with respect to 100 parts by mass of the total of the component (A) and the component (B). The film for semiconductor device sealing of any one of Claims 1-3 whose (E) component is 40-70 mass parts with respect to 100 mass parts of film | membrane for pre-installation type semiconductor sealing. . The semiconductor device containing the hardened | cured material of the film for semiconductor device sealing of any one of Claims 1-4 .