JP5981384B2 - Resin composition, resin film, semiconductor device and manufacturing method thereof - Google Patents

Description

  The present invention relates to a resin composition, a resin film, a semiconductor device, and a manufacturing method thereof.

  In recent years, the size of a wafer used for manufacturing a semiconductor device has been increased in size and thickness, and a technique for sealing these at the wafer level is required. Therefore, in addition to the conventional transfer molding method of solid type epoxy resin, a compression molding method using a liquid type epoxy resin has been proposed (Patent Document 1).

  However, in transfer molding, there is a concern that the wire may be deformed because the resin flows in a narrow portion, and there is a problem that a filling failure accompanying an increase in the sealing area is likely to occur. In addition, in the compression molding method, it is difficult to finely control the molding range at the end surface of the wafer, and it is not easy to optimize the fluidity and physical properties when the liquid sealing resin is poured into the molding machine. It was. In addition, due to the recent increase in wafer size and thinning of the wafer, warpage of the wafer after molding, which has not been a problem until now, has become a problem, and even better wafer protection performance is required. For this reason, it is possible to mold the wafers in a lump without causing problems such as defective filling on the wafer surface, and development of a wafer mold material having low warpage and good wafer protection performance after molding is desired. It was.

International Publication No. 2009/142065 Pamphlet

  The present invention has been made to solve the above-mentioned problems, and can mold a wafer in a lump (wafer mold), and particularly has a large diameter and good moldability for a thin film wafer, At the same time, to provide a resin composition and a resin film that can provide low warpage and good wafer protection performance after molding, can perform a molding process well, and can be suitably used for a wafer level package, It is another object of the present invention to provide a semiconductor device molded with the resin film and a method for manufacturing the semiconductor device.

［式中、Ｒ^１〜Ｒ^４は同一でも異なっていてもよい炭素原子数１〜８の１価炭化水素基を示す。また、ｍは１〜３００の整数、ｎは２または３であり、ａは正数、ｂは０又は正数である。ＸおよびＹは下記一般式（２）または（３）で示される２価の有機基である。

（式中、Ｚは

のいずれかより選ばれる２価の有機基であり、ｐは０又は１である。また、Ｒ^５は炭素原子数１〜４のアルキル基又はアルコキシ基であり、Ｒ^６は水素原子またはメチル基、エチル基を表し、相互に同一でも異なっていてもよい。ｈは０、１、２のいずれかである。）］

（Ｂ）熱硬化性樹脂、
（Ｃ）フィラー。 The present invention has been made to solve the above problems,
A resin composition comprising the following components (A), (B) and (C) is provided.
(A) a silicone resin having a weight average molecular weight of 3000 to 500000 represented by the following general formula (1):

[Wherein, R ^{1 to} R ⁴ represent a monovalent hydrocarbon group having 1 to 8 carbon atoms which may be the same or different. M is an integer of 1 to 300, n is 2 or 3, a is a positive number, and b is 0 or a positive number. X and Y are divalent organic groups represented by the following general formula (2) or (3).

(Where Z is

And a p is 0 or 1. R ⁵ represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and R ⁶ represents a hydrogen atom, a methyl group, or an ethyl group, and may be the same or different from each other. h is 0, 1, or 2. ]]

(B) thermosetting resin,
(C) Filler.

  Since such a resin composition can be formed into a film, the wafer can be molded in one batch (wafer mold), and has a large diameter and good mold performance and adhesion to a thin film wafer. , Low warpage, wafer protection and reliability, and a resin composition that can be suitably used for wafer level packages.

  Moreover, the quantity of the said (B) component is 5-100 mass parts with respect to 100 mass parts of said (A) component, and the mass fraction of the said (C) component with respect to the total mass is 30-90 mass%. It is preferable.

  Since such a resin composition can be easily formed into a film, the wafer can be easily molded in one batch (wafer mold), and the mold is even better for large-diameter and thin-film wafers. The resin composition is excellent in performance, adhesion, low warpage, wafer protection, and reliability, and becomes a resin composition that can be more suitably used for a wafer level package.

  The thermosetting resin is preferably an epoxy resin.

  If an epoxy resin is used as the thermosetting resin, the adhesion to the wafer and the wafer protection are further improved, so that it can be more suitably used for a wafer level package.

  Furthermore, it is preferable to contain at least one selected from an epoxy resin curing agent and an epoxy resin curing accelerator.

  Containing at least one selected from an epoxy resin curing agent and an epoxy resin curing accelerator is advantageous because the curing reaction can proceed appropriately and uniformly.

  It is preferable that the filler is silica.

  If the filler is silica, the wafer protection can be further improved, and the heat resistance, moisture resistance, strength, etc. can be further improved and the reliability can be improved.

  Moreover, this invention provides the resin film characterized by being formed using the said resin composition.

  If it is a resin film formed in a film shape, it will have good mold performance for large diameter, thin film wafers, and it is not necessary to pour resin when molding the wafers in a lump. This does not cause problems such as poor filling. Moreover, if it is a resin film formed using the said resin composition, it will become a wafer mold material which has the adhesiveness with respect to a wafer, and wafer protective property simultaneously.

  Furthermore, the present invention provides a method for manufacturing a semiconductor device, comprising: a step of attaching the resin film to a semiconductor wafer, molding the semiconductor wafer, and a step of separating the molded semiconductor wafer. provide.

  Thus, since the semiconductor wafer molded with the resin film has a small amount of warpage and is sufficiently protected, a high-quality semiconductor device with a high yield can be manufactured by separating the semiconductor wafer into individual pieces.

  Furthermore, the present invention provides a semiconductor device comprising a semiconductor wafer molded with a heat-cured film obtained by heat-curing the resin film and having the heat-cured film.

  In this way, a semiconductor wafer molded with a heat-cured film obtained by heat-curing a resin film is a wafer that is sufficiently protected with little warping, and a semiconductor device obtained by dividing it into a single piece has a high quality without warping. The semiconductor device can be made.

Since the resin composition of the present invention can be processed into a film shape, it has a good mold performance for a large diameter, thin film wafer. Moreover, since it is excellent in adhesiveness, low warpage, and wafer protection properties, it becomes possible to mold the wafer in a lump, so that the resin film can be suitably used for a wafer level package.
In addition, the semiconductor device and the manufacturing method thereof according to the present invention can provide a high-quality semiconductor device with a high yield.

  As described above, a wafer mold material that can mold a wafer in a lump without causing problems such as poor filling of the wafer surface, and has adhesion, low warpage and good wafer protection performance after molding. Development of was desired.

  Accordingly, as a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the following (A) silicone resin provides a resin composition excellent in adhesion to a wafer and low warpage after curing. In addition, the following (B) thermosetting resin provides adhesion to the wafer and wafer protection, and further (C) filler improves the wafer protection and the reliability of the cured resin composition. The present invention has been completed by finding that a resin film obtained from a resin composition comprising these components becomes a wafer mold material having both adhesion to the wafer and wafer protection.

Hereinafter, although the resin composition of this invention, the resin film obtained from it, a semiconductor device, and its manufacturing method are demonstrated in detail, this invention is not limited to these.
The resin composition of the present invention is
(A) silicone resin,
(B) thermosetting resin,
(C) Contains a filler.

<Resin composition>
[(A) Silicone resin]
In the present invention, the silicone resin as the component (A) functions as a film forming ability.
Moreover, when the obtained resin film is used as a wafer mold material, it provides adhesion to the wafer, low warpage, and good moldability.

［式中、Ｒ^１〜Ｒ^４は同一でも異なっていてもよい炭素原子数１〜８の１価炭化水素基を示す。また、ｍは１〜３００の整数、ｎは２または３であり、ａは正数、ｂは０又は正数である。ＸおよびＹは下記一般式（２）または（３）で示される２価の有機基である。

（式中、Ｚは

のいずれかより選ばれる２価の有機基であり、ｐは０又は１である。また、Ｒ^５は炭素原子数１〜４のアルキル基又はアルコキシ基であり、Ｒ^６は水素原子またはメチル基、エチル基を表し、相互に同一でも異なっていてもよい。ｈは０、１、２のいずれかである。）］

The silicone resin as the component (A) is a silicone resin having a weight average molecular weight of 3000 to 500,000 represented by the following general formula (1).

[Wherein, R ^{1 to} R ⁴ represent a monovalent hydrocarbon group having 1 to 8 carbon atoms which may be the same or different. M is an integer of 1 to 300, n is 2 or 3, a is a positive number, and b is 0 or a positive number. X and Y are divalent organic groups represented by the following general formula (2) or (3).

(Where Z is

And a p is 0 or 1. R ⁵ represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and R ⁶ represents a hydrogen atom, a methyl group, or an ethyl group, and may be the same or different from each other. h is 0, 1, or 2. ]]

  The silicone resin of the present invention contains a repeating unit represented by the above formula (1) and has a polystyrene-reduced weight average molecular weight of 3,000 to 500,000, preferably 5, as measured by GPC using tetrahydrofuran as an elution solvent. 000 to 200,000 polymers. a is a positive number, b is 0 or a positive number, and satisfies 0 <a / (a + b) ≦ 1, and preferably satisfies 0.1 ≦ a / (a + b) ≦ 0.6. Each unit may be bonded at random or may be bonded as a block polymer.

In the above formula (1), m is an integer of 1 to 300, and n is 2 or 3. X and Y are divalent organic groups represented by the above formula (2) or (3). R ¹ to R ⁴ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, and a phenyl group. Is mentioned. Among these, a methyl group and a phenyl group are preferable because of easy availability of raw materials.

In the above formula (2), R ⁵ independently of each other is an alkyl group or alkoxy group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, methyl, ethyl group, propyl group, tert-butyl group, methoxy group. And an ethoxy group. h is 0, 1 or 2, preferably 0.

In the above formula (2), Z is a divalent group selected from any of the groups shown below. p is 0 or 1.

In the above formula (2), R ⁶ is a hydrogen atom, a methyl group or an ethyl group, preferably a hydrogen atom.

  In X of the above formula (1), the ratio of the general formula (3) is preferably 10 mol% to 50 mol%.

（式中、Ｒ^１〜Ｒ^４は同一でも異なっていてもよい炭素原子数１〜８の１価炭化水素基を示し、ｍは１〜３００の整数である）

（式中、Ｚは

のいずれかより選ばれる２価の有機基であり、ｐは０又は１である。また、Ｒ^５は炭素原子数１〜４のアルキル基又はアルコキシ基であり、Ｒ^６は水素原子またはメチル基、エチル基を表し、相互に同一でも異なっていてもよい。ｈは０、１、２のいずれかである。）

((A) Silicone resin production method)
The silicone resin of the present invention has a metal catalyst using a compound selected from the compounds represented by the following general formula (4), the following general formula (5), the following general formula (6) and the following general formula (7). Then, it can be produced by addition polymerization.
In the above formula (1), when b = 0, it is produced without using a compound represented by the following formula (4).

(Wherein R ^{1 to} R ⁴ represent a monovalent hydrocarbon group having 1 to 8 carbon atoms which may be the same or different, and m is an integer of 1 to 300)

(Where Z is

And a p is 0 or 1. R ⁵ represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and R ⁶ represents a hydrogen atom, a methyl group, or an ethyl group, and may be the same or different from each other. h is 0, 1, or 2. )

Examples of the metal catalyst include platinum group metals such as platinum (including platinum black), rhodium and palladium; H ₂ PtCl ₄ · xH ₂ O, H ₂ PtCl ₆ · xH ₂ O, NaHPtCl ₆ · xH ₂ O, KHPtCl ₆ · xH ₂ O, Na ₂ PtCl ₆ · xH ₂ O, K ₂ PtCl ₄ · xH ₂ O, PtCl ₄ · xH ₂ O, PtCl ₂ , Na ₂ HPtCl ₄ · xH ₂ O (wherein x is 0 to 0) Platinum chloride, chloroplatinic acid and chloroplatinic acid salts, such as an integer of 6, preferably 0 or 6, and alcohol-modified chloroplatinic acid (for example, those described in US Pat. No. 3,220,972); Complexes of chloroplatinic acid and olefins (eg, US Pat. No. 3,159,601, US Pat. No. 3,159,662, and US Pat. No. 3,775,452). Described above); a platinum group metal such as platinum black or palladium supported on a carrier such as alumina, silica, carbon; rhodium-olefin complex; chlorotris (triphenylphosphine) rhodium (so-called Wilkinson catalyst); and chloride A complex of platinum, chloroplatinic acid or chloroplatinate and a vinyl group-containing siloxane (particularly a vinyl group-containing cyclic siloxane) can be used.

  The amount of the catalyst used may be a catalytic amount, and is 0.0001 to 0.1% by mass, preferably 0.001 to 0.01% by mass, based on the total amount of raw material compounds subjected to the reaction, as a platinum group metal. It is preferable. The addition reaction can be carried out without a solvent, but a solvent may be used as necessary. As the solvent, for example, hydrocarbon solvents such as toluene and xylene are preferable. The reaction temperature may be a temperature at which the catalyst is not deactivated and the polymerization can be completed in a short time, and is preferably 40 to 150 ° C, particularly preferably 60 to 120 ° C. What is necessary is just to select reaction time suitably with the kind and quantity of a polymer, for example, 0.5 to 100 hours, Especially 0.5 to 30 hours are preferable. When a solvent is used, it is subjected to vacuum distillation after completion of the reaction to distill off the solvent.

  The reaction method is not particularly limited. For example, the reaction method is represented by the compound represented by the formula (4), the compound represented by the formula (5), the compound represented by the formula (6), and the formula (7). In the case of reacting with the compound, first, the compounds represented by the formulas (6) and (7) are mixed and heated, and then the metal catalyst is added to the mixed solution, and then the formulas (4) and ( The compound represented by 5) is preferably added dropwise over 0.1 to 5 hours.

  The compounding ratio of each compound is the sum of the number of moles of hydrosilyl groups possessed by the compounds represented by the above formulas (4) and (5) and the compounds represented by the above formulas (6) and (7). The total number of moles of alkenyl groups should be such that the total number of moles of hydrosilyl groups relative to the total number of moles of alkenyl groups is 0.67 to 1.67, preferably 0.83 to 1.25. The weight average molecular weight of the polymer can be controlled by using a monoallyl compound such as o-allylphenol, or a monohydrosilane or monohydrosiloxane such as triethylhydrosilane as a molecular weight modifier.

[(B) Thermosetting resin]
(B) A component improves the adhesiveness to a wafer, and protection property to the resin composition of this invention. In this invention, a thermosetting resin is not specifically limited, For example, an epoxy resin, a phenol resin, a melamine resin, a urethane resin, a polyester resin etc. can be mentioned, Among these, an epoxy resin is preferable. The epoxy resin can undergo a crosslinking reaction with the epoxy group contained in the silicone resin (A). Therefore, when the thermosetting resin is an epoxy resin, the thermosetting resin and the silicone resin (A) undergo a crosslinking reaction when the resin composition is cured. Reliability is further improved.

  Epoxy resins include, for example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, or those hydrogenated thereto, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and other glycidyl ether type epoxy resins, hexahydrophthalic acid Examples include glycidyl ester epoxy resins such as glycidyl ester and dimer acid glycidyl ester, glycidyl amine epoxy resins such as triglycidyl isocyanurate and tetraglycidyl diaminodiphenylmethane, and preferably bisphenol A type epoxy resins and bisphenol F type epoxy resins. And phenol novolac type epoxy resins and cresol novolac type epoxy resins. Examples of these commercially available products include jER1001 (manufactured by Mitsubishi Chemical), Epicron 830S (manufactured by DIC), jER517 (manufactured by Mitsubishi Chemical), and EOCN103S (manufactured by Nippon Kayaku).

  Moreover, a phenol resin can also be used as a thermosetting resin. Examples of the phenol resin include resol type phenol resins and / or novolaks prepared from alkylphenols such as phenol, bisphenol A, pt-butylphenol, octylphenol, and p-cumylphenol, p-phenylphenol, cresol, and the like as raw materials. Type phenolic resin. A thermosetting resin may be used individually by 1 type, or may use 2 or more types together.

  Although the compounding quantity of a thermosetting resin is not specifically limited, It is good that it is 5-100 mass parts with respect to 100 mass parts of (A) component, Preferably it is 5-50 mass parts. If the compounding quantity of a thermosetting resin is in the said range, the adhesiveness and protective property of a resin composition will improve further. Moreover, since the hardened | cured material of this resin composition turns into the hardened | cured material excellent in reliability, it is preferable.

  Moreover, in addition to the said epoxy resin, the resin composition of this invention can contain an epoxy resin hardening | curing agent and / or an epoxy resin hardening accelerator further. By containing an epoxy resin curing agent and / or an epoxy resin curing accelerator, the curing reaction can be appropriately and uniformly advanced. The compounding amount of the epoxy resin curing agent is 1 to 50 parts by mass, preferably 2 to 20 parts by mass with respect to 100 parts by mass of the component (A), and the compounding amount of the epoxy resin curing accelerator is (A). It is good that it is 0.1-10 mass parts with respect to 100 mass parts of components, Preferably it is 0.2-5 mass parts.

  The epoxy resin curing agent is not particularly limited as long as it is usually used, but an aromatic curing agent and an alicyclic curing agent are more preferable from the viewpoint of heat resistance. Examples of the epoxy resin curing agent include amine-based curing agents, acid anhydride-based curing agents, boron trifluoride amine complex salts, and phenol resins. Examples of amine curing agents include aliphatic amine curing agents such as diethylenetriamine, triethylenetetramine and tetraethylenepentamine, alicyclic amine curing agents such as isophoronediamine, and aromatic amines such as diaminodiphenylmethane and phenylenediamine. Examples thereof include a system curing agent and dicyandiamide. Of these, aromatic amine curing agents are preferred. Examples of the acid anhydride curing agent include phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, and the like. The said epoxy resin hardening | curing agent may be used individually by 1 type, or may use 2 or more types together.

  Examples of the epoxy resin curing accelerator include 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and ethyl isocyanate compounds of these compounds, 2-phenylimidazole, 2-phenyl-4-methylimidazole. Imidazole compounds such as 2-phenyl-4-methyl-5-hydroxymethylimidazole and 2-phenyl-4,5-dihydroxymethylimidazole, 1,8-diazabicyclo (5.4.0) undecene-7 (DBU), DBU compounds such as 1,5-diazabicyclo (4.3.0) nonene-5 (DBN), DBU organic acid salt, DBU phenol resin salt, DBU derivative tetraphenylborate salt, triphenylphosphine, tributylphosphine Tris (p-methylphenyl) phos , Tris (p-methoxyphenyl) phosphine, tris (p-ethoxyphenyl) phosphine, triphenylphosphine / triphenylborate, triorganophosphines such as tetraphenylphosphine / tetraphenylborate, quaternary phosphonium salts, triethylene Tertiary amines such as ammonium triphenylborate and tetraphenylborate salts thereof. The said epoxy resin hardening accelerator may be used individually by 1 type, or may use 2 or more types together.

[(C) filler]
Component (C) can impart wafer protection to the resin composition of the present invention, and can further improve heat resistance, moisture resistance, strength, and the like, thereby improving reliability. Examples of fillers include silicates such as talc, calcined clay, unfired clay, mica, glass, titanium oxide, alumina, fused silica (fused spherical silica, fused crushed silica), oxides such as crystalline silica powder, calcium carbonate , Carbonates such as magnesium carbonate and hydrotalcite, hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate and calcium sulfite, zinc borate, and metaborate Examples thereof include borates such as barium oxide, aluminum borate, calcium borate, and sodium borate, and nitrides such as aluminum nitride, boron nitride, and silicon nitride. These fillers may be mixed singly or in combination of two or more. Among these, silica powder such as fused silica and crystalline silica is preferable. Examples of the silica powder include reinforcing silica such as fumed silica and precipitated silica; and crystalline silica such as quartz. Specifically, Aerosil R972, R974, R976 manufactured by Nippon Aerosil Co., Ltd .; SE-2050, SC-2050, SE-1050, SO-E1, SO-C1, SO-E2, and SO-E2 manufactured by Admatechs Co., Ltd. -C2, SO-E3, SO-C3, SO-E5, SO-C5; Musil 120A and Musil 130A manufactured by Shin-Etsu Chemical Co., Ltd. are exemplified.

The average particle diameter of the filler is not particularly limited, but is preferably 0.01 μm or more and 20 μm or less, and particularly preferably 0.01 μm or more and 10 μm or less. If the average particle diameter of the inorganic filler is not less than the above lower limit value, the inorganic filler is less likely to aggregate and the strength becomes high, which is preferable. Moreover, if it is below the said upper limit, since the fluidity | liquidity of the resin between chips | tips becomes high and a filling property becomes favorable, it is preferable. The average particle diameter can be determined by a particle size distribution measuring apparatus using a laser light diffraction method, and can be measured as a mass average value D ₅₀ (that is, a particle diameter or a median diameter when the cumulative mass is 50%). .

  The filler content is preferably 30% by mass or more and 90% by mass or less, more preferably 50% by mass or more and 85% by mass or less, based on the total mass of the resin composition of the present invention. If the filler content is not more than the above upper limit value, the film system performance is improved, the fluidity of the resin is increased, and the filling property is improved, which is preferable. Moreover, if it is more than the said lower limit, there exists an effect sufficiently.

Silane Coupling Agent The resin composition of the present invention may contain a silane coupling agent. By including the silane coupling agent, the adhesion of the resin composition to the adherend can be further enhanced. Examples of the silane coupling agent include an epoxy silane coupling agent and an aromatic-containing aminosilane coupling agent. These may be used alone or in combination of two or more. Although content of a silane coupling agent is not specifically limited, It is preferable to set it as 0.01 to 5 mass% of the total mass of the adhesive composition of this invention.

  Moreover, the resin composition of this invention may contain components other than the above. For example, various additives are appropriately added to improve the compatibility between the silicone resin (A) and the thermosetting resin (B), or to improve various properties such as storage stability or workability of the resin composition. May be. For example, an internal mold release agent such as fatty acid ester, glyceric acid ester, zinc stearate, calcium stearate, phenol-based, phosphorus-based or sulfur-based antioxidant can be added. Other optional components may be added to the resin composition of the present invention without solvent, but may be added after dissolving or dispersing in an organic solvent and preparing a solution or dispersion. The solvent can use the organic solvent demonstrated below as a solvent for preparing the dispersion liquid of a resin composition.

Organic solvent The above-mentioned other optional components may be added to the adhesive composition of the present invention without using a solvent, but are dissolved or dispersed in an organic solvent to form a solution or dispersion (hereinafter simply referred to as “solution”). It may be added after preparation. As this organic solvent, N, N-dimethylacetamide, methyl ethyl ketone, N, N-dimethylformamide, cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, toluene, methanol, ethanol, isopropanol, acetone, propylene glycol monomethyl ether , Propylene glycol monomethyl ether acetate and the like, preferably methyl ethyl ketone, cyclopentanone, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate. These organic solvents may be used alone or in combination of two or more.

<Resin film>
The resin composition of the present invention is preferably formed into a film. Such a resin film has good moldability especially for large-diameter and thin-film wafers, and it is not necessary to pour resin when molding the wafers in a lump. Therefore, wire deformation that can occur with conventional transfer molding, poor filling of the wafer surface, difficulty in controlling the molding range that can occur with compression molding, and problems with fluidity and physical properties of the liquid sealing resin are fundamentally eliminated. can do.

  Furthermore, the thickness of the resin film is preferably 100 μm or more and 700 μm or less. Such a thickness is preferable because the resin film is excellent in low warpage and protection.

  Accordingly, the present invention provides a resin film formed from the resin composition. Examples of the resin film include a resin film having a resin film formed from the resin composition of the present invention and a protective layer covering the resin film. What is demonstrated later can be used for this protective layer. Hereinafter, an example of the manufacturing method of the resin film of this invention is demonstrated.

(Method for producing resin film)
A resin composition solution prepared in advance by mixing (A) silicone resin, (B) thermosetting resin, (C) filler, and other optional components and an organic solvent as necessary is prepared in the present invention. Then, the resin composition solution is applied to the protective layer using a reverse roll coater, a comma coater or the like. The protective layer coated with the resin composition solution is passed through an in-line dryer, dried by removing the organic solvent at 80 to 160 ° C. for 2 to 20 minutes, and then pressed with another protective layer using a roll laminator. And the resin film of this invention is obtained by laminating | stacking.

・ Protective layer (protective film / release film)
The protective layer is not particularly limited as long as it can be removed without impairing the form of the resin film made of the resin composition of the present invention. Usually, a polyethylene (PE) film, a polypropylene (PP) film, a polymethylpentene ( And a plastic film such as a polyester film subjected to a release treatment.

(Wafer to be molded)
The wafer that is collectively molded with the resin film of the present invention is not particularly limited, but even a wafer having semiconductor elements (chips) loaded on its surface is a semiconductor wafer having semiconductor elements fabricated on its surface. May be. The resin film of the present invention has a good filling property with respect to such a wafer surface before molding, and has a low warpage after molding, and is excellent in the protection property of such a wafer. The resin film of the present invention is not particularly limited, but can be suitably used for molding a wafer having a large diameter such as 8 inches (200 mm) or 12 inches (300 mm) or a thin film wafer.

(Wafer molding method)
The method for molding the wafer using the resin film of the present invention is not particularly limited. For example, one protective film attached to the resin film is peeled off, and a vacuum laminator (product name: TEAM-100RF) manufactured by Takatori Co., Ltd. is used. ), The degree of vacuum is set to 50 to 1,000 Pa, for example, 100 Pa, the other release film and the resin film are brought into close contact with the wafer at 80 to 130 ° C., for example, 100 ° C., and returned to normal pressure. Thereafter, the substrate is cooled to 25 ° C., taken out from the vacuum laminator, and the other release film is peeled off.

<Semiconductor device>
Furthermore, the present invention provides a semiconductor device characterized in that a semiconductor wafer molded with a heat-cured film obtained by heat-curing the resin film is singulated and has a heat-cured film. According to the present invention, a semiconductor device obtained by dividing a wafer that is sufficiently protected with little warpage is a high-quality semiconductor device with a good yield.

<Method for Manufacturing Semiconductor Device>
Further, in the present invention, one of the protective films of the resin film is peeled off from the resin film, the resin film exposed on the surface is attached to the semiconductor wafer, the other release film is peeled off from the resin film, and the semiconductor wafer is molded. And a step of separating the molded semiconductor wafer into individual pieces.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is further demonstrated, this invention is not restrict | limited to the following Example.

[Synthesis Examples 1 to 3]
In the synthesis examples, the weight average molecular weight of each polymer was determined by using a GPC column TSKgel Super HZM-H (manufactured by Tosoh Corporation) under the analysis conditions of a flow rate of 0.6 ml / min, an elution solvent tetrahydrofuran, and a column temperature of 40 ° C. It was measured by gel permeation chromatography (GPC) using dispersed polystyrene as a standard.

The compounds used in Examples and Comparative Examples are shown below.

[Synthesis Example 1]
In a 3 L flask equipped with a stirrer, a thermometer, a nitrogen displacement device and a reflux condenser, 210 g (0.35 mol) of the compound represented by the above formula (S-1) and the above formula (S-2) are represented. After adding 27.9 g (0.15 mol) of the compound, 2000 g of toluene was added and heated to 70 ° C. Thereafter, 1.0 g of a chloroplatinic acid toluene solution (platinum concentration: 0.5 wt%) was added, and 77.8 g (0.4 mol) of the compound represented by the above formula (S-3) and the above formula (S-4) 309.4 g (0.1 mol) of the compound represented by formula (x = 40) was added dropwise over 1 hour (total number of moles of hydrosilyl group / total number of moles of alkenyl group = 1/1). After completion of the dropwise addition, the mixture was heated to 100 ° C. and aged for 6 hours, and then toluene was distilled off from the reaction solution under reduced pressure. The product obtained by GPC of the product obtained by GPC was 36,000. The obtained resin was shown to the following formula, this was made into resin (1), and it used for the Example and the comparative example.

[Synthesis Example 2]
After adding 300 g (0.5 mol) of the compound represented by the above formula (S-1) to a 3 L flask equipped with a stirrer, a thermometer, a nitrogen substitution device and a reflux condenser, 2100 g of toluene was added, and 70 Warmed to ° C. Thereafter, 1.0 g of a chloroplatinic acid toluene solution (platinum concentration: 0.5 wt%) was added, and 77.8 g (0.4 mol) of the compound represented by the above formula (S-3) and the above formula (S-4) The compound (x = 100) 753.4g (0.1mol) shown by this was dripped over 2 hours (Total number of moles of hydrosilyl group / Total number of moles of alkenyl group = 1/1). After completion of the dropwise addition, the mixture was heated to 100 ° C. and aged for 6 hours, and then toluene was distilled off from the reaction solution under reduced pressure. The product obtained by GPC of the product obtained by GPC had a weight average molecular weight of 52,000. The obtained resin was shown to the following formula, this was made into resin (2), and it used for the Example and the comparative example.

[Synthesis Example 3]
In a 3 L flask equipped with a stirrer, a thermometer, a nitrogen displacement device and a reflux condenser, 150 g (0.25 mol) of the compound represented by the above formula (S-1) and the above formula (S-2) are represented. After adding 46.5 g (0.25 mol) of the compound, 1000 g of toluene was added and heated to 70 ° C. Thereafter, 0.5 g of a chloroplatinic acid toluene solution (platinum concentration: 0.5 wt%) was added, and 48.6 g (0.25 mol) of the compound represented by the above formula (S-3) and the above formula (S-4). 181.5 g (0.25 mol) of the compound represented by formula (x = 8) was added dropwise over 1 hour (total number of moles of hydrosilyl group / total number of moles of alkenyl group = 1/1). After completion of the dropwise addition, the mixture was heated to 100 ° C. and aged for 6 hours, and the weight average molecular weight in terms of polystyrene measured by GPC of the product obtained by distilling off toluene from the reaction solution under reduced pressure was 27,000. The obtained resin was shown in the following formula, and this was used as Resin (3) and used in the examples.

[Comparative Synthesis Example 1]
In a 3 L flask equipped with a stirrer, a thermometer, a nitrogen substitution device and a reflux condenser, 151 g (0.35 mol) of the compound represented by the above formula (S-5) and the above formula (S-2) are represented. After adding 27.9 g (0.15 mol) of the compound, 2000 g of toluene was added and heated to 70 ° C. Thereafter, 1.0 g of a chloroplatinic acid toluene solution (platinum concentration: 0.5 wt%) was added, and 77.8 g (0.4 mol) of the compound represented by the above formula (S-3) and the above formula (S-4) 309.4 g (0.1 mol) of the compound represented by formula (x = 40) was added dropwise over 1 hour (total number of moles of hydrosilyl group / total number of moles of alkenyl group = 1/1). After completion of the dropwise addition, the mixture was heated to 100 ° C. and aged for 6 hours, and then toluene was distilled off from the reaction solution under reduced pressure. The product obtained by GPC of the product obtained by GPC was 38,000. The obtained resin was shown to the following formula, this was made into resin (4), and it used for the comparative example.

[Examples 1-6 and Comparative Examples 1-3]
<Preparation of resin composition>
In the composition described in Table 1 below, (A) the silicone resin synthesized in Synthesis Examples 1 to 3 (the above resins (1) to (3)), (B) a thermosetting resin, and (C) a filler were blended. . Further, cyclopentanone in an amount to give a solid component concentration of 70% by mass was added, stirred using a ball mill, mixed and dissolved and dispersed to prepare a resin composition dispersion. In addition, the unit of the numerical value which shows the compounding quantity in Table 1 is a "mass part". Comparative Example 1 is a resin composition containing no (B) thermosetting resin, Comparative Example 2 is a resin composition containing no (C) filler, and Comparative Example 3 is a silicone resin (A) of the present invention. Is a resin composition comprising a different silicone resin (resin (4) above).

Each component used for preparation of the resin composition is shown below.
(B) Thermosetting resin / EOCN-103S (trade name) (manufactured by Nippon Kayaku, epoxy equivalent: 209 to 219)
Here, the epoxy equivalent means the equivalent of the epoxy group per molecule of each component.

Further, the following epoxy resin curing agent and epoxy resin curing accelerator were used.
・ Epoxy resin curing agent:
Rekajit HH (trade name) (manufactured by Nippon Nippon Kayaku, hexahydrophthalic anhydride)
・ Epoxy resin curing accelerator:
Cureazole 2P4MHZ (trade name) (manufactured by Shikoku Chemicals, 2-phenyl-4-methyl-5-hydroxymethylimidazole)

(C) Filler silica (manufactured by Admatechs, average particle size 5.0 μm)

Release film (1): E7304 (manufactured by Toyobo Co., Ltd., 75 μm, peel force 200 mN / 50 mm)
Release film (2): E7302 (Toyobo Co., Ltd., 75 μm, peel force 90 mN / 50 mm)
Protective film: Polyethylene film (100 μm)

[Example 1]
(Formation of resin film)
Using a die coater as a film coater and using E7304 as a release film (1), the resin composition shown in Example 1 of Table 1 was coated on the release film. Subsequently, the resin film with a film thickness of 100 micrometers was formed on the said peeling film (1) by allowing the hot air circulation oven (length 4m) set to 100 degreeC to pass through for 5 minutes. Next, from above the resin film, a polyethylene film (thickness: 100 μm) is laminated using a laminating roll at a linear pressure of 10 N / cm, and a laminated film (1) comprising a release film (1) / resin film / protective film. Was made. A laminated film (2) was produced in the same manner as above except that E7302 was used as the release film (2) instead of the release film (1). Further, the respective polyethylene films of the obtained laminated films (1) and (2) are removed, the resin films are overlapped with each other, put into a hot roll laminator heated to 60 ° C., and a release film having a film thickness of 200 μm. A composite film consisting of (1) / resin film / release film (2) was formed.

[Examples 2-6, Comparative Examples 1-3]
A composite film having a film thickness of 200 μm was produced in the same manner as in Example 1.
In Example 6, a resin film having a film thickness of 500 μm was produced using the same resin composition as in Example 2.

[Mold of resin film on wafer]
A silicon wafer having a wafer thickness of 100 μm and a diameter of 8 inches (200 mm) was prepared. About the composite films of Examples 1 to 6 and Comparative Examples 1 to 3, the release film (2) was peeled off, and the inside of the vacuum chamber was evacuated using a vacuum laminator (manufactured by Takatori Co., Ltd., product name: TEAM-100RF). The temperature was set to 100 Pa, and the resin film was attached to the silicon wafer at 100 ° C. After returning to normal pressure, the silicon wafer was cooled to 25 ° C., taken out from the vacuum laminator, and the remaining release film (1) was peeled off.
The obtained wafer with a resin film was cured by heating at 180 ° C. for 2 hours in an inert oven.

[Evaluation 1: Wafer warpage amount]
The amount of wafer warpage after the resin film was cured was measured, and the obtained values are shown in Table 2.

[Evaluation 2: Wafer support]
Table 2 shows the results of determining the wafer support performance by measuring the amount of deflection of the wafer when the edge of the wafer is supported, and determining that it is good within 20 mm and that it is bad when it exceeds 20 mm.

[Evaluation 3: Adhesion]
Using a vacuum film laminator (temperature: 100 ° C., pressure: 100 Pa, TEAM-100, manufactured by Takatori Co., Ltd.), each resin film (25 μm) is 6-inch diameter semiconductor wafer (thickness: 625 μm, manufactured by Shin-Etsu Chemical Co., Ltd.). ). Subsequently, it cut | disconnected to the magnitude | size of 2 mm x 2 mm square using the dicing saw (DAD685, DISCO company make) provided with a dicing blade. A 2 mm × 2 mm square chip was bonded to a separately prepared 15 mm × 15 mm square silicon wafer (base substrate) through a resin film at 150 ° C. under a load of 50 mN. Then, it heated at 180 degreeC for 2 hours, the resin film was hardened, and the test piece was obtained. Five test pieces were manufactured for each and subjected to the following adhesive strength measurement test.

  Using a bond tester (Dage series 4000-PXY: manufactured by Dage), the resistance force applied when the semiconductor chip (2 mm × 2 mm) peels from the base substrate (15 mm × 15 mm silicon wafer) is measured, and the resin film layer The adhesion of was evaluated. The test conditions were a test speed of 200 μm / sec and a test height of 50 μm. The results are shown in Table 2. The numerical values shown in Table 2 are the average of the measured values of five test specimens each, and the higher the numerical value, the higher the adhesive strength of the adhesive sheet.

[Evaluation 4: Reliability]
A 10 mm × 10 mm square test piece was obtained by using a dicing saw (DAD685, manufactured by DISCO, spindle rotation speed: 40,000 rpm, cutting speed: 20 mm / sec) equipped with a dicing blade on the cured wafer with a resin film. . The obtained test pieces (each 10 pieces each) were subjected to a heat cycle test (holding at −25 ° C. for 10 minutes and holding at 125 ° C. for 10 minutes for 1,000 cycles), and from the resin film wafer after the heat cycle test The peeling state of was confirmed. Table 2 shows the results of determining that no peeling occurred at all, and determining that even one peeling occurred as defective.

  As a result of the above, it was found that the resin film obtained from the resin composition of the present invention has a smaller amount of wafer warpage as compared with the comparative example, and is excellent in wafer support, adhesion, and reliability.

  As described above, since the resin composition of the present invention can be formed into a film shape, the wafer can be molded in a lump (wafer molding), and can be used for a large diameter, thin film wafer. It was shown to have good moldability. Moreover, it was shown that the resin film obtained from the resin composition of the present invention is excellent in low warpage and wafer protection, and excellent in adhesion and reliability.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

Claims (9)

A resin composition comprising the following components (A), (B), and (C):
(A) a silicone resin having a weight average molecular weight of 3000 to 500000 represented by the following general formula (1):

[Wherein, R ^{1 to} R ⁴ represent a monovalent hydrocarbon group having 1 to 8 carbon atoms which may be the same or different. M is an integer of 1 to 300, n is 2 or 3, a is a positive number, and b is 0 or a positive number. X and Y are divalent organic groups represented by the following general formula (2) or (3). However, at least part or all of X and Y in the formula is a divalent organic group represented by the following general formula (2).

(Where Z is

And a p is 0 or 1. R ⁵ represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and R ⁶ represents a hydrogen atom, a methyl group, or an ethyl group, and may be the same or different from each other. h is 0, 1, or 2. ]]

(B) thermosetting resin,
(C) Filler.   The amount of the component (B) is 5 to 100 parts by mass with respect to 100 parts by mass of the component (A), and the mass fraction of the component (C) with respect to the total mass is 30 to 90% by mass. The resin composition according to claim 1, wherein   The resin composition according to claim 1 or 2, wherein the thermosetting resin is an epoxy resin.   Furthermore, the resin composition of Claim 3 containing at least one chosen from an epoxy resin hardening | curing agent and an epoxy resin hardening accelerator.   The resin composition according to claim 1, wherein the filler is silica.   A resin film formed using the resin composition according to any one of claims 1 to 5.   A method of manufacturing a semiconductor device, comprising: a step of attaching the resin film according to claim 6 to a semiconductor wafer, molding the semiconductor wafer, and a step of separating the molded semiconductor wafer. Wherein a is one having a resin film heat cured pressurized heat cured film of claim 6.   In the said General formula (1), X and Y are bivalent organic groups shown by the said General formula (2), The resin composition as described in any one of Claims 1-5 characterized by the above-mentioned.