JP2015126018A - Resin film for semiconductor device and method for manufacturing semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin film for a semiconductor device having a sufficient ion capture property even after the completion of heat hysteresis.SOLUTION: A resin film for a semiconductor device has a ratio B/A of a copper ion capture property A before thermal cure and a copper ion capture property B after thermal cure.

Description

  The present invention relates to a resin film for a semiconductor device and a method for manufacturing the semiconductor device.

  Conventionally, in a semiconductor device, metal ions (for example, copper ions) are generated from wiring (for example, copper wiring) formed on a substrate or a wire (for example, copper wire) that electrically connects the substrate and a semiconductor chip. However, it is known that malfunction may occur.

  Therefore, in recent years, it has been studied to prevent malfunction of a semiconductor device by adding an additive for capturing metal ions to a resin for bonding a semiconductor chip to a substrate such as a lead frame (for example, patents). Reference 1).

JP-A-2005-333085

  However, in the manufacture of semiconductor devices, since various heating processes are performed, there is a possibility that the additive may be thermally decomposed, and there is a problem that sufficient ion trapping properties may not be exhibited.

  The present invention has been made in view of the above-mentioned problems, and its object is to provide a resin film for a semiconductor device that has sufficient ion trapping properties even after passing through a thermal history, and a semiconductor device using the resin film for a semiconductor device. It is in providing the manufacturing method of.

  The inventors of the present application have conducted intensive research on resin films for semiconductor devices. As a result, surprisingly, in certain resin films for semiconductor devices, the ion scavenging property is the same after heat curing and before heat curing, or after heat curing, the ion scavenging property is better than before heat curing. As a result, the present invention has been completed.

That is, the resin film for a semiconductor device according to the present invention was immersed in a resin film for a semiconductor device having a weight of 2.5 g before thermosetting in 50 ml of an aqueous solution containing 10 ppm of copper ions and left at 120 ° C. for 20 hours. Subsequent immersion of the resin film for a semiconductor device having a weight of 2.5 g after being thermally cured at 175 ° C. for 5 hours in 50 ml of an aqueous solution containing X and 10 ppm of copper ions. When the copper ion concentration (ppm) in the aqueous solution after being left at 120 ° C. for 20 hours is Y, the copper ion capture rate A calculated by the following formula (1) and the following formula (2) are calculated. The ratio B / A with respect to the copper ion capture rate B is 1 or more.
Formula (1): [(10−X) / 10] × 100 (%)
Formula (2): [(10−Y) / 10] × 100 (%)

  According to the said structure, ratio B / A of the copper ion capture | acquisition rate A before thermosetting and the copper ion capture | acquisition rate B after thermosetting is 1 or more, and also after thermosetting compared with before thermosetting, Cation capturing ability does not decrease. Therefore, the semiconductor device has sufficient ion trapping properties even after passing through a thermal history.

  In the said structure, it is preferable that 5% weight reduction | decrease temperature is 200 degreeC or more.

  When the 5% weight reduction temperature is 200 ° C. or higher, the heat resistance of the entire resin film for semiconductor devices is excellent.

  In the said structure, it is preferable to contain the inorganic ion trapping agent which traps a cation.

  Inorganic ion scavengers are relatively difficult to thermally decompose. Therefore, when an inorganic ion scavenger is contained, it has more sufficient ion scavenging properties even after a thermal history.

  In the said structure, it is preferable that content of the said inorganic ion scavenger is 1 to 30 weight%.

  By setting the content of the inorganic ion scavenger to 1% by weight, cations can be captured efficiently, and by setting the content to 30% by weight or less, good film formability can be obtained.

  In the above-described configuration, a resin film for a semiconductor device having a weight of 2.5 g after being thermally cured at 175 ° C. for 5 hours in 50 ml of an aqueous solution having 10 ppm of copper ions is left at 120 ° C. for 20 hours. It is preferable that pH of the said aqueous solution is in the range of 4-6.

  Inorganic ion scavengers generally capture cations by ion exchange. Therefore, the cation trapping property is affected by pH. Specifically, when the pH becomes excessively acidic, the ability to capture cations may decrease. Therefore, the cation trapping property can be further improved by adjusting the pH within the range of 4 to 6.

In addition, a method for manufacturing a semiconductor device according to the present invention includes:
Preparing the resin film for a semiconductor device;
A die-bonding step of die-bonding a semiconductor chip on an adherend through the resin film for a semiconductor device.

  According to the said structure, ratio B / A of the copper ion capture | acquisition rate A before thermosetting of the resin film for semiconductor devices and the copper ion capture | acquisition rate B after thermosetting is 1 or more, Compared before thermosetting. Even after heat curing, the cation scavenging property does not decrease. Therefore, the semiconductor device has sufficient ion trapping properties even after passing through a thermal history. As a result, it is possible to suppress malfunction of the manufactured semiconductor device.

It is a cross-sectional schematic diagram which shows the die-bonding film with a dicing sheet which concerns on one Embodiment of this invention. It is a cross-sectional schematic diagram which shows the die-bonding film with a dicing sheet which concerns on other embodiment of this invention. It is a cross-sectional schematic diagram for demonstrating one manufacturing method of the semiconductor device which concerns on this embodiment.

  Below, the case where the resin film for semiconductor devices of this invention is a die-bonding film is demonstrated first as suitable embodiment of this invention. The die bond film which concerns on this embodiment can mention the thing of the state in which the dicing sheet is not bonded together in the die bond film with a dicing sheet demonstrated below. Therefore, hereinafter, a die bond film with a dicing sheet will be described, and the die bond film will be described therein.

  FIG. 1 is a schematic cross-sectional view showing a die bond film with a dicing sheet according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view showing another die-bonding film with a dicing sheet according to another embodiment of the present invention.

As shown in FIG. 1, a die bond film 10 with a dicing sheet has a configuration in which a die bond film 3 is laminated on a dicing sheet 11. The dicing sheet 11 is configured by laminating the pressure-sensitive adhesive layer 2 on the base material 1, and the die bond film 3 is provided on the pressure-sensitive adhesive layer 2. In addition, the structure which formed die-bonding film 3 'only in the workpiece | work affixing part may be sufficient as the die-bonding film with a dicing sheet like the die-bonding film 12 with a dicing sheet shown in FIG. The die bond film 3 ′ is different from the die bond film 3 only in shape, and various resins, additives, fillers, and the like constituting the film can be the same as the die bond film 3.
Below, each structure of the die-bonding film 10 with a dicing sheet shown in FIG. 1 is mainly demonstrated.

(Die bond film)
The die bond film 3 is obtained by immersing the die bond film 3 having a weight of 2.5 g before thermosetting in 50 ml of an aqueous solution having 10 ppm of copper ions, and leaving the solution at 120 ° C. for 20 hours. The die bond film 3 having a weight of 2.5 g after being thermally cured at 175 ° C. for 5 hours in 50 ml of an aqueous solution containing 10 ppm of copper ions and X) was immersed in the solution and left at 120 ° C. for 20 hours. When the copper ion concentration (ppm) in the aqueous solution is Y, the ratio B / of the copper ion trapping rate A calculated by the following formula (1) and the copper ion trapping rate B calculated by the following formula (2) A is 1 or more.
Formula (1): [(10−X) / 10] × 100 (%)
Formula (2): [(10−Y) / 10] × 100 (%)

  The ratio B / A is 1 or more, and preferably 1.1 or more. The ratio B / A is preferably large, but is 10 or less, for example. In the die bond film 3, the ratio B / A is 1 or more, and the cation trapping property does not decrease even after heat curing as compared with before heat curing. Therefore, the semiconductor device has sufficient ion trapping properties even after passing through a thermal history.

  The die bond film 3 preferably has a 5% weight loss temperature of 200 ° C. or higher, more preferably 250 ° C. or higher, and more preferably 300 ° C. or higher. When the 5% weight reduction temperature of the die bond film 3 is 200 ° C. or higher, the heat resistance of the die bond film 3 as a whole is excellent. The method for measuring the 5% weight loss temperature is according to the method described in the examples. The 5% weight reduction temperature of the die bond film 3 is selected from the resins, additives, fillers, and the like constituting the die bond film 3, and the manufacturing conditions for forming the die bond film 3 (for example, the drying temperature after coating film formation, The drying time can be adjusted.

  The die bond film 3 preferably contains an additive that captures cations. When the die-bonding film 3 contains an additive that captures cations, it is possible to easily wait for ion scavenging.

  Examples of the cation captured by the additive that captures the cation include Na, K, Ni, Cu, Cr, Co, Hf, Pt, Ca, Ba, Sr, Fe, Al, Ti, Zn, Mo, Examples include ions (cations) such as Mn and V. In particular, it is preferable that the additive for capturing the cation captures at least Cu ion (copper ion). This is because copper ions are likely to be generated in a large amount as compared with other ions, and are highly likely to have a great influence on the malfunction of the semiconductor device.

  Examples of the additive that captures the cation include an inorganic ion scavenger and a complex-forming compound that forms a complex with the cation. Of these, inorganic ion scavengers are preferred. This is because inorganic ion scavengers are relatively difficult to thermally decompose, and thus have a more sufficient ion scavenging property even after passing through a thermal history.

(Inorganic ion scavenger)
The inorganic ion scavenger is an inorganic ion exchanger that captures cations by ion exchange. The inorganic ion scavenger is preferably an inorganic zwitter ion scavenger that can capture not only cations but also anions. When the inorganic ion scavenger is a both ion scavenger, there is little change in pH. As a result, it is possible to suppress a decrease in ion trapping property over time. Specifically, ions that are released as counter ions when capturing cations (for example, hydrogen ions) are neutralized by ions that are released as counter ions when capturing anions (for example, hydroxide ions). To do. Since ion trapping is performed by an equilibrium reaction (ion exchange), ion exchange of target ions is promoted by reducing the concentration of counter ions.
In the present specification, the amphoteric ion scavenger refers to an inorganic amphoteric ion exchanger capable of trapping both a certain amount of both copper ions and chloride ions. Specifically, the inorganic both ion exchangers have a copper (II) ion distribution coefficient (Kd) of 10 or more determined according to the following copper (II) ion distribution coefficient measurement method, and the following ion exchange capacity: The ion exchange capacity (meq / g) calculated | required according to this measuring method can mention 0.5 or more.
<Measurement method of copper (II) ion partition coefficient>
Into a 100 ml plastic container, 5.0 g of an inorganic amphoteric ion exchanger and 50 ml of a test solution containing 0.01 N of copper (II) ions are put, sealed, and shaken at 25 ° C. for 24 hours. After shaking, the mixture is filtered with a 0.1 μm membrane filter, and the copper (II) ion concentration in the filtrate is measured with ICP-AES (SPS-1700HVR, manufactured by SII Nanotechnology Co., Ltd.). II) Obtain the ion distribution coefficient Kd. Kd (ml / g) is represented by (C ₀ -C) × V / (C × m), where C ₀ is the initial ion concentration, C is the test solution ion concentration, V is the test solution volume (ml), and m is inorganic. It is the weight (g) of both ion exchangers.
<Measurement method of ion exchange capacity>
1.0 g of inorganic both ion exchangers are immersed in 50 ml of saturated NaCl aqueous solution and left at room temperature for 20 hours. The amount of hydroxide ions generated by the inorganic amphoteric ion exchanger is quantified by titration with a 0.1N aqueous HCl solution to determine the ion exchange capacity (meq./g).

  The die bond film 3 was immersed in 50 ml of an aqueous solution containing 10 ppm of copper ions at a temperature of 175 ° C. for 5 hours, and the die bond film 3 having a weight of 2.5 g was immersed therein and left at 120 ° C. for 20 hours. The pH of the aqueous solution is preferably within the range of 4 to 6, more preferably within the range of 4.2 to 5.8, and even more preferably within the range of 4.4 to 5.5. . Inorganic ion scavengers generally capture cations by ion exchange. Therefore, the cation trapping property is affected by pH. Specifically, when the pH becomes excessively acidic, the ability to capture cations may decrease. Therefore, the cation trapping property can be further improved by adjusting the pH within the range of 4 to 6. Examples of the method for adjusting the pH within the range of 4 to 6 include a method using the following inorganic zwitterion scavenger. When an inorganic amphoteric ion scavenger is used, it is possible to suppress excessively acidic pH and maintain high ion trapping properties.

  The inorganic ion scavenger is not particularly limited, and various inorganic ion scavengers can be used. For example, oxidation of an element selected from the group consisting of antimony, bismuth, zirconium, titanium, tin, magnesium and aluminum Hydrates can be mentioned. These can be used alone or in combination of two or more. Of these, ternary oxide hydrates of magnesium, aluminum and zirconium are preferred. Since the ternary system of magnesium, aluminum and zirconium captures both cations and anions by ion exchange, the pH is maintained near neutral even when ions are captured. Therefore, better ion trapping properties can be obtained. Further, the three-component system of magnesium, aluminum and zirconium is particularly suitable for semiconductor applications that require antimony free.

  As a commercial item of the said inorganic ion scavenger, Toa Gosei Co., Ltd. brand name: IXEPLAS-A1, IXEPLAS-A2 etc. can be mentioned. These are inorganic zwitterion scavengers.

  The average particle diameter of the inorganic ion scavenger is preferably 0.1 to 1 μm, and more preferably 0.2 to 0.6 μm. By setting the average particle size of the inorganic ion scavenger to 1 μm or less, the specific surface area can be increased. As a result, the ion trapping property can be further improved. Moreover, the thickness of the die-bonding film 3 can be made thin by making the average particle diameter of the inorganic ion scavenger 1 μm or less. Moreover, dispersibility can be improved by making the average particle diameter of the inorganic ion scavenger 0.1 μm or more.

  The inorganic ion scavenger is preferably treated (pretreated) with a silane coupling agent. When the silane coupling treatment is performed, the dispersibility of the inorganic ion scavenger is improved, and the film forming property of the die bond film 3 is excellent. In particular, an inorganic ion scavenger having a smaller particle size is more likely to cause aggregation, but if silane coupling treatment is performed, dispersibility is improved. As a result, it is possible to suitably manufacture a thin die bond film 3 containing an inorganic ion scavenger. In addition, the present inventors have confirmed that even when the inorganic ion scavenger is treated with silane coupling, the cation scavenging property is not equal to or significantly lower than that in the untreated state.

  As the silane coupling agent, those containing a silicon atom, a hydrolyzable group and an organic functional group are preferable.

  The hydrolyzable group is bonded to the silicon atom.

  Examples of the hydrolyzable group include a methoxy group and an ethoxy group. Of these, a methoxy group is preferred because of its high hydrolysis rate and easy treatment.

  The number of hydrolyzable groups in the silane coupling agent can be cross-linked between the silane coupling agents while cross-linking with the inorganic ion scavenger. From the point that the entire agent can be surface-treated with a silane coupling agent, the number is preferably 2 to 3, more preferably 3.

  The organic functional group is bonded to the silicon atom.

  As an organic functional group, what contains an acryl group, a methacryl group, an epoxy group, a phenylamino group etc. is mentioned, for example. Of these, an acrylic group is preferred because it has no reactivity with the epoxy resin and the storage stability of the treated inorganic ion scavenger is good.

  In addition, since it will react with an epoxy resin when it has a functional group with high reactivity with an epoxy group, storage stability and fluidity | liquidity will fall. From the viewpoint of suppressing a decrease in fluidity, the organic functional group preferably does not contain a primary amino group, mercapto group or isocyanate group.

  The number of organic functional groups in the silane coupling agent is preferably one. Since the silicon atom has four bonds, if the number of organic functional groups is large, the number of hydrolyzable groups is insufficient.

  The silane coupling agent may further include an alkyl group bonded to the silicon atom. When the silane coupling agent contains an alkyl group, it is possible to make the reactivity lower than that of the methacryl group, and to prevent surface treatment bias due to abrupt reaction. Examples of the alkyl group include a methyl group and a dimethyl group. Of these, a methyl group is preferable.

  Specific examples of the silane coupling agent include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- Glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, N- Phenyl-3-aminopropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxyp Such as pills triethoxy silane.

  The method of treating the inorganic ion scavenger with the silane coupling agent is not particularly limited, and is a wet method in which the inorganic ion scavenger and the silane coupling agent are mixed in a solvent, and the inorganic ion scavenger and the silane coupling in the gas phase. Examples include a dry method in which the agent is treated.

  Although the processing amount of a silane coupling agent is not specifically limited, It is preferable to process 0.05-5 weight part of silane coupling agents with respect to 100 weight part of inorganic ion scavengers.

  The content of the additive for capturing the cation is preferably 1 to 30% by weight, more preferably 2 to 25% by weight, and further preferably 3 to 20% by weight. By setting the content of the additive for trapping cations to 1% by weight, cations can be trapped efficiently, and by setting the content to 30% by weight or less, good film formability can be obtained.

  The die bond film 3 preferably contains one or both of a thermoplastic resin and a thermosetting resin. Examples of the thermosetting resin include phenol resin, amino resin, unsaturated polyester resin, epoxy resin, polyurethane resin, silicone resin, and thermosetting polyimide resin. These resins can be used alone or in combination of two or more, and it is particularly preferable to use at least one of an epoxy resin and a phenol resin. Among these, it is preferable to use an epoxy resin. When the epoxy resin is contained, a high adhesive force between the die bond film 3 and the wafer can be obtained at a high temperature. As a result, it is difficult for water to enter the bonding interface between the die bond film 3 and the wafer, making it difficult for ions to move. Thereby, reliability is improved.

  The epoxy resin is not particularly limited as long as it is generally used as an adhesive composition, for example, bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol AF type. Biphenyl type, naphthalene type, fluorene type, phenol novolac type, orthocresol novolak type, trishydroxyphenylmethane type, tetraphenylolethane type, etc., bifunctional epoxy resin or polyfunctional epoxy resin, or hydantoin type, trisglycidyl isocyanurate Type or glycidylamine type epoxy resin is used. These can be used alone or in combination of two or more. Of these epoxy resins, novolac type epoxy resins, biphenyl type epoxy resins, trishydroxyphenylmethane type resins or tetraphenylolethane type epoxy resins are particularly preferred. This is because these epoxy resins are rich in reactivity with a phenol resin as a curing agent and are excellent in heat resistance and the like.

  Further, the phenol resin acts as a curing agent for the epoxy resin. Examples include resol-type phenolic resins and polyoxystyrenes such as polyparaoxystyrene. These can be used alone or in combination of two or more. Of these phenol resins, phenol novolac resins and phenol aralkyl resins are particularly preferred. This is because the connection reliability of the semiconductor device can be improved.

  The mixing ratio of the epoxy resin and the phenol resin is preferably such that, for example, the hydroxyl group in the phenol resin is 0.5 to 2.0 equivalents per 1 equivalent of the epoxy group in the epoxy resin component. . More preferred is 0.8 to 1.2 equivalents. That is, if the blending ratio of both is out of the above range, sufficient curing reaction does not proceed and the properties of the cured epoxy resin are likely to deteriorate.

  Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, polybutadiene resin, polycarbonate resin, heat Examples thereof include plastic polyimide resins, polyamide resins such as 6-nylon and 6,6-nylon, phenoxy resins, acrylic resins, saturated polyester resins such as PET and PBT, polyamideimide resins, and fluorine resins. These thermoplastic resins can be used alone or in combination of two or more. Of these thermoplastic resins, an acrylic resin that has few ionic impurities and high heat resistance and can ensure the reliability of the semiconductor element is particularly preferable.

  The acrylic resin is not particularly limited, and includes one or two or more esters of acrylic acid or methacrylic acid having a linear or branched alkyl group having 30 or less carbon atoms, particularly 4 to 18 carbon atoms. Examples thereof include a polymer (acrylic copolymer) as a monomer component. Examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, heptyl group, cyclohexyl group, 2- Examples include an ethylhexyl group, an octyl group, an isooctyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a lauryl group, a tridecyl group, a tetradecyl group, a stearyl group, an octadecyl group, and a dodecyl group.

  In addition, the other monomer forming the polymer is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Carboxyl group-containing monomers such as acid anhydride monomers such as maleic anhydride or itaconic anhydride, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4- (meth) acrylic acid 4- Hydroxybutyl, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate or (4-hydroxymethylcyclohexyl) -Methyla Hydroxyl group-containing monomers such as relate, styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate or (meth) Examples thereof include sulfonic acid group-containing monomers such as acryloyloxynaphthalene sulfonic acid, and phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl phosphate. These can be used alone or in combination of two or more.

  The blending ratio of the thermosetting resin is not particularly limited as long as the die-bonding film 3 exhibits a function as a thermosetting type when heated under predetermined conditions, but within a range of 5 to 60% by weight. It is preferable that it is within a range of 10 to 50% by weight.

  The die bond film 3 contains an epoxy resin, a phenol resin, and an acrylic resin, and the total amount of the epoxy resin and the phenol resin with respect to 100 parts by weight of the acrylic resin is preferably 10 to 2000 parts by weight. The amount is more preferably 10 to 1500 parts by weight, and still more preferably 10 to 1000 parts by weight. By making the total amount of the epoxy resin and the phenol resin with respect to 100 parts by weight of the acrylic resin 10 parts by weight or more, an adhesive effect due to curing can be obtained, and peeling can be suppressed. It is possible to suppress the workability from being deteriorated due to the weakening of the film.

  When the die-bonding film 3 is previously crosslinked to some extent, it is preferable to add a polyfunctional compound that reacts with the functional group at the molecular chain end of the polymer as a crosslinking agent. Thereby, the adhesive property under high temperature can be improved and heat resistance can be improved.

  A conventionally well-known thing can be employ | adopted as said crosslinking agent. In particular, polyisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, adducts of polyhydric alcohol and diisocyanate are more preferable. The addition amount of the crosslinking agent is usually preferably 0.05 to 7 parts by weight with respect to 100 parts by weight of the polymer. By setting the amount of the crosslinking agent to 7 parts by weight or less, it is possible to suppress a decrease in adhesive force. Moreover, cohesion force can be improved by setting it as 0.05 weight part or more. Moreover, you may make it include other polyfunctional compounds, such as an epoxy resin, together with such a polyisocyanate compound as needed.

  Moreover, a filler can be suitably mix | blended with the die-bonding film 3 according to the use. The blending of the filler makes it possible to improve the thermal conductivity to the die bond film 3 and adjust the elastic modulus. Examples of the filler include inorganic fillers and organic fillers, and inorganic fillers are preferable from the viewpoints of characteristics such as improved handleability, improved thermal conductivity, adjustment of melt viscosity, and imparting thixotropic properties. The inorganic filler is not particularly limited, and examples thereof include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, and aluminum borate whisker. , Boron nitride, crystalline silica, amorphous silica and the like. These can be used alone or in combination of two or more. From the viewpoint of improving thermal conductivity, aluminum oxide, aluminum nitride, boron nitride, crystalline silica, and amorphous silica are preferable. Further, from the viewpoint that the above properties are well balanced, crystalline silica or amorphous silica is preferable.

  The filler may have an average particle size of 0.005 to 10 μm. By setting the average particle diameter of the filler to 0.005 μm or more, the wettability to the adherend and the adhesiveness can be improved. Moreover, by setting it as 10 micrometers or less, while being able to make the effect of the filler added for provision of said each characteristic sufficient, heat resistance can be ensured. In addition, the average particle diameter of a filler is the value calculated | required, for example with the photometric type particle size distribution analyzer (The product made from HORIBA, apparatus name; LA-910).

  In addition to the additive which capture | acquires the said cation, other additives can be suitably mix | blended with the die-bonding film 3 as needed. Examples of other additives include an anion scavenger, a dispersant, an antioxidant, a silane coupling agent, and a curing accelerator. These can be used alone or in combination of two or more.

  The thickness of the die bond film 3 is not particularly limited, but is preferably 1 to 40 μm, more preferably 3 to 35 μm, and further preferably 5 to 30 μm. When the thickness is 40 μm or less and is relatively thin, the thickness of the entire semiconductor device using the die bond film 3 can be reduced. Further, when the thickness is 1 μm or more, good ion trapping properties can be exhibited.

(Dicing sheet)
The dicing sheet 11 has a configuration in which the pressure-sensitive adhesive layer 2 is laminated on the substrate 1.

  The base material 1 is a strength matrix of the die bond film with a dicing sheet 10. The substrate 1 preferably has ultraviolet transparency. Examples of the substrate 1 include low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, block copolymer polypropylene, homopolyprolene, polybutene, polymethylpentene, and the like. Polyolefin, ethylene-vinyl acetate copolymer, ionomer resin, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester (random, alternating) copolymer, ethylene-butene copolymer, ethylene -Hexene copolymers, polyesters such as polyurethane, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyetheretherketone, polyimide, polyetherimide, polyamide, wholly aromatic polyamide, polyester Phenyl sulphates id, aramid (paper), glass, glass cloth, fluorine resin, polyvinyl chloride, polyvinylidene chloride, cellulose resin, silicone resin, metal (foil), paper, and the like.

  Moreover, as a material of the base material 1, polymers, such as the crosslinked body of the said resin, are mentioned. The plastic film may be used unstretched or may be uniaxially or biaxially stretched as necessary. According to the resin sheet to which heat shrinkability is imparted by stretching or the like, the adhesive area between the pressure-sensitive adhesive layer 2 and the die bond film 3 is reduced by thermally shrinking the base material 1 after dicing, and the semiconductor chip can be recovered. Simplification can be achieved.

  The surface of the substrate 1 is chemically treated by conventional surface treatments such as chromic acid treatment, ozone exposure, flame exposure, high piezoelectric impact exposure, ionizing radiation treatment, etc. in order to improve adhesion and retention with adjacent layers. Alternatively, a physical treatment or a coating treatment with a primer (for example, an adhesive substance described later) can be performed. The base material 1 can be used by appropriately selecting the same kind or different kinds, and a blend of several kinds can be used as necessary.

  The thickness of the substrate 1 is not particularly limited and can be appropriately determined, but is generally about 5 to 200 μm.

  It does not restrict | limit especially as an adhesive used for formation of the adhesive layer 2, For example, common pressure sensitive adhesives, such as an acrylic adhesive and a rubber adhesive, can be used. The pressure-sensitive adhesive is an acrylic pressure-sensitive adhesive based on an acrylic polymer from the standpoint of cleanability with an organic solvent such as ultrapure water or alcohol for electronic components that are difficult to contaminate semiconductor wafers and glass. Is preferred.

  Examples of the acrylic polymer include (meth) acrylic acid alkyl esters (for example, methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester, t-butyl ester, pentyl ester, Isopentyl ester, hexyl ester, heptyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, nonyl ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester, tridecyl ester, tetradecyl ester, hexadecyl ester , Octadecyl esters, eicosyl esters, etc., alkyl groups having 1 to 30 carbon atoms, especially 4 to 18 carbon linear or branched alkyl esters, etc.) and Meth) acrylic acid cycloalkyl esters (e.g., cyclopentyl ester, acrylic polymers such as one or more was used as a monomer component of the cyclohexyl ester etc.). In addition, (meth) acrylic acid ester means acrylic acid ester and / or methacrylic acid ester, and (meth) of the present invention has the same meaning.

  The acrylic polymer contains units corresponding to other monomer components copolymerizable with the (meth) acrylic acid alkyl ester or cycloalkyl ester, if necessary, for the purpose of modifying cohesive force, heat resistance and the like. You may go out. Examples of such monomer components include, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; maleic anhydride Acid anhydride monomers such as itaconic anhydride; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate Hydroxyl group-containing monomers such as 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate; Styrene Contains sulfonic acid groups such as phonic acid, allylsulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, (meth) acrylamidepropanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalenesulfonic acid Monomers; Phosphoric acid group-containing monomers such as 2-hydroxyethyl acryloyl phosphate; acrylamide, acrylonitrile and the like. One or more of these copolymerizable monomer components can be used. The amount of these copolymerizable monomers used is preferably 40% by weight or less based on the total monomer components.

  Furthermore, since the acrylic polymer is crosslinked, a polyfunctional monomer or the like can be included as a monomer component for copolymerization as necessary. Examples of such polyfunctional monomers include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) An acrylate etc. are mentioned. These polyfunctional monomers can also be used alone or in combination of two or more. The amount of the polyfunctional monomer used is preferably 30% by weight or less of the total monomer components from the viewpoint of adhesive properties and the like.

  The acrylic polymer can be obtained by subjecting a single monomer or a mixture of two or more monomers to polymerization. The polymerization can be performed by any method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization and the like. From the viewpoint of preventing contamination of a clean adherend, the content of the low molecular weight substance is preferably small. From this point, the number average molecular weight of the acrylic polymer is preferably 100,000 or more, more preferably about 200,000 to 3,000,000, and particularly preferably about 300,000 to 1,000,000.

  In addition, an external cross-linking agent can be appropriately employed for the pressure-sensitive adhesive in order to increase the number average molecular weight of an acrylic polymer as a base polymer. Specific examples of the external crosslinking method include a method of adding a so-called crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound, a melamine crosslinking agent, and reacting them. When using an external cross-linking agent, the amount used is appropriately determined depending on the balance with the base polymer to be cross-linked, and further depending on the intended use as an adhesive. In general, about 5 parts by weight or less, further 0.1 to 5 parts by weight is preferably blended with respect to 100 parts by weight of the base polymer. Furthermore, you may use additives, such as conventionally well-known various tackifiers and anti-aging agent, other than the said component as needed to an adhesive.

  The pressure-sensitive adhesive layer 2 can be formed of a radiation curable pressure-sensitive adhesive. The radiation curable pressure-sensitive adhesive can increase the degree of cross-linking by irradiation with radiation such as ultraviolet rays, and can easily reduce its adhesive strength, and a portion 2a corresponding to the work pasting portion of the pressure-sensitive adhesive layer 2 shown in FIG. The difference in adhesive strength with the other part 2b can be provided by irradiating only with radiation.

  Further, by curing the radiation curable pressure-sensitive adhesive layer 2 in accordance with the die bond film 3 ′ shown in FIG. 2, the portion 2 a having a significantly reduced adhesive force can be easily formed. Since the die bond film 3 ′ is attached to the portion 2 a that has been cured and has reduced adhesive strength, the interface between the portion 2 a and the die bond film 3 ′ of the pressure-sensitive adhesive layer 2 has a property of being easily peeled off during pick-up. On the other hand, the portion not irradiated with radiation has a sufficient adhesive force, and forms the portion 2b. In addition, you may perform irradiation of the radiation to an adhesive layer after dicing and before pick-up.

  As described above, in the pressure-sensitive adhesive layer 2 of the die-bonding film with a dicing sheet 10 shown in FIG. 1, the portion 2 b formed of the uncured radiation-curable pressure-sensitive adhesive adheres to the die-bonding film 3 and is retained when dicing. Power can be secured. In this way, the radiation curable pressure-sensitive adhesive can support the die bond film 3 for fixing a chip-like work (semiconductor chip or the like) to an adherend such as a substrate with a good balance of adhesion and peeling. In the pressure-sensitive adhesive layer 2 of the die-bonding film with a dicing sheet 11 shown in FIG. 2, the portion 2b can fix the wafer ring.

  As the radiation-curable pressure-sensitive adhesive, those having a radiation-curable functional group such as a carbon-carbon double bond and exhibiting adhesiveness can be used without particular limitation. As the radiation curable pressure sensitive adhesive, for example, an addition type radiation curable pressure sensitive adhesive in which a radiation curable monomer component or an oligomer component is blended with a general pressure sensitive pressure sensitive adhesive such as an acrylic pressure sensitive adhesive or a rubber pressure sensitive adhesive. An agent can be illustrated.

  Examples of the radiation curable monomer component to be blended include urethane oligomer, urethane (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol. Examples include stall tetra (meth) acrylate, dipentaerystol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butanediol di (meth) acrylate, and the like. Examples of the radiation curable oligomer component include various oligomers such as urethane, polyether, polyester, polycarbonate, and polybutadiene, and those having a molecular weight in the range of about 100 to 30,000 are suitable. The compounding amount of the radiation-curable monomer component or oligomer component can be appropriately determined in accordance with the type of the pressure-sensitive adhesive layer, and the amount capable of reducing the adhesive strength of the pressure-sensitive adhesive layer. Generally, the amount is, for example, about 5 to 500 parts by weight, preferably about 40 to 150 parts by weight with respect to 100 parts by weight of the base polymer such as an acrylic polymer constituting the pressure-sensitive adhesive.

  In addition to the additive-type radiation curable adhesive described above, the radiation curable pressure-sensitive adhesive has a carbon-carbon double bond in the polymer side chain or main chain or at the main chain terminal as a base polymer. Intrinsic radiation curable pressure sensitive adhesives using Intrinsic radiation curable adhesives do not need to contain oligomer components, which are low molecular components, or do not contain many, so the oligomer components do not move through the adhesive over time and are stable. This is preferable because an adhesive layer having a layered structure can be formed.

  As the base polymer having a carbon-carbon double bond, those having a carbon-carbon double bond and having adhesiveness can be used without particular limitation. As such a base polymer, those having an acrylic polymer as a basic skeleton are preferable. Examples of the basic skeleton of the acrylic polymer include the acrylic polymers exemplified above.

  The method for introducing the carbon-carbon double bond into the acrylic polymer is not particularly limited, and various methods can be adopted, but it is easy in terms of molecular design to introduce the carbon-carbon double bond into the polymer side chain. It is. For example, after a monomer having a functional group is previously copolymerized with an acrylic polymer, a compound having a functional group capable of reacting with the functional group and a carbon-carbon double bond is converted into a radiation curable carbon-carbon double bond. A method of performing condensation or addition reaction while maintaining the above.

  Examples of combinations of these functional groups include carboxylic acid groups and epoxy groups, carboxylic acid groups and aziridyl groups, hydroxyl groups and isocyanate groups, and the like. Among these combinations of functional groups, a combination of a hydroxyl group and an isocyanate group is preferable because of easy tracking of the reaction. Moreover, the functional group may be on either side of the acrylic polymer and the compound as long as the acrylic polymer having the carbon-carbon double bond is generated by a combination of these functional groups. In the preferable combination, it is preferable that the acrylic polymer has a hydroxyl group and the compound has an isocyanate group. In this case, examples of the isocyanate compound having a carbon-carbon double bond include methacryloyl isocyanate, 2-methacryloyloxyethyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, and the like. Further, as the acrylic polymer, those obtained by copolymerizing the above-exemplified hydroxy group-containing monomers, ether compounds of 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, or the like are used.

  As the intrinsic radiation curable pressure-sensitive adhesive, the base polymer (particularly acrylic polymer) having the carbon-carbon double bond can be used alone, but the radiation curable monomer does not deteriorate the characteristics. Components and oligomer components can also be blended. The radiation-curable oligomer component or the like is usually in the range of 30 parts by weight, preferably in the range of 0 to 10 parts by weight with respect to 100 parts by weight of the base polymer.

  The radiation curable pressure-sensitive adhesive contains a photopolymerization initiator when cured by ultraviolet rays or the like. Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α, α′-dimethylacetophenone, 2-methyl-2-hydroxypropio Α-ketol compounds such as phenone and 1-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- ( Acetophenone compounds such as methylthio) -phenyl] -2-morpholinopropane-1; benzoin ether compounds such as benzoin ethyl ether, benzoin isopropyl ether and anisoin methyl ether; ketal compounds such as benzyldimethyl ketal; 2-naphthalenesulfonyl Black Aromatic sulfonyl chloride compounds such as 1; photoactive oxime compounds such as 1-phenone-1,1-propanedione-2- (o-ethoxycarbonyl) oxime; benzophenone, benzoylbenzoic acid, 3,3′-dimethyl Benzophenone compounds such as -4-methoxybenzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 Thioxanthone compounds such as 1,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; camphorquinone; halogenated ketone; acyl phosphinoxide; acyl phosphonate. The compounding quantity of a photoinitiator is about 0.05-20 weight part with respect to 100 weight part of base polymers, such as an acryl-type polymer which comprises an adhesive.

  Examples of radiation curable pressure-sensitive adhesives include photopolymerizable compounds such as addition polymerizable compounds having two or more unsaturated bonds and alkoxysilanes having an epoxy group disclosed in JP-A-60-196956. And a rubber-based pressure-sensitive adhesive and an acrylic pressure-sensitive adhesive containing a photopolymerization initiator such as a carbonyl compound, an organic sulfur compound, a peroxide, an amine, and an onium salt-based compound.

  The radiation curable pressure-sensitive adhesive layer 2 can contain a compound that is colored by irradiation with radiation, if necessary. By including a compound to be colored in the pressure-sensitive adhesive layer 2 by irradiation with radiation, only the irradiated portion can be colored. That is, the portion 2a corresponding to the workpiece pasting portion 3a shown in FIG. 1 can be colored. Accordingly, whether or not the pressure-sensitive adhesive layer 2 has been irradiated with radiation can be immediately determined by visual observation, the workpiece pasting portion 3a can be easily recognized, and workpieces can be easily pasted together. In addition, when detecting a semiconductor chip by an optical sensor or the like, the detection accuracy is increased, and no malfunction occurs when the semiconductor chip is picked up.

  A compound that is colored by radiation irradiation is a compound that is colorless or light-colored before radiation irradiation, but becomes colored by radiation irradiation. Preferable specific examples of such compounds include leuco dyes. As the leuco dye, conventional triphenylmethane, fluoran, phenothiazine, auramine, and spiropyran dyes are preferably used. Specifically, 3- [N- (p-tolylamino)]-7-anilinofluorane, 3- [N- (p-tolyl) -N-methylamino] -7-anilinofluorane, 3- [ N- (p-tolyl) -N-ethylamino] -7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, crystal violet lactone, 4,4 ', 4 "-trisdimethyl Examples include aminotriphenylmethanol, 4,4 ′, 4 ″ -trisdimethylaminotriphenylmethane, and the like.

  Developers preferably used together with these leuco dyes include conventionally used initial polymers of phenol formalin resins, aromatic carboxylic acid derivatives, electron acceptors such as activated clay, and further change the color tone. In some cases, various known color formers can be used in combination.

  Such a compound that is colored by irradiation with radiation may be once dissolved in an organic solvent or the like and then included in the radiation-curable adhesive, or may be finely powdered and included in the pressure-sensitive adhesive. The use ratio of this compound is 10% by weight or less in the pressure-sensitive adhesive layer 2, preferably 0.01 to 10% by weight, and more preferably 0.5 to 5% by weight. If the proportion of the compound exceeds 10% by weight, the radiation applied to the pressure-sensitive adhesive layer 2 will be absorbed too much by this compound, so that the portion 2a of the pressure-sensitive adhesive layer 2 will be insufficiently cured and will be sufficiently sticky. Power may not decrease. On the other hand, in order to sufficiently color, it is preferable that the ratio of the compound is 0.01% by weight or more.

  When the pressure-sensitive adhesive layer 2 is formed of a radiation curable pressure-sensitive adhesive, a part of the pressure-sensitive adhesive layer 2 is radiated so that the pressure-sensitive adhesive strength of the portion 2a in the pressure-sensitive adhesive layer 2 is smaller than the pressure-sensitive adhesive strength of the other portion 2b. It may be irradiated.

  Examples of the method for forming the portion 2a on the pressure-sensitive adhesive layer 2 include a method in which after the radiation-curable pressure-sensitive adhesive layer 2 is formed on the support substrate 1, the portion 2a is partially irradiated with radiation to be cured. It is done. The partial radiation irradiation can be performed through a photomask in which a pattern corresponding to the portion 3b other than the workpiece pasting portion 3a is formed. Moreover, the method etc. of irradiating and hardening | curing an ultraviolet-ray spotly are mentioned. The radiation curable pressure-sensitive adhesive layer 2 can be formed by transferring what is provided on the separator onto the support substrate 1. Partial radiation curing can also be performed on the radiation curable pressure-sensitive adhesive layer 2 provided on the separator.

  In the case where the pressure-sensitive adhesive layer 2 is formed of a radiation curable pressure-sensitive adhesive, all or a part of at least one side of the support substrate 1 other than the part corresponding to the workpiece pasting part 3a is shielded from light. The portion 2a with reduced adhesive strength can be formed by irradiating with radiation after forming the radiation-curable pressure-sensitive adhesive layer 2 on the substrate and curing the portion corresponding to the workpiece pasting portion 3a. . As a light shielding material, what can become a photomask on a support film can be prepared by printing, vapor deposition, or the like. According to this manufacturing method, the die-bonding film 10 with a dicing sheet of this invention can be manufactured efficiently.

  In addition, when curing inhibition by oxygen occurs during irradiation, it is desirable to block oxygen (air) from the surface of the radiation curable pressure-sensitive adhesive layer 2 by some method. For example, a method of coating the surface of the pressure-sensitive adhesive layer 2 with a separator, a method of irradiating ultraviolet rays or the like in a nitrogen gas atmosphere, and the like can be mentioned.

  The thickness of the pressure-sensitive adhesive layer 2 is not particularly limited, but is preferably about 1 to 50 μm from the viewpoint of preventing chipping of the chip cut surface and compatibility of fixing and holding the adhesive layer. Preferably it is 2-30 micrometers, Furthermore, 5-25 micrometers is preferable.

(Manufacturing method of die bond film with dicing sheet)
The die bond film 10 with a dicing sheet is produced as follows, for example.
First, the base material 1 can be formed by a conventionally known film forming method. Examples of the film forming method include a calendar film forming method, a casting method in an organic solvent, an inflation extrusion method in a closed system, a T-die extrusion method, a co-extrusion method, and a dry lamination method.

  Next, after a pressure-sensitive adhesive composition solution is applied onto the substrate 1 to form a coating film, the coating film is dried under predetermined conditions (heat-crosslinked as necessary), and the pressure-sensitive adhesive layer 2 is formed. Form. It does not specifically limit as a coating method, For example, roll coating, screen coating, gravure coating, etc. are mentioned. As drying conditions, for example, the drying temperature is 80 to 150 ° C. and the drying time is 0.5 to 5 minutes. Moreover, after apply | coating an adhesive composition on a separator and forming a coating film, the coating film may be dried on the said drying conditions, and the adhesive layer 2 may be formed. Then, the adhesive layer 2 is bonded together with the separator on the base material 1. Thereby, the dicing sheet 11 is produced.

The die bond film 3 is produced as follows, for example.
First, a resin composition solution that is a material for forming the die bond film 3 is prepared. If necessary, the resin composition solution may be added with a cation-capturing additive, a thermosetting resin, a thermoplastic resin, a filler, or the like into a container and dissolved in an organic solvent so as to be uniform. Can be obtained by stirring.

  The organic solvent is not particularly limited as long as it can uniformly dissolve, knead, or disperse the components constituting the die bond film 3, and a conventionally known organic solvent can be used. Examples of such a solvent include ketone solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, acetone, methyl ethyl ketone, and cyclohexanone, toluene, xylene, and the like. Methyl ethyl ketone, cyclohexanone, and the like are preferably used because they have a high drying rate and can be obtained at low cost.

  Next, the resin composition solution is applied on the base separator to a predetermined thickness to form a coating film, and then the coating film is dried under predetermined conditions to form an adhesive layer (die bond film 3). To do. It does not specifically limit as a coating method, For example, roll coating, screen coating, gravure coating, etc. are mentioned. As drying conditions, for example, the drying temperature is 70 to 160 ° C. and the drying time is 1 to 5 minutes. Moreover, after apply | coating a resin composition solution on a separator and forming a coating film, the coating film may be dried on the said drying conditions, and the die-bonding film 3 may be formed. Then, the die bond film 3 is bonded together with a separator on a base material separator.

  Subsequently, the separator is peeled off from each of the dicing sheet 11 and the die bond film 3, and the die bond film 3 and the pressure-sensitive adhesive layer 2 are bonded to each other so as to be a bonding surface. Bonding can be performed by, for example, pressure bonding. At this time, the lamination temperature is not particularly limited, and is preferably 30 to 50 ° C., for example, and more preferably 35 to 45 ° C. Moreover, a linear pressure is not specifically limited, For example, 0.1-20 kgf / cm is preferable and 1-10 kgf / cm is more preferable. Next, the base material separator on the die bond film 3 is peeled, and the die bond film 10 with a dicing sheet according to the present embodiment is obtained.

(Method for manufacturing semiconductor device)
The method for manufacturing a semiconductor device according to this embodiment includes a step of preparing the thermosetting die bond film,
A die-bonding step of die-bonding a semiconductor chip on an adherend via the thermosetting die-bonding film (hereinafter also referred to as a first embodiment).
Moreover, the method of manufacturing a semiconductor device according to the present embodiment includes a step of preparing the die bond film with a dicing sheet described above,
A bonding step of bonding the thermosetting die-bonding film of the die-bonding film with the dicing sheet and the back surface of the semiconductor wafer;
Dicing the semiconductor wafer together with the thermosetting die bond film to form a chip-shaped semiconductor chip;
A pick-up step of picking up the semiconductor chip together with the thermosetting die-bonding film from the die-bonding film with the dicing sheet;
And a die-bonding step of die-bonding the semiconductor chip on an adherend via the thermosetting die-bonding film (hereinafter also referred to as a second embodiment).
The semiconductor device manufacturing method according to the first embodiment is different from the semiconductor device manufacturing method according to the second embodiment in that the die bonding film with a dicing sheet is used. The manufacturing method is different in that the die bond film is used alone, and is common in other points. In the method for manufacturing a semiconductor device according to the first embodiment, after preparing a die bond film and performing a step of bonding it to a dicing sheet, thereafter, the method is the same as the method for manufacturing a semiconductor device according to the second embodiment. It can be. Therefore, hereinafter, a method for manufacturing a semiconductor device according to the second embodiment will be described.

  In the method for manufacturing a semiconductor device according to this embodiment, first, a die bond film with a dicing sheet is prepared (preparing step). The die-bonding film 10 with a dicing sheet is used as follows by appropriately separating a separator arbitrarily provided on the die-bonding film 3. Hereinafter, the case where the die bond film with dicing sheet 10 is used will be described as an example with reference to FIG.

  First, the semiconductor wafer 4 is pressure-bonded onto the semiconductor wafer bonding portion 3a of the die bond film 3 in the die bond film 10 with a dicing sheet, and this is bonded and held and fixed (bonding step). This step is performed while pressing with a pressing means such as a pressure roll. The attaching temperature at the time of mounting is not specifically limited, For example, it is preferable to exist in the range of 40-90 degreeC.

  Next, dicing of the semiconductor wafer 4 is performed (dicing process). Thereby, the semiconductor wafer 4 is cut into a predetermined size and separated into individual pieces, and the semiconductor chip 5 is manufactured. Although the method of dicing is not particularly limited, for example, the dicing is performed from the circuit surface side of the semiconductor wafer 4 according to a conventional method. Further, in this step, for example, a cutting method called full cut for cutting up to the die bond film 10 with a dicing sheet can be adopted. It does not specifically limit as a dicing apparatus used at this process, A conventionally well-known thing can be used. Moreover, since the semiconductor wafer is bonded and fixed by the die bond film 10 with a dicing sheet, chip breakage and chip jump can be suppressed, and damage to the semiconductor wafer 4 can be suppressed.

  Next, the semiconductor chip 5 is picked up in order to peel off the semiconductor chip adhered and fixed to the die bond film 10 with a dicing sheet (pickup step). The pickup method is not particularly limited, and various conventionally known methods can be employed. For example, a method of pushing up each semiconductor chip 5 from the die bond film with dicing sheet 10 side with a needle and picking up the pushed semiconductor chip 5 with a pickup device, etc. can be mentioned.

  As pick-up conditions, the needle push-up speed is preferably 5 to 100 mm / sec, and more preferably 5 to 10 mm / sec in terms of preventing chipping.

  Here, when the pressure-sensitive adhesive layer 2 is an ultraviolet curable type, the pickup is performed after the pressure-sensitive adhesive layer 2 is irradiated with ultraviolet rays. Thereby, the adhesive force with respect to the die-bonding film 3 of the adhesive layer 2 falls, and peeling of the semiconductor chip 5 becomes easy. As a result, the pickup can be performed without damaging the semiconductor chip 5. Conditions such as irradiation intensity and irradiation time at the time of ultraviolet irradiation are not particularly limited, and may be set as necessary. Moreover, the above-mentioned thing can be used as a light source used for ultraviolet irradiation. In addition, when the adhesive layer is preliminarily irradiated and cured and this cured adhesive layer and the die bond film are bonded together, the ultraviolet irradiation here is unnecessary.

  Next, the picked-up semiconductor chip 5 is bonded and fixed to the adherend 6 via the die-bonding film 3 (die-bonding process). Examples of the adherend 6 include a lead frame, a TAB film, a substrate, and a separately manufactured semiconductor chip. The adherend 6 may be, for example, a deformable adherend that can be easily deformed or a non-deformable adherend (such as a semiconductor wafer) that is difficult to deform.

  A conventionally well-known thing can be used as said board | substrate. As the lead frame, a metal lead frame such as a Cu lead frame or a 42 Alloy lead frame, or an organic substrate made of glass epoxy, BT (bismaleimide-triazine), polyimide, or the like can be used. However, the present invention is not limited to this, and includes a circuit board that can be used by mounting a semiconductor chip and electrically connecting to the semiconductor chip.

Next, since the die bond film 3 is a thermosetting type, the semiconductor chip 5 is bonded and fixed to the adherend 6 by thermosetting to improve the heat resistance (thermosetting step). The heating temperature can be 80 to 200 ° C, preferably 100 to 175 ° C, more preferably 100 to 140 ° C. The heating time can be 0.1 to 24 hours, preferably 0.1 to 3 hours, more preferably 0.2 to 1 hour. Moreover, you may perform thermosetting on pressurization conditions. The pressurization condition is preferably in a range of 1~20kg / cm ^2, in the range of 3~15kg / cm ² is more preferable. Thermal curing under pressure can be performed, for example, in a chamber filled with an inert gas. In addition, what the semiconductor chip 5 adhere | attached and fixed to the board | substrate etc. via the die-bonding film 3 can use for a reflow process.

  The shear bond strength of the die-bonding film 3 after thermosetting is preferably 0.2 MPa or more with respect to the adherend 6, more preferably 0.2 to 10 MPa. When the shear bond strength of the die bond film 3 is at least 0.2 MPa or more, the bonding surface between the die bond film 3 and the semiconductor chip 5 or the adherend 6 by the ultrasonic vibration or heating in the wire bonding process. No shear deformation occurs. That is, the semiconductor chip does not move due to ultrasonic vibration during wire bonding, thereby preventing the success rate of wire bonding from decreasing.

  Next, if necessary, as shown in FIG. 3, the tip of the terminal portion (inner lead) of the adherend 6 and an electrode pad (not shown) on the semiconductor chip 5 are electrically connected by a bonding wire 7. (Wire bonding process). As the bonding wire 7, for example, a gold wire, an aluminum wire, a copper wire or the like is used. The temperature at the time of wire bonding is 80 to 250 ° C, preferably 80 to 220 ° C. The heating time is several seconds to several minutes. The connection is performed by a combination of vibration energy by ultrasonic waves and crimping energy by applying pressure while being heated so as to be within the temperature range. This step can be performed without thermosetting the die bond film 3. Further, the semiconductor chip 5 and the adherend 6 are not fixed by the die bond film 3 in the process of this step.

  Next, as necessary, as shown in FIG. 3, the semiconductor chip 5 is sealed with a sealing resin 8 (sealing step). This step is performed to protect the semiconductor chip 5 and the bonding wire 7 mounted on the adherend 6. This step can be performed by molding a sealing resin with a mold. As the sealing resin 8, for example, an epoxy resin is used. Although the heating temperature at the time of resin sealing is normally performed at 175 degreeC for 60 to 90 second, this invention is not limited to this, For example, it can cure at 165 to 185 degreeC for several minutes. Thereby, the sealing resin is cured, and the semiconductor chip 5 and the adherend 6 are fixed through the die bond film 3. That is, in the present invention, even when the post-curing step described later is not performed, the die-bonding film 3 can be fixed in this step, which contributes to the reduction in the number of manufacturing steps and the manufacturing time of the semiconductor device. Can do. In this sealing step, a method of embedding the semiconductor chip 5 in a sheet-like sealing sheet (see, for example, JP 2013-7028 A) can also be employed.

  Next, heating is performed as necessary to completely cure the insufficiently cured sealing resin 8 in the sealing process (post-curing process). Even when the die bond film 3 is not completely thermoset in the sealing step, the die bond film 3 can be completely thermoset together with the sealing resin 8 in this step. Although the heating temperature in this process changes with kinds of sealing resin, it exists in the range of 165-185 degreeC, for example, and heating time is about 0.5 to 8 hours.

  Thereby, the semiconductor device shown in FIG. 3 is obtained. The semiconductor device manufactured in this way has the ratio B / A of 1 or more, and has a die bond film 3 having sufficient ion trapping properties even after passing through a thermal history, and therefore causes cations. It is possible to suppress malfunctions that occur.

  In addition, the manufacturing method of the semiconductor device according to the present embodiment performs wire bonding without passing through the thermosetting process by heat treatment of the die bond film 3 after the temporary fixing by the die bonding process, and further, the semiconductor chip 5 is sealed with a sealing resin. It may be sealed and the sealing resin may be cured (post-cured). In this case, the shear adhesive force at the time of temporary fixing of the die bond film 3 is preferably 0.2 MPa or more, more preferably 0.2 to 10 MPa with respect to the adherend 6. Even if the wire bonding step is performed without passing through the heating step, the die bond film 3 and the semiconductor are bonded by the ultrasonic vibration or heating in the step, when the shear bonding force at the time of temporary fixing of the die bond film 3 is at least 0.2 MPa. Shear deformation does not occur on the bonding surface with the chip 5 or the adherend 6. That is, the semiconductor chip does not move due to ultrasonic vibration during wire bonding, thereby preventing the success rate of wire bonding from decreasing. Temporary fixing means that the die-bonding film is cured (in a semi-cured state) to such an extent that the curing reaction of the thermosetting die-bonding film does not proceed completely so as not to hinder the subsequent steps. A state in which the semiconductor chip 5 is fixed. In addition, when performing wire bonding without passing through the thermosetting process by the heat processing of a die-bonding film, the said post-curing process is equivalent to the thermosetting process in this specification.

  In addition, the die-bonding film with a dicing sheet of this invention can be used suitably also when laminating | stacking a some semiconductor chip and carrying out three-dimensional mounting. At this time, the die bond film and the spacer may be laminated between the semiconductor chips, or only the die bond film may be laminated between the semiconductor chips without laminating the spacers. Is possible.

  In the embodiment described above, the case where the resin film for a semiconductor device of the present invention is a die bond film has been described. However, the resin film for a semiconductor device according to the present invention is not limited to this example as long as it is used in a semiconductor device, and is a flip chip for forming on the back surface of a semiconductor element flip-chip connected on an adherend. The film for type | mold semiconductor back surfaces may be sufficient, and the sealing film for sealing a semiconductor element may be sufficient.

  Hereinafter, preferred embodiments of the present invention will be described in detail by way of example. However, the materials, blending amounts, and the like described in the examples are not intended to limit the gist of the present invention only to those unless otherwise specified.

The components used in the examples will be described.
Acrylic copolymer: Teisan resin SG-P3 manufactured by Nagase ChemteX Corporation (weight average molecular weight: 850,000, glass transition temperature: 12 ° C.)
Phenol resin: MEH-7851SS manufactured by Meiwa Kasei Co., Ltd. (phenol resin having a biphenylaralkyl skeleton, softening point 67 ° C., hydroxyl group equivalent 203 g / eq.)
Epoxy resin: YDCN-700-2 (o-cresol novolak type epoxy resin, epoxy equivalent 200, softening point 61 ° C.) manufactured by Nippon Steel Chemical Co., Ltd.
Inorganic filler: SO-E2 (fused spherical silica, average particle size 0.5 μm) manufactured by Admatechs
Additive for trapping cations: IXEPLAS-A1 manufactured by Toa Gosei Co., Ltd. (3-component oxide hydrate of magnesium, aluminum and zirconium, average particle size 0.5 μm)
Additive for trapping cations: BT-120 (1,2,3-benzotriazole) manufactured by Johoku Chemical Industry Co., Ltd.
Additive for trapping cations: IXE-100 manufactured by Toa Gosei Co., Ltd. (zirconium-based oxidized hydrate, average particle size 1.0 μm)

  Note that IXEPLAS-A1 and IXE-100 as additives for capturing cations were subjected to surface treatment in advance. The surface treatment was performed by a dry method, and was treated with a silane coupling agent in an amount shown in Table 1 (silane coupling agent treatment amount). As a silane coupling agent, Shin-Etsu Chemical KBM503 (3-methacryloxypropyltriethoxysilane) was used. Moreover, when using BT-120 as an additive which captures cations, the silane coupling agent was dissolved in an organic solvent together with other components.

[Examples and comparative examples]
According to the blending ratio shown in Table 1, each component was dissolved and dispersed in methyl ethyl ketone as an organic solvent to obtain a resin composition solution having a concentration of 20% by weight. The resin composition solution was applied on a release treatment film made of a polyethylene terephthalate film having a thickness of 38 μm after the silicone release treatment, and then dried at 110 ° C. for 5 minutes. Thereby, a resin film having a thickness of 25 μm was obtained.

(Calculation of ratio B / A)
[1. Calculation of copper ion capture rate A of resin film before thermosetting]
Each resin film (thickness 25 μm) was cut out and bent in an amount of 2.5 g, placed in a cylindrical sealed Teflon (registered trademark) container having a diameter of 58 mm and a height of 37 mm, and a 10 ppm copper (II) ion aqueous solution ( 50 ml of CuCl ₂ aqueous solution was added. Then, it was left to stand at 120 degreeC for 20 hours in the constant temperature dryer (Espec Co., Ltd. product, PV-231). Then, it cooled to room temperature. After taking out the film, the concentration of copper ions in the aqueous solution (copper ion concentration X) was measured using ICP-AES (manufactured by SII Nanotechnology, SPS-1700HVR).
Then, the copper ion capture | acquisition rate A of the resin film before thermosetting was computed by following formula (1). The results are shown in Table 1.
Formula (1): [(10−X) / 10] × 100 (%)

[2. Calculation of copper ion capture rate B of resin film after thermosetting]
Each resin film (thickness 25 μm) was cut out so that the weight after peeling the release treatment film was 2.5 g, bent, and then thermally cured at 175 ° C. for 5 hours. Next, the release treatment film was peeled off, put into a cylindrical sealed Teflon (registered trademark) container having a diameter of 58 mm and a height of 37 mm, and 50 ml of 10 ppm copper (II) ion aqueous solution (CuCl ₂ aqueous solution) was added. . Then, it was left to stand at 120 degreeC for 20 hours in the constant temperature dryer (Espec Co., Ltd. product, PV-231). Then, it cooled to room temperature. After taking out the film, the concentration of copper ions (copper ion concentration Y) in the aqueous solution was measured using ICP-AES (manufactured by SII Nanotechnology, Inc., SPS-1700HVR).
Then, the copper ion capture | acquisition rate B of the resin film after thermosetting was computed by following formula (2). The results are shown in Table 1.
Formula (2): [(10−Y) / 10] × 100 (%)

  Based on the calculated copper ion capture rate A and copper ion capture rate B, the ratio B / A was calculated. The results are shown in Table 1.

(Measurement of 5% weight loss temperature)
10 mg of the sample was weighed and measured with a differential thermal balance (TG-DTA (manufactured by Rigaku Corporation)) in an air atmosphere at a heating rate of 10 ° C./min between 40 and 550 ° C. The temperature when the weight decreased by 5% was read.

(PH of aqueous solution after copper ion capture)
The aqueous solution (aqueous solution when the copper ion concentration Y was measured) obtained in the above “2. Calculation of copper ion capture rate B of resin film after thermosetting” was used as a castany ACT pH meter (D-51, stock Measured using a company Horiba Seisakusho. The results are shown in Table 1.
In addition, pH of 10 ppm copper (II) ion aqueous solution before immersing a resin film was 5.6.
In Example 1 and Example 2 using IXEPASE-A1, the pH is between 4.5 and 5.5, and the pH becomes acidic even after copper ions are captured by ion exchange. Was suppressed. For this reason, it is presumed that the ion-supplementability is kept high even after thermosetting.
On the other hand, in Comparative Example 2 using IXE-100, the pH was about 3.5 and the acidity was strong. For this reason, it is presumed that the ion-supplementability after thermosetting has decreased.

Claims (6)

A resin film for a semiconductor device,
The resin film for a semiconductor device weighing 2.5 g before thermosetting is immersed in 50 ml of an aqueous solution containing 10 ppm of copper ions, and the copper ion concentration (ppm) in the aqueous solution after being left at 120 ° C. for 20 hours. X A resin film for a semiconductor device having a weight of 2.5 g after being thermally cured at 175 ° C. for 5 hours in 50 ml of an aqueous solution having 10 ppm of copper ions is immersed in the aqueous solution and left at 120 ° C. for 20 hours. The ratio B / A of the copper ion trapping rate A calculated by the following formula (1) and the copper ion trapping rate B calculated by the following formula (2) when the copper ion concentration (ppm) is Y Is a resin film for a semiconductor device, wherein
Formula (1): [(10−X) / 10] × 100 (%)
Formula (2): [(10−Y) / 10] × 100 (%)   The resin film for a semiconductor device according to claim 1, wherein a 5% weight reduction temperature is 200 ° C. or more.   The resin film for a semiconductor device according to claim 1, further comprising an inorganic ion scavenger that traps cations.   The resin film for a semiconductor device according to claim 3, wherein the content of the inorganic ion scavenger is 1 to 30% by weight.   A resin film for a semiconductor device having a weight of 2.5 g after being thermally cured at 175 ° C. for 5 hours in 50 ml of an aqueous solution having 10 ppm of copper ions, and the pH of the aqueous solution after being left at 120 ° C. for 20 hours. 5 is within the range of 4-6, The resin film for semiconductor devices of Claim 3 or 4 characterized by the above-mentioned. Preparing a resin film for a semiconductor device according to any one of claims 1 to 5,
A die-bonding step of die-bonding a semiconductor chip on an adherend through the resin film for a semiconductor device.

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