WO2016152271A1 - Resin composition, sheet-shaped resin composition integrated with rear-surface grinding tape, sheet-shaped resin composition integrated with dicing tape, method for manufacturing semiconductor device, and semiconductor device - Google Patents

Abstract

The present invention is a resin composition used to seal an interface between an adherend and a semiconductor element that is flipchip-bonded to the adherend, wherein the resin composition contains a radical reactive compound, a thermoplastic resin, and an inorganic filler, and the proportion of the radical reactive compound relative to the constituents of the entire resin composition, excluding the inorganic filler, is 18.5 weight% or more.

Description

Resin composition, tape-integrated sheet-shaped resin composition for back grinding, dicing tape-integrated sheet-shaped resin composition, semiconductor device manufacturing method, and semiconductor device

The present invention relates to a resin composition, a tape-integrated sheet-shaped resin composition for back grinding, a dicing tape-integrated sheet-shaped resin composition, a method for manufacturing a semiconductor device, and a semiconductor device.

2. Description of the Related Art Conventionally, a sheet-like resin composition used for a flip chip type semiconductor device in which a semiconductor chip is mounted on a substrate by flip chip bonding (flip chip connection), and sealing a gap between the semiconductor chip and the substrate A sheet-shaped resin composition used for the purpose is known (see, for example, Patent Document 1).

Patent No. 4438973

In the sheet-like resin composition as in Patent Document 1, an epoxy resin is used as a thermosetting resin and a curing agent is used.

However, in the epoxy resin curing reaction, the temperature range from the curing start temperature to the curing end temperature is relatively wide. For this reason, the present inventors have found that there is a problem that the curing reaction proceeds gradually even at low temperatures, resulting in poor storage stability.
As a method for solving this problem, there has been considered a method in which a curing agent is employed so that the reaction is started at such a high temperature that the curing reaction does not proceed during storage. However, when such a curing agent is used, heating at a higher temperature and longer time is required in the curing reaction in the manufacturing process of the semiconductor device, and the manufacturing efficiency is lowered.

The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a resin composition that has good storage stability and has fast curability in a semiconductor device manufacturing process. Moreover, it is providing the tape-integrated sheet-like resin composition for back surface grinding which has the said resin composition. Moreover, it is providing the dicing tape integrated sheet-like resin composition which has the said resin composition. Moreover, it is providing the manufacturing method of the semiconductor device using the said sheet-like resin composition. Moreover, it is providing the semiconductor device manufactured using the said resin composition.

The inventors of the present application have found that the above-mentioned problems can be solved by adopting the following configuration, and have completed the present invention.

That is, the present invention is a resin composition used for interface sealing between an adherend and a semiconductor element flip-chip connected on the adherend,
Containing a radical reactive compound, a thermoplastic resin and an inorganic filler,
The ratio of the radical reactive compound to the component excluding the inorganic filler from the entire resin composition is 18.5% by weight or more.

In radical-reactive compounds, once a radical is generated and a reaction (for example, an addition reaction) starts, this radical reaction proceeds in a chain. On the other hand, the reaction does not proceed unless radicals are generated. Therefore, while no radicals are generated at room temperature, if the radicals are generated under conditions that are higher than room temperature but relatively low, both room temperature storage and fast curability can be achieved. Under the present circumstances, it becomes possible to perform the said interface sealing suitably by making the content rate of the said radical reactive compound into the said numerical range.

In the above configuration, an epoxy resin may be contained.

When an epoxy resin is further contained, it is preferable in terms of improving connection reliability.

In the above configuration, it is preferable that the thermosetting rate after heating at 120 ° C. for 10 minutes is 40% or less and the thermosetting rate after heating at 200 ° C. for 5 seconds is 20% or more.

When the thermal curing rate after heating at 120 ° C. for 10 minutes is 40% or less, the progress of the curing reaction at a low temperature is suppressed. Therefore, it is more excellent in storage stability.
In addition, when the thermal curing rate after heating at 200 ° C. for 5 seconds is 20% or more, the curing reaction can proceed in a short time under conditions that are not so high in the curing reaction in the semiconductor device manufacturing process. . As a result, manufacturing efficiency can be further improved.

The thermosetting rate is a value obtained from reaction heat obtained by differential scanning calorimetry (DSC), assuming that the state before heating is 0% and the state of complete thermosetting is 100%. More details will be described later.

The resin composition is preferably in the form of a sheet.

When the resin composition is in sheet form, it is excellent in handleability.

Further, the back-grinding tape-integrated sheet-shaped resin composition according to the present invention is characterized in that the sheet-shaped resin composition is laminated on the back-grinding tape.

According to the tape-integrated sheet-like resin composition for backside grinding according to the present invention, since the sheet-like resin composition is previously laminated on the backside grinding tape, in the semiconductor device manufacturing process, for backside grinding. The process etc. which affix a tape on a sheet-like resin composition can be skipped. Moreover, the said resin composition contains a radical reactive compound, a thermoplastic resin, and an inorganic filler, The ratio of the said radical reactive compound with respect to the component remove | excluding the said inorganic filler from the said whole resin composition is 18. Since it is 5 weight% or more, room temperature preservability and quick curability can be made compatible. Under the present circumstances, it becomes possible to perform the said interface sealing suitably by making the content rate of the said radical reactive compound into the said numerical range.

The dicing tape-integrated sheet-shaped resin composition according to the present invention is characterized in that the sheet-shaped resin composition is laminated on a dicing tape.

According to the dicing tape-integrated sheet-shaped resin composition according to the present invention, since the sheet-shaped resin composition is previously laminated on the dicing tape, the dicing tape is formed into the sheet-shaped resin composition in the semiconductor device manufacturing process. The process of attaching to an object can be omitted. Moreover, the said resin composition contains a radical reactive compound, a thermoplastic resin, and an inorganic filler, The ratio of the said radical reactive compound with respect to the component remove | excluding the said inorganic filler from the said whole resin composition is 18. Since it is 5 weight% or more, room temperature preservability and quick curability can be made compatible. Under the present circumstances, it becomes possible to perform the said interface sealing suitably by making the content rate of the said radical reactive compound into the said numerical range.

In addition, a method for manufacturing a semiconductor device according to the present invention includes:
Step A for preparing a chip with a sheet-shaped resin composition in which the sheet-shaped resin composition is attached to a bump forming surface of a semiconductor chip;
Step B for preparing a mounting substrate on which electrodes are formed;
The sheet-shaped resin composition-attached chip is attached to the mounting substrate with the sheet-shaped resin composition as a bonding surface, and the bumps formed on the semiconductor chip and the mounting substrate are formed. Step C for making the electrodes face each other;
After the step C, the step D of heating and semi-curing the sheet-shaped resin composition,
After the step D, the method includes a step E of heating at a higher temperature than the heating in the step D to join the bump and the electrode and curing the sheet-like composition.

According to the method for manufacturing a semiconductor device of the present invention, the thermosetting rate after heating at 120 ° C. for 10 minutes is 40% or less, and the thermosetting rate after heating at 200 ° C. for 5 seconds is 20% or more. Since the sheet-like resin composition is used, the curing reaction starts and ends early even if the temperature is not greatly increased after the process C until the semi-curing process of the process D. Since the process D can be completed quickly, the efficiency of the semiconductor device manufacturing process can be improved.

According to the present invention, it is possible to provide a resin composition that has good storability and has fast curability in the semiconductor device manufacturing process. Moreover, the tape-integrated sheet-like resin composition for back surface grinding which has the said sheet-like resin composition can be provided. Moreover, the dicing tape integrated sheet-like resin composition which has the said sheet-like resin composition can be provided. Moreover, the manufacturing method of the semiconductor device using the said sheet-like resin composition can be provided.

It is a cross-sectional schematic diagram which shows the tape integrated sheet-like resin composition for back surface grinding which concerns on one Embodiment of this invention. It is a cross-sectional schematic diagram for demonstrating the manufacturing method of the semiconductor device which concerns on one Embodiment of this invention. It is a cross-sectional schematic diagram for demonstrating the manufacturing method of the semiconductor device which concerns on one Embodiment of this invention. It is a cross-sectional schematic diagram for demonstrating the manufacturing method of the semiconductor device which concerns on one Embodiment of this invention. It is a cross-sectional schematic diagram for demonstrating the manufacturing method of the semiconductor device which concerns on one Embodiment of this invention. It is a cross-sectional schematic diagram for demonstrating the manufacturing method of the semiconductor device which concerns on one Embodiment of this invention. It is a cross-sectional schematic diagram for demonstrating the manufacturing method of the semiconductor device which concerns on one Embodiment of this invention. It is a cross-sectional schematic diagram for demonstrating the manufacturing method of the semiconductor device which concerns on one Embodiment of this invention. It is a cross-sectional schematic diagram for demonstrating the manufacturing method of the semiconductor device which concerns on one Embodiment of this invention. It is a cross-sectional schematic diagram for demonstrating the manufacturing method of the semiconductor device which concerns on one Embodiment of this invention. It is a cross-sectional schematic diagram for demonstrating the manufacturing method of the semiconductor device which concerns on one Embodiment of this invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.

[Tape-integrated sheet-shaped resin composition for back grinding]
FIG. 1 is a schematic cross-sectional view showing a back-grinding tape-integrated sheet-shaped resin composition according to an embodiment of the present invention. As shown in FIG. 1, the back-grinding tape-integrated sheet-shaped resin composition 100 according to this embodiment includes a back-grinding tape 12 and a sheet-shaped resin composition 10 laminated on the back-grinding tape 12. Is provided. The back grinding tape 12 includes a substrate 12a and an adhesive layer 12b, and the adhesive layer 12b is provided on the substrate 12a. The sheet-like resin composition 10 is provided on the pressure-sensitive adhesive layer 12b. The sheet-shaped resin composition 10 does not have to be laminated on the entire surface of the back surface grinding tape 12 as shown in FIG. 1, and has a size sufficient for bonding to the semiconductor wafer 16 (see FIG. 2). What is necessary is just to be provided.

(Sheet-shaped resin composition)
The sheet-shaped resin composition 10 has a gap (sea surface) between the semiconductor chip 22 (corresponding to the semiconductor element of the present invention) and the mounting substrate 50 when the semiconductor chip 22 is mounted on the mounting substrate 50 (see FIG. 9). Has a function of sealing. The mounting substrate 50 corresponds to the adherend of the present invention. In this embodiment, the case where the adherend of the present invention is the mounting substrate 50 will be described. However, the adherend of the present invention is not limited to this example, and may be, for example, another semiconductor element. Good. That is, the resin composition of the present invention may perform interface sealing between another semiconductor element as an adherend and a semiconductor element flip-chip connected on the other semiconductor element.

The sheet-shaped resin composition 10 contains a radical reactive compound, a thermoplastic resin, and an inorganic filler.

The radical reactive compound is a compound in which an addition reaction proceeds in a chain manner by a radical reaction. The radical-reactive compound is a compound having one or more radical-reactive double bonds in one molecule and having a weight average molecular weight of 10,000 or less.

Examples of the compound having one or more radical-reactive double bonds in one molecule include epoxy (meth) acrylate resins and bismaleimide resins. Moreover, the compound which has an acryloyl group, an allyl group, and a vinyl group can be mentioned. Epoxy (meth) acrylate means epoxy acrylate or epoxy methacrylate.

The molecular weight (weight average molecular weight) of the epoxy (meth) acrylate resin is not particularly limited, but is preferably 100 to 10,000, and more preferably 200 to 1,000. A weight average molecular weight of 100 to 10000 is preferable in that the cohesive force of the cured product becomes strong. The measurement of a weight average molecular weight can be calculated | required in polystyrene conversion by GPC method.

Specific examples of the epoxy (meth) acrylate resin include bisphenol A type epoxy (meth) acrylates such as ethoxylated (3) bisphenol A diacrylate.

The content of the radical reactive compound is such that the ratio of the radical reactive compound to the component excluding the inorganic filler from the entire sheet resin composition is 18.5% by weight or more. The ratio of the radical reactive compound is preferably 25% by weight or more. Since the ratio of the radical reactive compound is 18.5% by weight or more, the interface sealing can be suitably performed. The proportion of the radical reactive compound is preferably 80% by weight or less, more preferably 60% by weight or less, from the viewpoint of connection reliability.

The sheet-shaped resin composition 10 preferably contains a radical generator. The radical generator generates radicals at least by heating.

Examples of radical generators that generate radicals upon heating include organic peroxides and inorganic peroxides such as benzoyl peroxide (BPO), potassium persulfate, and dicumyl peroxide, and azobisisobutyronitrile (AIBN). ) And the like.

The content of the radical generator with respect to the entire sheet-shaped resin composition 10 is preferably in the range of 0.01 to 5% by weight, preferably in the range of 0.1 to 1% by weight, from the viewpoint of reaction rate. It is more preferable that

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. Among these thermoplastic resins, an acrylic resin that has few ionic impurities and high heat resistance and can ensure the reliability of the semiconductor chip is particularly preferable. In this specification, the thermoplastic resin has a weight average molecular weight of more than 10,000, and may contain a radical-reactive carbon-carbon double bond in the molecule.

The acrylic resin is not particularly limited, and includes one or more esters of acrylic acid or methacrylic acid ester having a linear or branched alkyl group having 30 or less carbon atoms, particularly 4 to 18 carbon atoms. Examples include polymers as components. Examples of the alkyl group include 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 -Ethylhexyl group, octyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, lauryl group, tridecyl group, tetradecyl group, stearyl group, octadecyl group, dodecyl group and the like.

The acrylic resin preferably has a hydroxyl group or an epoxy group. When the acrylic resin has a hydroxyl group or an epoxy group, it reacts with the epoxy resin, and the adhesive strength after thermosetting can be maintained high. In addition, when the acrylic resin has a hydroxyl group or an epoxy group, the hydroxyl group and the epoxy group are relatively less reactive than other functional groups (for example, a carboxyl group). , Excellent storage stability (especially storage stability at room temperature). That is, when the acrylic resin has a hydroxyl group or an epoxy group, it has excellent storability and can maintain high adhesive strength after thermosetting.
In addition, the acrylic resin does not deny that it contains a functional group other than a hydroxyl group and an epoxy group (for example, a carboxyl group, an amino group, an isocyanate group, etc.) within a range not departing from the spirit of the present invention. Preferably it does not contain.

The acrylic resin containing an epoxy group is preferably a copolymer of a monomer containing an epoxy group (epoxy group-containing monomer) and a monomer not containing an epoxy group, and the mixing ratio is storability, and The selection can be made in consideration of the rapid curability in the manufacturing process of the semiconductor device. Specifically, for example, when the total amount of raw material monomers is 100 parts by weight, the blending ratio of the epoxy group-containing monomer and the monomer not containing an epoxy group is 0.1 to 30 parts by weight of the epoxy group-containing monomer, epoxy group It is preferable to use 70 to 99.9 parts by weight of the monomer containing no benzene. In addition, the said mixture ratio is a mixture ratio in case an epoxy group containing monomer has one epoxy group in 1 monomer. Therefore, when the number of epoxy groups contained in one epoxy group-containing monomer is other than 1, the blending ratio can be made in accordance with the case of 1.

The acrylic resin containing a hydroxyl group is preferably a copolymer of a monomer containing a hydroxyl group (hydroxyl group-containing monomer) and a monomer not containing a hydroxyl group, and the mixing ratio is storability. In addition, the selection can be made in consideration of the rapid curability in the manufacturing process of the semiconductor device. Specifically, for example, when the total amount of raw material monomers is 100 parts by weight, the blending ratio of the hydroxyl group-containing monomer and the monomer not containing hydroxyl group is 0.1-30 parts by weight of hydroxyl group-containing monomer, hydroxyl group It is preferable to use 70 to 99.9 parts by weight of the monomer containing no benzene. In addition, the said mixture ratio is a mixture ratio in case a hydroxyl group containing monomer has one hydroxyl group in 1 monomer. Therefore, when the number of hydroxyl groups possessed by one hydroxyl group-containing monomer is other than 1, the blending ratio can be set according to the case of 1.

The acrylic resin containing an epoxy group preferably has an epoxy value of 0.001 to 10 eq / kg, and more preferably 0.01 to 2 eq / kg. By setting the epoxy value to 0.01 eq / kg or more, heat resistance reliability (adhesive strength, etc.) after thermosetting can be ensured. Moreover, room temperature preservability can be improved by setting it as 2 eq / kg or less. The epoxy value is measured as follows.
(Measurement method of epoxy value)
About 3 to 4 g of the sample is precisely weighed into a 100 ml conical flask, and 10 ml of chloroform is added to dissolve it. Further, 30 ml of acetic acid, 5 ml of tetraethylammonium bromide solution and 4 to 6 drops of crystal violet indicator are added, and the mixture is titrated with a 0.1 mol / L perchloric acid acetic acid normal solution while stirring with a magnetic stirrer. A blank test is performed in the same manner. And an epoxy value is obtained by the following formula.
(Epoxy value) = ((V−B) × 0.1 × F) / (W × N)
W: g number of accurately weighed sample B: ml number of 0.1 mol / L perchloric acid acetic acid normal solution required for blank test V: 0.1 mol / L perchloric acid acetic acid normal solution required for titration of sample ml number F: 0.1 mol / L factor of perchloric acid acetic acid normal solution N: solid content (%)

The acrylic resin preferably has a weight average molecular weight of 3 × 10 ⁵ or more, and more preferably 4 × 10 ⁵ or more, from the viewpoint of film formability. When the thermoplastic resin contains an acrylic resin having a weight average molecular weight of 3 × 10 ⁵ or more, the resin composition is easily formed into a sheet. The weight average molecular weight is measured by GPC (gel permeation chromatography) and is a value calculated in terms of polystyrene.

The content of the thermoplastic resin with respect to the entire sheet-shaped resin composition 10 is preferably 1% by weight or more, and more preferably 3% by weight or more. When it is 1% by weight or more, good flexibility is obtained. On the other hand, the content of the thermoplastic resin in the resin component is preferably 40% by weight or less, more preferably 30% by weight or less, and further preferably 25% by weight or less. Good thermal reliability is acquired as it is 30 weight% or less.

The inorganic filler enables, for example, improvement of thermal conductivity, adjustment of storage elastic modulus, and the like.

Examples of the inorganic filler include ceramics such as silica, clay, gypsum, calcium carbonate, barium sulfate, alumina oxide, beryllium oxide, silicon carbide and silicon nitride, and inorganic powder such as carbon. These can be used alone or in combination of two or more. Among these, silica, particularly fused silica is preferably used.

The average particle size of the inorganic filler is preferably within the range of 10 to 1000 nm, more preferably within the range of 20 to 500 nm, and even more preferably within the range of 50 to 300 nm. In the present invention, inorganic fillers having different average particle diameters may be combined so that the average particle diameter as a whole falls within the above numerical range. When the average particle size of the inorganic filler is 10 nm or more, a film can be easily formed. On the other hand, when the average particle size of the inorganic filler is 500 nm or less, transparency can be imparted to the film. The average particle diameter is a value determined by a photometric particle size distribution meter (manufactured by HORIBA, apparatus name: LA-910).

The blending amount of the inorganic filler is preferably set to 50 to 1400 parts by weight with respect to 100 parts by weight of the organic resin component. Particularly preferred is 100 to 900 parts by weight. When the blending amount of the inorganic filler is 50 parts by weight or more, heat resistance and strength are improved. Moreover, fluidity | liquidity is securable by setting it as 1400 weight part or less. Thereby, it can prevent that adhesiveness and embedding fall.

The sheet-like resin composition 10 preferably contains an epoxy resin. Including an epoxy resin is preferable in terms of connection reliability. In particular, when the sheet-shaped resin composition 10 includes a thermoplastic resin and the thermoplastic resin has a functional group that undergoes a crosslinking reaction with an epoxy group, it is preferable to include an epoxy resin.

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. When using a thiol-based curing agent as a curing agent, from the viewpoint of reactivity with thiol-based curing agents and versatility, among the epoxy resins, bisphenol A type, biphenyl type, naphthalene type, phenol novolac type, orthocresol novolak A mold is particularly preferred.

The content of the epoxy resin with respect to the entire sheet-shaped resin composition 10 is preferably in the range of 0.1 to 50% by weight and in the range of 0.4 to 20% by weight from the viewpoint of connection reliability. It is more preferable.

In this embodiment, an epoxy resin may be included. Further, a curing agent may be included.

The sheet-shaped resin composition 10 may contain a thermosetting accelerator. The thermosetting accelerator is not particularly limited and can be appropriately selected from known thermosetting accelerators. A thermosetting accelerator can be used individually or in combination of 2 or more types. As the thermosetting accelerator, for example, amine-based curing accelerators, phosphorus-based curing accelerators, imidazole-based curing accelerators, boron-based curing accelerators, phosphorus-boron-based curing accelerators, and the like can be used. Among these, from the viewpoints of reactivity and solubility, organic compounds containing nitrogen atoms in the molecule (for example, amine-based curing accelerators and imidazole-based curing accelerators) are preferable.

The content of the thermosetting accelerator is preferably 0.001 to 1 part by weight, and more preferably 0.01 to 0.5 part by weight with respect to 100 parts by weight of the epoxy resin. When it is 0.001 part by weight or more, it can be sufficiently cured, and when it is 1 part by weight or less, good storage stability can be maintained.

In addition to the inorganic filler, other additives can be appropriately added to the sheet-shaped resin composition 10 as necessary. Examples of other additives include flame retardants, silane coupling agents, ion trapping agents, pigments such as carbon black, and the like. Examples of the flame retardant include antimony trioxide, antimony pentoxide, brominated epoxy resin, and the like. These can be used alone or in combination of two or more. Examples of the silane coupling agent include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and the like. These compounds can be used alone or in combination of two or more. Examples of the ion trapping agent include hydrotalcites and bismuth hydroxide. These can be used alone or in combination of two or more. In addition, a flux such as an organic acid can be added for the purpose of removing the oxide film of the solder at the time of mounting.

Although the thickness (total thickness in the case of a multilayer) of the sheet-shaped resin composition 10 is not particularly limited, it is preferably 5 μm or more and 500 μm or less in consideration of the strength and fillability of the cured resin. Note that the thickness of the sheet-shaped resin composition 10 can be appropriately set in consideration of the width of the gap between the chip 22 and the mounting substrate 50.

The sheet-like resin composition 10 preferably has a thermosetting rate of 40% or less after heating at 120 ° C. for 10 minutes, more preferably 35% or less, and further preferably 30% or less. When the sheet-like resin composition 10 has a thermosetting rate of 40% or less after being heated at 120 ° C. for 10 minutes, the progress of the curing reaction at a low temperature is further suppressed. Accordingly, the storage stability in the state of the sheet-shaped resin composition is excellent.
In addition, the sheet-like resin composition 10 preferably has a thermosetting rate after heating at 200 ° C. for 5 seconds of 20% or more, more preferably 25% or more, and further preferably 30% or more. . The sheet-like resin composition 10 has a heat curing rate of 20% or more after being heated at 200 ° C. for 5 seconds, under a condition that is not so high in the curing reaction in the semiconductor device manufacturing process, and in a short time. Can be further advanced. As a result, manufacturing efficiency can be further improved.
The thermosetting rate after heating the sheet-like resin composition 10 at 120 ° C. for 10 minutes and the thermosetting rate after heating at 200 ° C. for 5 seconds are the types of curing agents contained in the sheet-like resin composition 10 and It can be controlled by the type of curing accelerator, the content of curing accelerator, various additives, and the like.

The thermosetting rate is obtained by measuring the calorific value using differential scanning calorimetry (DSC). Specifically, first, a sheet-shaped resin composition that has not been heat-cured is prepared, and the temperature is set to 350 ° C. (the thermosetting reaction is assumed to be completely completed from −10 ° C. under a temperature rising rate of 10 ° C./min. The amount of heat generated when the temperature is raised to (the temperature of reaction of the uncured sample) is measured. Moreover, the sample which heated the sheet-shaped resin composition before thermosetting on predetermined conditions (The heating for 10 minutes at 120 degreeC or the heating for 5 seconds at 200 degreeC) is created.
Next, the heat generated when the sample heated under the predetermined conditions was heated from −10 ° C. to 350 ° C. (temperature at which the thermosetting reaction was completely completed) at a temperature increase rate of 10 ° C./min. The amount (the amount of reaction heat of the sample thermally cured under a predetermined condition) is measured. Then, a thermosetting rate is obtained by the following formula (1). The calorific value is determined using the area surrounded by the straight line connecting the two points of the rising temperature of the exothermic peak and the reaction end temperature measured with a differential scanning calorimeter and the peak.

Formula (1):
Thermal curing rate = [{(reaction heat amount of uncured sample) − (reaction heat amount of sample thermally cured under predetermined conditions)} / (reaction heat amount of uncured sample)] × 100 (%)

The sheet-shaped resin composition 10 is prepared so that the peak temperature of thermosetting is within a range of 130 ° C. to 190 ° C. when measured under a temperature rising condition of 10 ° C./min in differential scanning calorimetry. preferable. Examples of the method for adjusting the peak temperature of thermosetting so as to be within the range of 130 ° C. to 190 ° C. include a method of adjusting depending on the type of the curing accelerator and the content of the curing accelerator.

The sheet-like resin composition 10 preferably has a viscosity at 120 ° C. of 0.1 kPa · s to 20 kPa · s, more preferably 0.5 kPa · s to 15 kPa · s, and more preferably 1 kPa · s to 1 kPa · s. More preferably, it is 10 kPa · s or less. If the viscosity at 120 ° C. of the sheet-shaped resin composition 10 is 0.1 kPa · s or more, void expansion when the temperature is raised from the temperature in Step C to the temperature in the semi-curing step D can be suppressed. On the other hand, a sheet-like resin composition can be embedded in the unevenness | corrugation of the board | substrate for mounting as it is 20 kPa * s or less.

The sheet-like resin composition 10 has a viscosity change rate X1 of 0 to 70% between a viscosity at 120 ° C. after storage for 1 month at a temperature of 25 ° C. and a viscosity at 120 ° C. before storage. It is preferably within the range, and more preferably within the range of 0 to 40%. The viscosity change rate X1 is an absolute value of a value obtained by the following formula.
[Viscosity change rate X1 (%)] = [100 × {(viscosity at 120 ° C. after storage for one month) − (viscosity at 120 ° C. before storage)} / (viscosity at 120 ° C. before storage)]

The sheet-like resin composition 10 preferably has a minimum melt viscosity of less than 200 ° C. within a range of 10 Pa · s to 5000 Pa · s, more preferably within a range of 50 Pa · s to 3000 Pa · s, and 100 Pa · s. More preferably, it is in the range of s to 2000 Pa · s. When the minimum melt viscosity at less than 200 ° C. of the sheet-shaped resin composition 10 is in the range of 10 Pa · s to 5000 Pa · s, the bump 18 formed on the semiconductor chip 22 and the mounting substrate 50 are formed in Step C described later. The formed electrode 52 can be opposed to the sheet-shaped resin composition 10 while being easily embedded.

The minimum melt viscosity at less than 200 ° C. of the sheet-shaped resin composition 10 refers to the minimum melt viscosity at less than 200 ° C. before thermosetting.

The minimum melt viscosity at less than 200 ° C. of the sheet-shaped resin composition 10 can be controlled by selecting the constituent material of the sheet-shaped resin composition 10. In particular, it can be controlled by selecting a thermoplastic resin. Specifically, for example, when a low molecular weight resin is used as the thermoplastic resin, the minimum melt viscosity at less than 200 ° C. can be reduced. For example, when a high molecular weight resin is used, the minimum melt viscosity at less than 200 ° C. Can be increased.

The sheet-shaped resin composition 10 is produced as follows, for example. First, a resin composition solution that is a material for forming the sheet-shaped resin composition 10 is prepared. As described above, the resin composition solution contains the resin composition, filler, and other various additives.

Next, the resin composition solution is applied on the base separator so as to have a predetermined thickness to form a coating film, and then the coating film is dried under predetermined conditions to form the sheet-shaped resin composition 10. 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, a drying temperature of 70 to 160 ° C. and a drying time of 1 to 5 minutes are performed.

(Back grinding tape)
The back grinding tape 12 includes a base material 12a and an adhesive layer 12b laminated on the base material 12a.

The base material 12a is a strength matrix of the back-grinding tape-integrated sheet-shaped resin composition 100. For example, polyolefins such as low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, block copolymer polypropylene, homopolyprolene, polybutene, polymethylpentene, ethylene-acetic acid Vinyl copolymer, ionomer resin, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester (random, alternating) copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, Polyester such as polyurethane, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyetheretherketone, polyimide, polyetherimide, polyamide, wholly aromatic polyamide, polyphenyls Fuido, aramid (paper), glass, glass cloth, fluorine resin, polyvinyl chloride, polyvinylidene chloride, cellulose resin, silicone resin, metal (foil), and paper. In the case where the pressure-sensitive adhesive layer 12b is of an ultraviolet curable type, the base material 12a is preferably permeable to ultraviolet rays.

The base material 12a can be appropriately selected from the same type or different types, and can be used by blending several types as necessary. Conventional surface treatment can be applied to the surface of the substrate 12a. In order to impart antistatic ability to the base material 12a, a conductive material vapor deposition layer having a thickness of about 30 to 500 mm and made of metal, alloy, oxides thereof, or the like is provided on the base material 12a. it can. The substrate 12a may be a single layer or two or more layers.

The thickness of the substrate 12a can be determined as appropriate and is generally about 5 μm to 200 μm, preferably 35 μm to 120 μm.

The base material 12a may contain various additives (for example, a colorant, a filler, a plasticizer, an anti-aging agent, an antioxidant, a surfactant, a flame retardant, etc.).

The pressure-sensitive adhesive used for forming the pressure-sensitive adhesive layer 12b is not particularly limited as long as it can hold the semiconductor wafer during back surface grinding of the semiconductor wafer and can be peeled from the semiconductor wafer after back surface grinding. For example, a general pressure-sensitive adhesive such as an acrylic pressure-sensitive adhesive or a rubber-based pressure-sensitive adhesive can be used. The pressure-sensitive adhesive is an acrylic pressure-sensitive adhesive based on an acrylic polymer from the standpoint of cleanability of semiconductor components such as semiconductor wafers and glass with organic solvents such as ultrapure water and alcohol. Is preferred.

Examples of the acrylic polymer include those using acrylic acid ester as a main monomer component. Examples of the acrylic esters 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, in particular, linear or branched alkyl esters having 4 to 18 carbon atoms) Beauty (meth) acrylic acid cycloalkyl esters (e.g., cyclopentyl ester, cyclohexyl ester, etc.), etc. One or acrylic polymer using two or more of the monomer component thereof. 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 includes units corresponding to the 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 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; The Sulfonic acid groups such as lensulfonic acid, allylsulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, (meth) acrylamidepropanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalenesulfonic acid Containing monomers; Phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl 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) Examples include acrylates. 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 carried out 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, it is preferable that the content of the low molecular weight substance is small. From this point, the number average molecular weight of the acrylic polymer is preferably 300,000 or more, more preferably about 400,000 to 3 million.

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 in which a so-called crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound, or a melamine crosslinking agent is added and reacted. 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. Generally, about 5 parts by weight or less, more preferably 0.1 to 5 parts by weight, is preferably added to 100 parts by weight of the base polymer. Furthermore, additives such as various conventionally known tackifiers and anti-aging agents may be used for the pressure-sensitive adhesive, if necessary, in addition to the above components.

The pressure-sensitive adhesive layer 12b 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 can be easily picked up. Examples of radiation include X-rays, ultraviolet rays, electron beams, α rays, β rays, and neutron rays.

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. Examples of radiation curable adhesives include additive radiation curable adhesives in which radiation curable monomer components and oligomer components are blended with general pressure sensitive adhesives such as the above acrylic adhesives and rubber adhesives. 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 thereof 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 urethane, polyether, polyester, polycarbonate, and polybutadiene oligomers, and those having a weight average molecular weight in the range of about 100 to 30000 are suitable. The compounding amount of the radiation curable monomer component or oligomer component can be appropriately determined in such an amount that the adhesive force of the pressure-sensitive adhesive layer can be reduced depending on the type of the pressure-sensitive adhesive layer. In general, 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 a 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 as a base polymer in the polymer side chain or main chain or at the main chain terminal. Intrinsic radiation curable adhesives using Intrinsic radiation-curable pressure-sensitive 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, an acrylic polymer having a basic skeleton is 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. However, the carbon-carbon double bond can be easily introduced into the polymer side chain for easy molecular design. . For example, after a monomer having a functional group is copolymerized in advance 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. Examples of the method include 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. 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. In addition, the functional group may be on either side of the acrylic polymer and the above compound as long as the acrylic polymer having the carbon-carbon double bond is generated by the combination of these functional groups. In the above preferred 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. 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, a base polymer having a carbon-carbon double bond (particularly an acrylic polymer) 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 is usually in the range of 30 parts by weight, preferably in the range of 0 to 10 parts by weight, based on 100 parts by weight of the base polymer.

The radiation curable pressure-sensitive adhesive preferably 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-naphthalenesulfo D Aromatic sulfonyl chloride compounds such as luchloride; 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 blending amount of the photopolymerization initiator is, for example, about 0.05 to 20 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 the case where curing is inhibited by oxygen during irradiation, it is desirable to block oxygen (air) from the surface of the radiation-curing pressure-sensitive adhesive layer 12b by some method. Examples thereof include a method of coating the surface of the pressure-sensitive adhesive layer 12b with a separator, and a method of irradiating radiation such as ultraviolet rays in a nitrogen gas atmosphere.

The pressure-sensitive adhesive layer 12b has various additives (for example, colorants, thickeners, extenders, fillers, tackifiers, plasticizers, anti-aging agents, antioxidants, surfactants, cross-linking agents, etc. ) May be included.

Although the thickness of the pressure-sensitive adhesive layer 12b is not particularly limited, it 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 sheet-shaped resin composition 10. The thickness is preferably 2 to 30 μm, more preferably 5 to 25 μm.

(Production method of tape-integrated sheet-shaped resin composition for back surface grinding)
The back-grinding tape-integrated sheet-like resin composition 100 can be produced, for example, by separately producing the back-grinding tape 12 and the sheet-like resin composition 10 and finally bonding them together.

(Method for manufacturing semiconductor device)
Next, a method for manufacturing a semiconductor device according to an embodiment of the present invention will be described. 2 to 11 are schematic sectional views for explaining a method for manufacturing a semiconductor device according to an embodiment of the present invention.

The manufacturing method of the semiconductor device according to this embodiment is as follows:
Preparing a chip with a sheet-shaped resin composition in which a sheet-shaped resin composition is attached to a bump-forming surface of a semiconductor chip; and
Step B for preparing a mounting substrate on which electrodes are formed;
The sheet-shaped resin composition-attached chip is attached to the mounting substrate with the sheet-shaped resin composition as a bonding surface, and the bumps formed on the semiconductor chip and the mounting substrate are formed. Step C for making the electrodes face each other;
After the step C, the step D of heating and semi-curing the sheet-shaped resin composition,
After the step D, at least a step E of heating at a higher temperature than the heating in the step D, bonding the bumps and the electrodes, and curing the sheet-like composition is included.

[Step of preparing chip with sheet-shaped resin composition]
In the method for manufacturing a semiconductor device according to the present embodiment, first, as shown in FIG. 8, a chip 40 with a sheet-like resin composition is prepared (step A). Hereinafter, a specific method for preparing the chip 40 with sheet-shaped resin composition will be described with reference to FIGS.

(Preparation method of chip with sheet-shaped resin composition)
The method for preparing a chip with a sheet-shaped resin composition according to this embodiment is a sheet-shaped resin composition of a bump-forming surface 22a on which a bump 18 of a semiconductor wafer 16 is formed and a tape-integrated sheet-shaped resin composition 100 for back grinding. 10, a bonding process for grinding the back surface 16b of the semiconductor wafer 16, a wafer fixing process for bonding the dicing tape 11 to the back surface 16b of the semiconductor wafer 16, a peeling process for peeling the back surface grinding tape 12, a semiconductor It includes a dicing step of dicing the wafer 16 to form the semiconductor chip 40 with the sheet-shaped resin composition, and a pickup step of peeling the semiconductor chip 40 with the sheet-shaped resin composition from the dicing tape 11.

<Lamination process>
In the bonding step, the bump forming surface 22a on which the bumps 18 of the semiconductor wafer 16 are formed and the sheet-shaped resin composition 10 of the back-grinding tape-integrated sheet-shaped resin composition 100 are bonded (see FIG. 2).

A plurality of bumps 18 are formed on the bump forming surface 22a of the semiconductor wafer 16 (see FIG. 2). The height of the bump 18 is determined according to the application, and is generally about 5 to 100 μm. Of course, the height of each bump 18 in the semiconductor wafer 16 may be the same or different.

It is preferable that the height X (μm) of the bump 18 formed on the surface of the semiconductor wafer 16 and the thickness Y (μm) of the sheet-shaped resin composition 10 satisfy the relationship of 0.5 ≦ Y / X ≦ 2. . More preferably, 0.5 ≦ Y / X ≦ 1.5, and still more preferably 0.8 ≦ Y / X ≦ 1.3.

When the height X (μm) of the bump 18 and the thickness Y (μm) of the sheet-shaped resin composition 10 satisfy the above relationship, the space between the semiconductor chip 22 and the mounting substrate 50 is sufficiently filled. In addition, the sheet-like resin composition 10 can be prevented from excessively protruding from the space, and contamination of the semiconductor chip 22 by the sheet-like resin composition 10 can be prevented. When the heights of the bumps 18 are different, the height of the highest bump 18 is used as a reference.

First, the separator arbitrarily provided on the sheet-shaped resin composition 10 of the tape-integrated sheet-shaped resin composition 100 for back grinding is appropriately peeled to form bumps 18 of the semiconductor wafer 16 as shown in FIG. The formed bump forming surface 22a and the sheet-shaped resin composition 10 are opposed to each other, and the sheet-shaped resin composition 10 and the semiconductor wafer 16 are bonded (mounting).

The method of bonding is not particularly limited, but a method by pressure bonding is preferable. The pressure for pressure bonding is preferably 0.1 MPa or more, more preferably 0.2 MPa or more. When the pressure is 0.1 MPa or more, the unevenness of the bump forming surface 22a of the semiconductor wafer 16 can be embedded satisfactorily. Moreover, the upper limit of the pressure for pressure bonding is not particularly limited, but is preferably 1 MPa or less, more preferably 0.5 MPa or less.

The bonding temperature is preferably 40 ° C. or higher, more preferably 60 ° C. or higher. When the temperature is 40 ° C. or higher, the viscosity of the sheet-shaped resin composition 10 is reduced, and the unevenness of the semiconductor wafer 16 can be filled without a gap. Further, the bonding temperature is preferably 100 ° C. or lower, more preferably 80 ° C. or lower. When the temperature is 100 ° C. or lower, bonding can be performed while suppressing the curing reaction of the sheet-shaped resin composition 10.

Bonding is preferably performed under reduced pressure, for example, 1000 Pa or less, preferably 500 Pa or less. A minimum is not specifically limited, For example, it is 1 Pa or more.

<Grinding process>
In the grinding step, the surface (that is, the back surface) 16b opposite to the bump forming surface 22a of the semiconductor wafer 16 is ground (see FIG. 3). The thin processing machine used for the back surface grinding of the semiconductor wafer 16 is not particularly limited, and examples thereof include a grinding machine (back grinder) and a polishing pad. Further, the back surface grinding may be performed by a chemical method such as etching. The back surface grinding is performed until the semiconductor wafer 16 has a desired thickness (for example, 20 to 700 μm).

<Wafer fixing process>
After the grinding step, the dicing tape 11 is attached to the back surface 16b of the semiconductor wafer 16 (see FIG. 4). The dicing tape 11 has a structure in which an adhesive layer 11b is laminated on a substrate 11a. The base material 11a and the pressure-sensitive adhesive layer 11b can be suitably produced by using the components and the manufacturing methods shown in the paragraphs of the base material 12a and the pressure-sensitive adhesive layer 12b of the back grinding tape 12.

<Peeling process>
Next, the back surface grinding tape 12 is peeled off (see FIG. 5). Thereby, the sheet-shaped resin composition 10 is exposed.

When the back surface grinding tape 12 is peeled off, if the pressure sensitive adhesive layer 12b has radiation curability, the pressure sensitive adhesive layer 12b is irradiated with radiation to harden the pressure sensitive adhesive layer 12b, so that peeling can be easily performed. Can do. The radiation dose may be set as appropriate in consideration of the type of radiation used and the degree of curing of the pressure-sensitive adhesive layer.

<Dicing process>
In the dicing process, as shown in FIG. 6, the semiconductor wafer 40 and the sheet-shaped resin composition 10 are diced to form the diced semiconductor chip 40 with the sheet-shaped resin composition. Dicing is performed according to a conventional method from the bump forming surface 22a on which the sheet-shaped resin composition 10 of the semiconductor wafer 16 is bonded. For example, a cutting method called full cut that cuts up to the dicing tape 11 can be adopted. It does not specifically limit as a dicing apparatus used at this process, A conventionally well-known thing can be used.

In addition, when expanding the dicing tape 11 following the dicing step, the expansion can be performed using a conventionally known expanding apparatus.

<Pickup process>
As shown in FIG. 7, the semiconductor chip 40 with a sheet-shaped resin composition is peeled from the dicing tape 11 (the semiconductor chip 40 with a sheet-shaped resin composition is picked up). The pickup method is not particularly limited, and various conventionally known methods can be employed.

Here, when the adhesive layer 11b of the dicing tape 11 is an ultraviolet curable type, the pickup is performed after the adhesive layer 11b is irradiated with ultraviolet rays. Thereby, the adhesive force with respect to the semiconductor chip 22 of the adhesive layer 11b falls, and peeling of the semiconductor chip 22 becomes easy.

Thus, the preparation of the semiconductor chip 40 with the sheet-shaped resin composition is completed.

Chip 40 with a sheet-shaped resin composition obtained as described above includes a semiconductor chip 22 on which bumps 18 are formed and a sheet-shaped resin composition 10 that is attached to a bump forming surface 22a of semiconductor chip 22. (See FIG. 8). In the chip 40 with the sheet-shaped resin composition, the bumps 18 are embedded in the sheet-shaped resin composition 10, and the bump forming surface 22 a of the semiconductor chip 22 is attached to the sheet-shaped resin composition 10.

The thickness of the semiconductor chip 22 is not particularly limited, but can be set as appropriate within a range of 10 to 1000 μm, for example.

The height of the bumps 18 formed on the semiconductor chip 22 is not particularly limited, but can be set as appropriate within a range of 2 to 300 μm, for example.

The constituent material of the bump 18 is not particularly limited, but is preferably solder, Sn—Pb, Pb—Sn—Sb, Sn—Sb, Sn—Pb—Bi, Bi—Sn, Sn—Cu. Sn-Pb-Cu, Sn-In, Sn-Ag, Sn-Pb-Ag, Pb-Ag, and Sn-Ag-Cu solders. Among these, those having a melting point within the range of 210 to 230 ° C. can be preferably used, and among the above solders, for example, Sn—Ag system is preferable.

[Process for preparing mounting substrate]
Further, as shown in FIG. 9, a mounting substrate 50 having an electrode 52 formed on the surface 50a is prepared (step B).

As the mounting substrate 50, various substrates such as a lead frame and a circuit substrate (such as a wiring circuit substrate) can be used. The material of such a substrate is not particularly limited, and examples thereof include a ceramic substrate and a plastic substrate. Examples of the plastic substrate include an epoxy substrate, a bismaleimide triazine substrate, and a polyimide substrate.
Further, a semiconductor wafer can be used as the mounting substrate 50.

[Step of making bumps formed on semiconductor chip and electrodes formed on mounting substrate face each other]
After the step A and the step B, as shown in FIG. 10, a chip 40 with a sheet-like resin composition is attached to a mounting substrate 50 with the sheet-like resin composition 10 as a bonding surface, and a semiconductor. The bumps 18 formed on the chip 22 are opposed to the electrodes 52 formed on the mounting substrate 50 (step C). Specifically, first, the sheet-shaped resin composition 10 of the chip-shaped resin composition-attached chip 40 is arranged to face the mounting substrate 50, and then a flip-chip bonder is used to insert the chip with the sheet-shaped resin composition. Apply pressure from 40 side. Thereby, the bump 18 and the electrode 52 are opposed to each other while being embedded in the sheet-shaped resin composition 10. The temperature at the time of bonding is preferably 100 to 200 ° C., more preferably 150 to 190 ° C. However, the temperature is preferably lower than the melting point of the solder. Further, the pressure at the time of bonding is preferably 0.01 to 10 MPa, more preferably 0.1 to 1 MPa.
When the bonding temperature is 150 ° C. or higher, the viscosity of the sheet-shaped resin composition 10 is lowered, and the unevenness can be filled without a gap. Moreover, bonding becomes possible, suppressing the hardening reaction of the sheet-like resin composition 10 as the temperature of bonding is 200 degrees C or less.
At this time, when the minimum melt viscosity at less than 200 ° C. of the sheet-shaped resin composition 10 is in the range of 10 Pa · s to 5000 Pa · s, the bumps 18 formed on the semiconductor chip 22 and the mounting substrate 50 are formed. The electrode 52 can be opposed to the sheet-shaped resin composition 10 while being easily embedded.

[Step of semi-curing sheet resin composition]
After the step C, the sheet-shaped resin composition 10 is heated and semi-cured (step D). The heating temperature in the step D is preferably 100 to 230 ° C., more preferably 150 to 210 ° C. The heating temperature in the step D is preferably lower than the melting point of the solder. The heating time is preferably in the range of 1 to 300 seconds, and more preferably in the range of 3 to 120 seconds.
At this time, if the thermal curing rate after heating the sheet-shaped resin composition 10 at 200 ° C. for 5 seconds is 20% or more, the temperature does not have to be increased greatly after the process C until the semi-curing process of the process D. The curing reaction begins and ends earlier. Since the process D can be completed quickly, the efficiency of the semiconductor device manufacturing process can be improved.

[Step of bonding the bump and the electrode and curing the sheet-like composition]
After the step D, heating is performed at a higher temperature than the heating in the step D, and as shown in FIG. 11, the bumps 18 and the electrodes 52 are joined, and the sheet-like composition 10 is cured (step E). FIG. 11 shows a state in which the bump 18 is made of solder, and the bump 18 and the electrode 52 are joined (electrically connected) by melting the bump 18.
The heating temperature at this time is preferably 180 to 400 ° C., and more preferably 200 to 300 ° C. The heating time is preferably in the range of 1 to 300 seconds, and more preferably in the range of 3 to 120 seconds.

As described above, in this embodiment, the bumps 18 are solders having a melting point in the range of 180 to 260 ° C., and the step D is a step of heating in the range of 100 to 230 ° C. The heating in the step D The temperature is preferably lower than the melting point of the solder. When solder having a melting point in the range of 180 to 260 ° C. is used, the solder is not melted by the heating in the step D. On the other hand, the sheet-like resin composition 10 is semi-cured. That is, in the process D, the sheet-shaped resin composition 10 is semi-cured in a mode in which the solder is not melted. In the process D, since solder is not melted, the solder basically does not flow in the process D.
Then, in this process E, it heats at a temperature higher than the heating in the said process D, fuses the bump 18 and the electrode 52 by melting the solder, and hardens the sheet-like composition 10. At the stage of step E, since the sheet-shaped resin composition 10 is already semi-cured, the resin constituting the sheet-shaped resin composition 10 is difficult to flow. Therefore, even if the solder is melted for bonding the bump 18 and the electrode 52, the solder is prevented from flowing along with the flow of the sheet-shaped resin composition 10. As a result, it is possible to further suppress occurrence of a short circuit or contact failure due to the solder flow.

Thus, the semiconductor device 60 is obtained.

In embodiment mentioned above, the case where the tape integrated sheet-like resin composition for back surface grinding was used as process A which prepares the chip | tip with a sheet-like resin composition was demonstrated. However, step A in the present invention is not limited to this example. For example, you may prepare using a dicing tape integrated sheet-like resin composition. The dicing tape-integrated sheet-shaped resin composition includes a dicing tape and a sheet-shaped resin composition. The dicing tape includes a base material and an adhesive layer, and the adhesive layer is provided on the base material. The sheet-shaped resin composition is provided on the pressure-sensitive adhesive layer. The dicing tape can employ the same configuration as the back grinding tape described above.
Specifically, the method for preparing the chip with sheet-shaped resin composition is a method of bonding a bump forming surface on which a bump of a semiconductor wafer is formed and a sheet-shaped resin composition of a dicing tape-integrated sheet-shaped resin composition. A dicing step of dicing the semiconductor wafer to form a semiconductor chip with a sheet-like resin composition, and a pickup step of peeling the semiconductor chip with a sheet-like resin composition from a dicing tape.

Moreover, you may prepare using the single sheet-like resin composition as the process A which prepares the semiconductor chip with a sheet-like resin composition.
Specifically, a method for preparing a chip with a sheet-shaped resin composition using a single sheet-shaped resin composition is, for example, a process of bonding a bump-formed surface on which a bump of a semiconductor wafer is formed and a sheet-shaped resin composition. A bonding process, a process of bonding a back surface grinding tape to the surface opposite to the semiconductor wafer bonding surface of the sheet-shaped resin composition, a grinding process of grinding the back surface of the semiconductor wafer, and a dicing tape applied to the back surface of the semiconductor wafer Wafer fixing step, peeling step for peeling back surface grinding tape, dicing step for dicing semiconductor wafer to form semiconductor chip with sheet resin composition, and pickup for peeling semiconductor chip with sheet resin composition from dicing tape Process.
Further, as another example of the process A for preparing a semiconductor chip with a sheet-shaped resin composition using a single sheet-shaped resin composition, a bump-forming surface on which a bump of a semiconductor wafer is formed, a sheet-shaped resin composition, Bonding process, bonding the dicing tape to the surface of the sheet-shaped resin composition opposite to the semiconductor wafer bonding surface, dicing the semiconductor wafer to form a semiconductor chip with the sheet-shaped resin composition And a pick-up step of peeling the semiconductor chip with the sheet-shaped resin composition from the dicing tape.

Further, in the above-described embodiment, the case where the sheet-shaped resin composition of the present invention is one that seals the gap between the semiconductor chip and the mounting substrate (so-called underfill sheet) has been described. However, the sheet-shaped resin composition of the present invention is not particularly limited as long as it is used for manufacturing a semiconductor device, that is, for manufacturing a semiconductor device. For example, it may be a die bond film for die bonding a semiconductor element to an adherend, or a flip chip type semiconductor back film for forming on the back surface of a semiconductor element flip chip connected on the adherend. The sealing film for sealing a semiconductor element may be sufficient.

In the above-described embodiment, the case where the resin composition of the present invention is in the form of a sheet has been described. However, in the present invention, the resin composition is not limited to a sheet shape, and may be a liquid or a semisolid at room temperature. When it is in liquid form, it can be used by filling the interface between the adherend and the semiconductor element flip-chip connected on the adherend by capillary action or the like. Further, in the case of a semi-solid state at room temperature, it can be used by being melted when heated and filled by capillary action.

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 scope of the present invention only to those unless otherwise limited.

<Preparation of sheet-shaped resin composition>
The following components were dissolved in methyl ethyl ketone in the proportions shown in Table 1 to prepare an adhesive composition solution having a solid content concentration of 25.4 to 60.6% by weight.
Hydroxyl group-containing acrylic polymer: Acrylic acid ester-based polymer having a hydroxyl group composed mainly of ethyl acrylate-methyl methacrylate (trade name “Paracron W-197C”, manufactured by Negami Kogyo Co., Ltd., weight average molecular weight: 4 × 10 ⁵ )
Epoxy group-containing polymer 1: Epoxy group-containing acrylate ester polymer (trade name “Taisan Resin SG-P3”, manufactured by Nagase ChemteX Corporation, epoxy, mainly composed of ethyl acrylate-butyl acrylate-acrylonitrile) Value: 0.21 eq / kg, weight average molecular weight: 8.5 × 10 ⁵ )
Epoxy group-containing polymer 2: Acrylic ester-based polymer containing an epoxy group (epoxy value: 0.7 eq / kg, weight average molecular weight: 9.3 × 10 ⁵ )
Epoxy group-containing polymer 3: An acrylic acid ester-based polymer containing an epoxy group (epoxy value: 0.88 eq / kg, weight average molecular weight: 9.3 × 10 ⁵ )
Epoxy resin 1: Trade name “Epicoat 1004”, JER Corporation Epoxy resin 2: Trade name “Epicoat 828”, JER Corporation Epoxy resin 3: Trade name “DA-MGIC”, Shikoku Kasei Co., Ltd. Phenolic curing Agent: Trade name “MEH-7851H”, manufactured by Meiwa Kasei Co., Ltd. Radical reactive compound 1: (epoxy acrylate resin: trade name “CN-104NS”, manufactured by Sartomer, having no epoxy group. Weight average molecular weight 10,000 Less than.)
Radical reactive compound 2: (Epoxy acrylate resin: trade name “Unidic V-5500”, manufactured by DIC Corporation, has no epoxy group. Weight average molecular weight of 10,000 or less.)
Radical reactive compound 3: (maleimide resin: trade name “BMI-2300”, manufactured by Daiwa Kasei Kogyo Co., Ltd., weight average molecular weight 10,000 or less)
Flux: 2-phenoxybenzoic acid Inorganic filler: spherical silica (trade name “SO-25R”, manufactured by Admatechs Co., Ltd., average particle size: 500 nm)
Thermosetting accelerator: Imidazole-based curing accelerator (trade name “2PHZ-PW”, manufactured by Shikoku Kasei Co., Ltd.)
Radical generator: Organic peroxide (trade name “Park Mill D”, manufactured by NOF Corporation)

For Examples 1 to 10 and Comparative Example 3, the solution of this adhesive composition was used as a release liner (separator) on a release treatment film made of a polyethylene terephthalate film having a thickness of 38 μm and subjected to a silicone release treatment. After coating, the sheet-shaped resin compositions according to Examples 1 to 10 and Comparative Example 3 were prepared by drying at 120 ° C. for 3 minutes. In Examples 1 to 10 and Comparative Example 3, all thicknesses were set to 35 μm.

For Comparative Example 1 and Comparative Example 2, this adhesive composition solution was applied as a release liner (separator) onto a release-treated film made of a polyethylene terephthalate film having a thickness of 38 μm and subjected to silicone release treatment. Then, the sheet-like resin composition which concerns on the comparative example 1 and the comparative example 2 was produced by making it dry at 130 degreeC for 2 minute (s). In Comparative Example 1 and Comparative Example 2, all the thicknesses were 35 μm.

(Measurement of thermosetting rate after heating at 120 ° C. for 10 minutes)
About the sheet-like resin composition of an Example and a comparative example, the thermosetting rate after heating at 120 degreeC for 10 minutes was measured as follows. For the measurement, a differential scanning calorimeter manufactured by TA Instruments, product name “Q2000” was used.
First, the temperature of the sheet-shaped resin composition that has not been heat-cured is increased from −10 ° C. to 350 ° C. (the temperature at which the thermosetting reaction is assumed to be completely completed) at a temperature increase rate of 10 ° C./min. The calorific value (reaction calorie of the uncured sample) was measured. At this time, the exothermic peak temperature was also read. This value is shown in Table 1.
In addition, a sample was prepared by heating the sheet-shaped resin composition at 120 ° C. for 10 minutes, and 350 ° C. (it was assumed that the thermosetting reaction was completely completed from −10 ° C. under the temperature increase rate of 10 ° C./min. The amount of heat generated when the temperature was raised to (temperature) (the amount of reaction heat of the sample heated at 200 ° C. for 10 seconds) was measured. Then, the thermosetting rate was obtained by the following formula (1a).
Formula (1a):
Thermal curing rate = [{(reaction heat amount of uncured sample) − (reaction heat amount of sample heated at 120 ° C. for 10 minutes)} / (reaction heat amount of uncured sample)] × 100 (%)
The calorific value is determined using the area surrounded by the straight line connecting the two points of the rising temperature of the exothermic peak and the reaction end temperature measured with a differential scanning calorimeter and the peak.
The results are shown in Table 1.

(Measurement of thermosetting rate after heating at 200 ° C. for 5 seconds)
About the sheet-like resin composition of an Example and a comparative example, the thermosetting rate after heating at 200 degreeC for 5 second was measured as follows. For the measurement, a differential scanning calorimeter manufactured by TA Instruments, product name “Q2000” was used.
First, the temperature of the sheet-shaped resin composition that has not been heat-cured is increased from −10 ° C. to 350 ° C. (the temperature at which the thermosetting reaction is assumed to be completely completed) at a temperature increase rate of 10 ° C./min. The calorific value (reaction calorie of the uncured sample) was measured.
In addition, a sample was prepared by heating the sheet-shaped resin composition at 200 ° C. for 5 seconds, and the temperature was set to 350 ° C. (the thermosetting reaction was completely completed from −10 ° C. under the temperature increase rate of 10 ° C./min. The amount of heat generated when the temperature was raised to (temperature) (the amount of reaction heat of the sample heated at 200 ° C. for 10 seconds) was measured. Then, the thermosetting rate was obtained by the following formula (1b).
Formula (1b):
Thermal curing rate = [{(reaction heat amount of uncured sample) − (reaction heat amount of sample heated at 200 ° C. for 5 seconds)} / (reaction heat amount of uncured sample)] × 100 (%)
The calorific value is determined using the area surrounded by the straight line connecting the two points of the rising temperature of the exothermic peak and the reaction end temperature measured with a differential scanning calorimeter and the peak.
The results are shown in Table 1.

[Preservation evaluation]
First, the static viscosity of the sheet-shaped resin composition not subjected to thermosetting treatment was measured with a rotary viscometer (manufactured by Thermo Fisher Scientific, product name “HAAKE MARSIII”). The measurement conditions were a gap of 100 μm, a rotating plate diameter of 20 mm, a heating rate of 10 ° C./min, and a shear rate of 5 (1 / s), and the viscosity at 80 ° C. to 230 ° C. was measured.
Moreover, the viscosity was measured in the same manner as described above for a sheet-like resin composition that was left (stored) for a period of one month at a temperature of 25 ° C.
The measured viscosities at 120 ° C. before and after storage were compared, and based on the viscosity before storage, the case where the viscosity after storage was 200% or less was evaluated as ◯, and the case where it was larger than 200% was evaluated as ×. The reason for setting the evaluation criteria as described above is that, when the viscosity change is 200% or less, the bonding at the time of mounting becomes good. The results are shown in Table 1. Table 1 also shows the measured viscosities at 120 ° C. before and after storage.
Table 1 also shows the viscosity change rate X1 between the viscosity at 120 ° C. after storage for 1 month at a temperature of 25 ° C. and the viscosity at 120 ° C. before storage. The viscosity change rate X1 is an absolute value of a value obtained by the following formula.
[Viscosity change rate X1 (%)] = [100 × {(viscosity at 120 ° C. after 1 month storage) − (viscosity at 120 ° C. before storage)} / (viscosity at 120 ° C. before storage)]

[Void evaluation]
A sheet-shaped resin composition having a thickness of 40 μm was attached to a test vehicle manufactured by Waltz Co., Ltd. (a wafer having a thickness of 725 μm on which bumps having a height of 40 μm were formed). The pasting conditions were a temperature of 60 ° C. and a pasting pressure of 0.5 Mpa under a vacuum degree of 100 Pa. As a result, a sample A having a form as shown in FIG. 8 was obtained.

Next, a mounting substrate (electrode height: 15 μm) having electrodes was attached to the sample A. For the pasting, a flip chip bonder (FC3000W) manufactured by Toray Engineering Co., Ltd. was used. The pasting conditions were a load: 0.5 Mpa, held at 200 ° C. for 10 seconds, and then held at 260 ° C. for 10 seconds.

The obtained sample after mounting was polished in parallel with the chip (wafer) to expose the sheet-shaped resin composition. The void state of the exposed resin portion was confirmed with an optical microscope (200 times), and when no void (maximum diameter: more than 3 μm) was confirmed, “◯”, the occurrence of a void was confirmed even at one location. Cases were evaluated as “x”. The results are shown in Table 1. In the examples, since the sheet-shaped resin composition was sufficiently semi-cured when held at 200 ° C. for 10 seconds, it is considered that expansion of voids was suppressed. On the other hand, in Comparative Example 2, it is considered that the expansion of the void was not suppressed because the sheet-shaped resin composition was not sufficiently cured when held at 200 ° C. for 10 seconds.

 

 

DESCRIPTION OF SYMBOLS 10 Sheet-like resin composition 18 Bump 22 Semiconductor chip 22a Bump formation surface 40 Chip with sheet-like resin composition 50 Mounting substrate 52 Electrode 60 Semiconductor device

Claims (9)

1. A resin composition used for interfacial sealing between an adherend and a semiconductor element flip-chip connected on the adherend,
   Containing a radical reactive compound, a thermoplastic resin and an inorganic filler,
   The resin composition, wherein a ratio of the radical reactive compound to a component excluding the inorganic filler from the whole resin composition is 18.5% by weight or more.
2. The resin composition according to claim 1, comprising an epoxy resin.
3. The thermosetting rate after heating at 120 ° C. for 10 minutes is 40% or less,
   The resin composition according to claim 1 or 2, wherein a thermosetting rate after heating at 200 ° C for 5 seconds is 20% or more.
4. The resin composition according to any one of claims 1 to 3, wherein the thermoplastic resin is an acrylic resin having a hydroxyl group or an epoxy group.
5. 4. The resin composition according to claim 1, wherein the resin composition is in the form of a sheet.
6. 6. A tape-integrated sheet-like resin composition for back grinding, wherein the sheet-like resin composition according to claim 5 is laminated on a back grinding tape.
7. 6. A sheet-shaped resin composition integrated with a dicing tape, wherein the sheet-shaped resin composition according to claim 5 is laminated on a dicing tape.
8. Preparing a chip with a sheet-like resin composition, wherein the sheet-like resin composition according to claim 5 is attached to a bump-forming surface of a semiconductor chip; and
   Step B for preparing a mounting substrate on which electrodes are formed;
   The sheet-shaped resin composition-attached chip is attached to the mounting substrate with the sheet-shaped resin composition as a bonding surface, and the bumps formed on the semiconductor chip and the mounting substrate are formed. Step C for making the electrodes face each other;
   After the step C, the step D of heating and semi-curing the sheet-shaped resin composition,
   After the step D, the semiconductor device includes the step E of heating at a temperature higher than the heating in the step D, bonding the bump and the electrode, and curing the sheet-like composition. Production method.
9. A semiconductor device manufactured using the sheet-like resin composition according to claim 5.

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