TW201535632A - Resin film for semiconductor device, and method for manufacturing semiconductor device - Google Patents

Abstract

Resin film for semiconductor device containing an inorganic ion scavenger that has been subjected to a silane coupling treatment.

Description

Resin film for semiconductor device, and method for manufacturing semiconductor device

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

It is known that in a conventional semiconductor device, a wiring (for example, a copper wiring) formed on a substrate or a metal wire (for example, a copper wire) electrically connecting the substrate to the semiconductor wafer generates metal ions (for example, copper ions). And cause a malfunction.

On the other hand, in the past, attempts have been made to form a fracture layer (deformation) on the back surface of a semiconductor wafer, and to capture cations by the fracture layer and to remove extrinsic gettering.

However, in recent years, as semiconductor devices have become thinner, semiconductor wafers have also become thinner. Therefore, when the fracture layer is formed, there is a problem that the wafer strength before cutting into a semiconductor wafer is remarkably lowered. On the other hand, in large-diameter wafers, mirror polishing is performed for high flattening, and a fracture layer cannot be formed.

Therefore, in the past, it has been used to form a fine fracture layer, which has a certain degree of copper ion trapping while suppressing the decrease in wafer strength. Catching the dry polish (gettering dry polish) technique. However, even in this method, the wafer strength is lowered by dry polishing, and the wafer which is thinner afterwards cannot be sufficiently strong.

Therefore, in recent years, it has been reviewed for The wafer is then added with an additive for trapping metal ions to the resin on the substrate such as the lead frame to prevent malfunction of the semiconductor device (see, for example, Patent Document 1).

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-333085

Patent Document 1 describes a compound which forms a complex compound with a metal ion as an additive for trapping a metal ion, and specific examples include at least one selected from the group consisting of a benzotriazole, a triazine, and the isocyanuric acid additive. Compound. Such an organic complex-forming compound is soluble in a solvent and is suitable for thinning, and conversely, heat resistance is poor. In the production of a semiconductor device, the organic complex-forming compound may undergo thermal decomposition or the like due to various heating steps, and there is a problem that ion trapping property cannot be sufficiently exhibited.

On the other hand, when an additive made of an inorganic material is used as an additive for trapping metal ions, heat resistance is excellent, but the smaller the particle diameter, the more likely it is to cause aggregation, and there is a problem that it cannot be used for a thin resin sheet.

The present invention has been completed in view of the aforementioned problems, and its purpose A resin film for a semiconductor device which is thin and has sufficient ion trapping properties after a thermal history, and a method for producing a semiconductor device using the resin film for a semiconductor device are provided.

The present inventors conducted a resin film for a semiconductor device. Active research. As a result, it has been found that when the inorganic ion scavenger treated with the decane coupling treatment is contained, the ion trapping property is hardly lowered, and the dispersibility of the resin film for a semiconductor device is good, and thus the present invention has been completed.

That is, the resin film for a semiconductor device of the present invention is characterized by containing an inorganic ion scavenger treated by a decane coupling treatment.

According to the above configuration, since the inorganic ion scavenger is contained, the heat resistance is excellent. Further, since the inorganic ion scavenger is subjected to a decane coupling treatment, the dispersibility of the resin film for a semiconductor device is good. Further, the ion trapping property of the inorganic ion scavenger treated by the decane coupling treatment is almost equal to that before the treatment. According to this configuration, according to the above configuration, it is possible to have a thin shape and to have sufficient ion trapping property after the heat history.

In the above configuration, the inorganic ion scavenger preferably has an average particle diameter of 0.6 μm or less.

By setting the average particle diameter of the inorganic ion scavenger to 0.6 μm or less, the thickness of the resin film for a semiconductor device can be made thinner. Further, when the average particle diameter of the inorganic ion scavenger is 0.6 μm or less, the specific surface area can be increased. As a result, ion trapping can be further improved Sex.

In the above configuration, the inorganic ion scavenger is preferably trapped An inorganic two-ion trapping agent for capturing cations and anions.

The aforementioned inorganic ion scavenger is for capturing cations and anions In the case of the two ion trapping agents, the change in pH is small. As a result, the decrease in ion trapping property due to the passage of time can be suppressed.

In the above configuration, the content of the inorganic ion scavenger is higher than It is preferably 1 to 30% by weight.

By setting the content of the aforementioned inorganic ion scavenger to 1 The amount of % can effectively capture cations, and is 30% by weight or less to obtain good film formability.

In the above configuration, a resin film for a semiconductor device having a weight of 2.5 g after heat-hardening at 175 ° C for 5 hours is immersed in 50 ml of an aqueous solution having 10 ppm of copper ions, and the copper ion in the aqueous solution is allowed to stand at 120 ° C for 20 hours. When the concentration (ppm) is Y, the copper ion trapping ratio B calculated by the following formula (2) is preferably 10% or more: Formula (2): [(10-Y)/10] × 100 (%).

When the copper ion trapping rate B after thermal curing is 10% or more, the ion trapping property is more sufficiently obtained.

In the above configuration, a resin film for a semiconductor device having a weight of 2.5 g before thermosetting is immersed in 50 ml of an aqueous solution having 10 ppm of copper ions, and the copper ion concentration (ppm) in the aqueous solution after being left at 120 ° C for 20 hours is set to X, and immersed in a resin film for a semiconductor device having a weight of 2.5 g after heat-hardening at 175 ° C for 5 hours, When the copper ion concentration (ppm) in the aqueous solution after being left at 120 ° C for 20 hours in 50 ml of an aqueous solution of 10 ppm of copper ions is Y, the copper ion capture ratio A calculated by the following formula (1) is expressed by the following formula ( 2) The ratio B/A of the calculated copper ion trapping ratio B is preferably 1 or more, and the formula (1): [(10-X)/10] × 100 (%)

Formula (2): [(10-Y)/10] × 100 (%).

When the ratio B/A of the copper ion trapping rate A before thermal hardening and the copper ion trapping rate B after thermosetting is 1 or more, the cation trapping property after thermosetting is not lowered as compared with that before thermosetting. Accordingly, sufficient ion trapping property is obtained even after passing through the thermal history in the manufacture of the semiconductor device.

In the above configuration, the thickness is preferably in the range of 1 to 40 μm.

When the thickness is in the range of 1 to 40 μm, the thickness of the entire semiconductor device can be reduced by using the resin film for a semiconductor device.

Further, the method of manufacturing a semiconductor device of the present invention includes the steps of: preparing a resin film for a semiconductor device, and a step of solidifying a semiconductor wafer on the adherend by a resin film for the semiconductor device. .

According to the above configuration, the resin film for a semiconductor device contains an inorganic ion scavenger and is excellent in heat resistance. Further, since the inorganic ion scavenger is subjected to a decane coupling treatment, the dispersibility of the resin film for a semiconductor device is good. Further, the ion trapping property of the inorganic ion scavenger treated by the decane coupling treatment is almost equal to that before the treatment. Therefore, the semiconductor device manufactured using the resin film for a semiconductor device described above can be made thin and has sufficient separation Sub-capture.

1‧‧‧Substrate

2‧‧‧Adhesive layer

2a‧‧‧ Attached part

2b‧‧‧Other parts

3‧‧‧Crystalline film

3'‧‧‧Crystalline film

3a‧‧‧Working part attachment

3b‧‧‧Parts other than the attached part of the workpiece

4‧‧‧Semiconductor wafer

5‧‧‧Semiconductor wafer

6‧‧‧Adhesive body

7‧‧‧bonded metal wire

8‧‧‧ Sealing resin

10‧‧‧Crystal film with dicing flakes

11‧‧‧Cleaved thin slices

12‧‧‧Cladding film with dicing flakes

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a solid crystal film with a dicing sheet according to an embodiment of the present invention.

Fig. 2 is a schematic cross-sectional view showing a solid crystal film with a dicing sheet according to another embodiment of the present invention.

Fig. 3 is a schematic cross-sectional view showing a method of manufacturing a semiconductor device of the embodiment.

Hereinafter, first, a tree for a semiconductor device of the present invention The case where the lipid film is a die-bonded film will be described as a preferred embodiment of the present invention. In the die-bonded film of the present embodiment, the solid crystal film with a dicing sheet described below is in a state in which the dicing sheet is not bonded. Therefore, in the following, a solid crystal film with a diced sheet will be described, and a solid crystal film will be described.

1 is a view showing a crystal cut sheet according to an embodiment of the present invention. A schematic cross-sectional view of a solid crystal film. Fig. 2 is a schematic cross-sectional view showing another solid crystal film with a dicing sheet according to another embodiment of the present invention.

As shown in FIG. 1, the die-bonded film 10 with a dicing sheet has The solid crystal film 3 is laminated on the sliced sheet 11. The dicing sheet 11 is formed by laminating an adhesive layer 2 on the substrate 1, and the die-bonding film 3 is disposed on the substrate 1 Adhesive layer 2 on. Further, the solid crystal film with the dicing sheet may be formed by forming the solid crystal film 3' only in the portion to which the workpiece is attached, as in the case of the solid crystal film 12 with the dicing sheet shown in Fig. 2 . The die-bonded film 3' and the die-bonded film 3 are different in shape only, and various resins, additives, fillers, and the like constituting the film can be used in the same manner as the die-bonded film 3.

Hereinafter, the respective configurations of the die-bonded film 10 with the dicing sheet shown in Fig. 1 will be mainly described.

(solid crystal film)

The solid crystal film 3 contains an inorganic ion scavenger treated with a decane coupling agent. The inorganic ion scavenger may be an inorganic cation scavenger that mainly captures a cation, or an inorganic anion scavenger that mainly captures an anion. In addition, the inorganic ion scavenger may also be an inorganic two ion scavenger that captures cations and anions.

Examples of the cation captured by the inorganic ion scavenger include Na, K, Ni, Cu, Cr, Co, Hf, Pt, Ca, Ba, Sr, Fe, Al, Ti, Zn, Mo, Mn, V, and the like. Ion (cation).

(inorganic ion trapping agent)

The inorganic ion scavenger is an inorganic ion exchanger that captures ions by ion exchange. Specifically, the inorganic cation scavenger is an inorganic cation exchanger that captures a cation by ion exchange, and the inorganic anion scavenger is an inorganic anion exchanger that captures anions by ion exchange, and inorganic two ions. The capture agent is an inorganic two ion exchanger that captures both cations and anions by ion exchange. Since the inorganic ion scavenger is hard to thermally decompose, it has sufficient ion trapping property after the heat history. Among the above inorganic ion scavengers, it is preferred to capture at least Cu ions (copper ions). The reason for this is that copper ions are likely to be generated in a large amount compared to other ions, and there is a high possibility that the operation failure of the semiconductor device is greatly affected. Further, the inorganic ion scavenger is preferably an inorganic two ion scavenger. When the inorganic ion scavenger is a two ion scavenger that captures a cation and an anion, the pH changes little. As a result, the decrease in ion trapping property over time can be suppressed. Specifically, an ion (for example, a hydrogen ion) released as a counter ion when capturing a cation is neutralized as an ion (for example, hydroxide ion) released as a counter ion when an anion is captured. 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 inorganic two-ion trapping agent refers to an inorganic two-ion exchanger that can capture a certain amount or more of copper ions and chloride ions. Specific examples of the inorganic two-ion exchanger include a copper (II) ion partition coefficient (Kd) obtained by a method for measuring a copper (II) ion partition coefficient described below, which is 10 or more, and is determined based on the following ion exchange capacity. The ion exchange capacity (meq/g) obtained by the method is 0.5 or more.

<Method for Measuring Copper (II) Ion Partition Coefficient>

50 ml of a test solution containing 5.0 g of an inorganic two ion exchanger and 0.01 N of copper (II) ions was fed into a 100 ml polyethylene container, which was tied and shaken at 25 ° C for 24 hours. After the vibration, the membrane was filtered through a 0.1 μm membrane filter, and the copper (II) ion concentration in the filtrate was measured by ICP-AES (SII. Nanotecnology, SPS-1700HVR) to determine the copper (II) ion distribution. Coefficient Kd. Kd (ml / g) is expressed by (C ₀ - C) × V / (C × m), C ₀ is the initial ion concentration, C is the test solution ion concentration, V is the test liquid volume (ml), m is inorganic The weight (g) of the two ion exchangers.

<Method for Measuring Ion Exchange Capacity>

1.0 g of the inorganic two ion exchanger was immersed in 50 ml of a saturated NaCl aqueous solution and allowed to stand at room temperature for 20 hours. The amount of hydroxide ions generated by the inorganic two ion exchanger was quantified by titration with a 0.1 N aqueous HCl solution, and the ion exchange capacity (meq./g) was determined.

The above inorganic ion scavenger is not particularly limited and can be used. Examples of the various inorganic ion scavengers include oxidized hydrates of elements selected from the group consisting of ruthenium, osmium, zirconium, titanium, tin, magnesium, and aluminum. These may be used alone or in combination of two or more. Among them, the three components of magnesium, aluminum and zirconium are preferably oxidized hydrates. The three components of magnesium, aluminum and zirconium are trapped in the vicinity of neutrality even if the pH of the trapped ions is captured by ion exchange to capture both ions of the cation and the anion. Therefore, better ion trapping properties are obtained. In addition, the three components of magnesium, aluminum and zirconium are particularly suitable for use in semiconductor applications where flawlessness is required.

Commercial products of the aforementioned inorganic ion scavengers can be cited as East Asia Trade names manufactured by Synthetic Co., Ltd.: IXEPLAS-A1, IXEPLAS-A2, etc. These are all inorganic two ion trapping agents.

The average particle diameter of the aforementioned inorganic ion scavenger is preferably 0.6 μm. Hereinafter, it is more preferably 0.55 μm or less, and still more preferably 0.5 μm or less. By When the average particle diameter of the inorganic ion scavenger is 0.6 μm or less, the thickness of the die-bonded film 3 can be made thin. Further, by setting the average particle diameter of the inorganic ion scavenger to 0.6 μm or less, the specific surface area can be increased. As a result, the ion trapping property can be further improved. In addition, the lower limit of the average particle diameter of the inorganic ion scavenger is not particularly limited, but may be 0.1 μm or more in terms of difficulty in dispersion of the resin when the particle diameter is too small.

As described above, the aforementioned inorganic ion scavenger is decane coupled Processing (pre-processing). Since it is subjected to a decane coupling treatment, the inorganic ion scavenger has good dispersibility and is excellent in film formability of the die-bonded film 3. In particular, the inorganic ion scavenger having a small particle size is likely to cause aggregation, but when the decane coupling treatment is performed, the dispersibility is improved. As a result, the thickness of the solid crystal thin film 3 containing the inorganic ion trapping agent can be preferably produced. Further, the inventors have confirmed that even if the inorganic ion scavenger is subjected to the decane coupling treatment, the cation trapping property is the same as or unreducedly compared with the untreated state.

The decane coupling agent is preferably one containing a halogen atom, a hydrolyzable group, and an organic functional group.

The hydrolyzable group is bonded to a ruthenium atom.

The hydrolyzable group is exemplified by a methoxy group, an ethoxy group or the like. Among them, a methoxy group is preferred because the hydrolysis rate is fast and easy to handle.

The hydrolyzable group in the decane coupling agent can crosslink the inorganic ion scavenger while cross-linking the decane coupling agents to each other. Even if the crosslinking point of the surface of the inorganic ion scavenger is small, the surface of the argon coupling agent can be treated with inorganic ions. In terms of the whole agent, it is preferably 2 to 3, more preferably 3

The organofunctional group is bonded to a deuterium atom.

The organic functional group is exemplified by, for example, an acrylonitrile group or a methyl group. An acrylonitrile group, an epoxy group, a phenylamine group or the like. Among them, the reactivity with the epoxy resin is not obtained, and the storage stability of the inorganic ion scavenger to be treated is preferably an acrylonitrile group.

Further, since it has a functional group having high reactivity with an epoxy group When it reacts with the epoxy resin, it retains stability and fluidity. From the viewpoint of suppressing the decrease in fluidity, the organic functional group is preferably one which does not contain a primary amino group, a mercapto group or an isocyanate group.

The number of organic functional groups in the decane coupling agent is preferably one. Since the ruthenium atom has four bonds, the number of organic functional groups in the case of multiple hydrolysis is insufficient.

The decane coupling agent may further contain a bond to a ruthenium atom. alkyl. By allowing the decane coupling agent to contain an alkyl group, the reactivity can be made lower than that of the methacryl oxime group, whereby the surface treatment due to the violent reaction can be prevented from being biased. The alkyl group is exemplified by methyl group, dimethyl group and the like. Among them, a methyl group is preferred.

The decane coupling agent is specifically exemplified as 2-(3,4-epoxycyclohexane Ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldimethoxy Decane, 3-glycidoxypropylmethyldiethoxydecane, dimethyldimethoxydecane, dimethyldiethoxydecane, methyltrimethoxydecane, methyltriethoxydecane Phenyltrimethoxydecane, phenyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxysulfonium Alkane, 3-methacryloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxylate Basear, 3-methylpropenyloxypropyltriethoxydecane, and the like.

a method for treating an inorganic ion scavenger with a decane coupling agent There is no particular limitation, and examples thereof include a wet method in which an inorganic ion scavenger and a decane coupling agent are mixed in a solvent, a dry method in which an inorganic ion scavenger and a decane coupling agent are treated in a gas phase, and the like.

The amount of the decane coupling agent to be treated is not particularly limited, but is relatively It is preferably treated with 0.05 to 5 parts by weight of a decane coupling agent per 100 parts by weight of the inorganic ion scavenger.

The content of the additive for capturing the aforementioned cation is preferably from 1 to 30 The amount % is more preferably from 3 to 35% by weight, still more preferably from 5 to 30% by weight. By setting the content of the additive for capturing the cation to 1% by weight, the cation can be effectively trapped, and by setting it as 30% by weight or less, good film formability can be obtained.

The solid crystal film 3 preferably contains a thermoplastic resin and thermosetting Either or both of the resins. The thermosetting resin is exemplified by a phenol resin, an amine resin, an unsaturated polyester resin, an epoxy resin, a polyurethane resin, a polyoxyxylene resin, or a thermosetting polyimide resin. These resins may be used singly or in combination of two or more kinds. In particular, at least one of an epoxy resin and a phenol resin is preferably used. Among them, epoxy resins are preferably used. When an epoxy resin is contained, a high adhesion force of the die-bonded film 3 and the wafer at a high temperature can be obtained. As a result, water does not easily enter the bonding interface between the die bonding film 3 and the wafer, making it difficult to move ions. Thereby, the reliability is improved.

The foregoing epoxy resin is generally used as an adhesive composition. The user is not particularly limited, and 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, or the like can be used. Difunctional epoxy resin or polyfunctional epoxy resin such as quinone type, phenol novolak type, o-cresol novolac type, trihydroxyphenylmethane type, tetrahydroxyphenylethane type, or hydantoin An epoxy resin such as a triglycidyl isocyanurate type or a glycidylamine type. These may be used singly or in combination of two or more. Among these epoxy resins, a novolac type epoxy resin, a biphenyl type epoxy resin, a trishydroxyphenylmethane type resin or a tetrahydroxyphenylethane type epoxy resin is preferred. Since these epoxy resins are highly reactive with a phenol resin as a curing agent, they are excellent in heat resistance.

Further, the phenol resin is used as the hard epoxy resin For example, a phenol novolak resin, a phenol aralkyl resin, a cresol novolak resin, a third butyl phenol novolak resin, a nonylphenol novolak resin, and the like, and a novolac type phenol resin, A polyoxystyrene such as a benzenediol type phenol resin or a polyparamethoxystyrene. These may be used alone or in combination of two or more. Among these phenol resins, phenol novolac resin and phenol aralkyl resin are preferred. The reason for this is that the connection reliability of the semiconductor device can be improved.

The ratio of the epoxy resin to the phenol resin is preferably as an example. For example, the epoxy group in the epoxy resin component is blended in an amount of from 0.5 to 2.0 equivalents per one equivalent of the hydroxyl group in the phenol resin. More preferably, it is 0.8 to 1.2 equivalents. That is, if the blending ratio of the two deviates from the above range, it cannot be fully performed. The hardening reaction easily deteriorates the properties of the cured epoxy resin.

The aforementioned thermoplastic resin is exemplified by natural rubber and butyl rubber. Glue, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, polybutadiene resin, polycarbonate resin, thermoplastic polymer Imine resin, polyamide resin such as 6-nylon or 6,6-nylon, phenoxy resin, acrylic resin, saturated polyester resin such as PET or PBT, polyamidoximine resin or fluororesin. These thermoplastic resins may be used singly or in combination of two or more kinds. Among these thermoplastic trees, an acrylic resin having a small amount of ionic impurities and high heat resistance and ensuring reliability of a semiconductor element is preferable.

The acrylic resin is not particularly limited and is listed as A polymer (acrylic acid copolymer) having a carbon number of 30 or less, particularly one or two or more kinds of acrylic acid or methacrylic acid ester having a linear or branched alkyl group having 4 to 18 carbon atoms, and a monomer component (acrylic acid copolymer). The aforementioned alkyl groups are exemplified by, for example, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl, pentyl, isopentyl, hexyl, heptyl, cyclohexyl, 2-B. Hexyl, octyl, isooctyl, decyl, isodecyl, decyl, isodecyl, undecyl, lauryl, tridecyl, tetradecyl, stearyl, octadecyl Or dodecyl and the like.

Further, the other monomers forming the aforementioned polymer are not particularly limited. The system is exemplified by various carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxy amyl acrylate, itaconic acid, maleic acid, fumaric acid or crotonic acid, maleic anhydride or itaconic anhydride. And other anhydride monomers, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate Ester, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, (methyl) Various hydroxyl group-containing monomers such as 12-hydroxylauryl acrylate or (4-hydroxymethylcyclohexyl)methyl acrylate, styrenesulfonic acid, allylsulfonic acid, 2-(methyl)propenylamine-2- a sulfonic acid group-containing monomer such as methyl propane sulfonic acid, (meth) acrylamide propylene sulfonic acid, sulfopropyl (meth) acrylate or (meth) propylene phthaloxy naphthalene sulfonic acid, or 2 Various phosphate group-containing monomers such as hydroxyethyl acryloyl phosphatidyl phosphate. These may be used alone or in combination of two or more.

The proportion of the aforementioned thermosetting resin is as long as it is in a specific strip The solid crystal film 3 can be made to function as a thermosetting type when heated under the condition, and is not particularly limited, but is preferably in the range of 5 to 60% by weight, more preferably 10 to 50% by weight. Inside.

The solid crystal film 3 especially contains epoxy resin, phenol resin and C The total amount of the epoxy resin and the phenol resin relative to 100 parts by weight of the acrylic resin is preferably from 10 to 2,000 parts by weight, more preferably from 10 to 1,500 parts by weight, still more preferably from 10 to 1,000 parts by weight. By setting the total amount of the epoxy resin and the phenol resin in an amount of 10 parts by weight or more based on 100 parts by weight of the acrylic resin, the adhesion effect can be obtained by hardening, and peeling can be suppressed, and it can be suppressed by setting it as 2000 parts by weight or less. The film is fragile and the workability is suppressed from being lowered.

When the solid crystal film 3 is pre-crosslinked to a certain extent, it is preferable to add and A polyfunctional compound which reacts with a functional group at the end of the molecular chain of the polymer or the like serves as a crosslinking agent. Thereby, the subsequent characteristics at high temperatures can be improved, and heat resistance can be achieved. Improvement of sex.

The aforementioned crosslinking agent can be used in the past. Especially, with A A polyisocyanate compound such as phenyl diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, or an adduct of a polyhydric alcohol and a diisocyanate is more preferable. The amount of the crosslinking agent added is usually preferably from 0.05 to 7 parts by weight based on 100 parts by weight of the polymer. By setting the amount of the crosslinking agent to 7 parts by weight or less, the decrease in the adhesion force can be suppressed. Further, by setting the amount to 0.05 part by weight or more, the cohesive force can be improved. Further, other polyfunctional compounds such as an epoxy resin may be contained together with the polyisocyanate compound as needed.

In addition, the solid crystal film 3 can be appropriately formulated according to its use. filler. The mixing of the filler can improve the thermal conductivity to the die bonding film 3, adjust the modulus of elasticity, and the like. The filler is exemplified by an inorganic filler and an organic filler, but is preferably an inorganic filler from the viewpoint of improving workability, improving thermal conductivity, adjusting melt viscosity, and imparting characteristics such as thixotropic properties. The inorganic filler is not particularly limited, and examples thereof include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium citrate, magnesium citrate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, and aluminum borate whisker. Boron nitride, crystalline ceria, amorphous ceria, and the like. These may be used alone or in combination of two or more. From the viewpoint of improving thermal conductivity, alumina, aluminum nitride, boron nitride, crystalline cerium oxide, and amorphous cerium oxide are preferred. Further, it is preferable to use crystalline ceria or amorphous ceria based on the viewpoint that the balance of the above characteristics is good.

The filler may have an average particle diameter of 0.005 to 10 μm. By The average particle diameter of the filler is set to 0.005 μm or more, so that the pair can be adhered The wettability and adhesion of the body became good. In addition, when it is 10 μm or less, the effect of the filler added to impart the above-described respective characteristics can be made sufficient, and heat resistance can be ensured. Further, the average particle diameter of the filler is, for example, a value obtained by a photometric particle size distribution meter (manufactured by HORIBA, device name: LA-910).

Further, in the solid crystal film 3, in addition to capturing the aforementioned cation In addition to the additives, other additives may be appropriately formulated as needed. Other additives are exemplified by an anion scavenger, a dispersant, an antioxidant, a decane coupling agent, a hardening accelerator, and the like. These may be used alone or in combination of two or more.

The thickness of the solid crystal film 3 is not particularly limited, and is preferably 1 to 40 μm, more preferably 3 to 35 μm, and even more preferably 5 to 30 μm. When the thickness is 40 μm or less, the thickness of the semiconductor device using the die-bonded film 3 can be made thinner. Further, when the thickness is 1 μm or more, good ion trapping properties can be exhibited.

The solid crystal film 3 is preferably thermally hardened at 175 ° C for 5 hours. Then, the solid crystal film 3 having a weight of 2.5 g was immersed in 50 ml of an aqueous solution having 10 ppm of copper ions, and when the copper ion concentration (ppm) in the aqueous solution was set to Y after being left at 120 ° C for 2 hours, the following formula (2) was used. The calculated copper ion trap rate B was 10% or more. The copper ion capture rate B is preferably 10% or more, more preferably 20% or more. When the copper ion capture rate B is 30% or more, the ion trapping property is more sufficiently obtained.

Formula (2): [(10-Y)/10] × 100 (%)

The solid crystal film 3 is a solid crystal having a weight of 2.5 g before thermal curing. The film 3 was immersed in 50 ml of an aqueous solution having 10 ppm of copper ions, and the copper ion concentration (ppm) in the aqueous solution after standing at 120 ° C for 20 hours was set to X, and the weight after heat hardening at 175 ° C for 5 hours was 2.5. When the solid crystal film 3 of g is immersed in 50 ml of a copper ion aqueous solution having 10 ppm, and the copper ion concentration (ppm) in the aqueous solution after being left at 120 ° C for 20 hours is Y, the copper is calculated by the following formula (1). The ratio B/A of the ion trapping rate A to the copper ion trapping ratio B calculated by the following formula (2) is preferably 1 or more.

Formula (1): [(10-X)/10] × 100 (%)

Formula (2): [(10-Y)/10] × 100 (%)

The above is more preferably 1 or more than B/A, and more preferably 1.1 or more. Further, the ratio B/A is preferably larger, for example, 10 or less. When the ratio B/A of the solid crystal film 3 is 1 or more, the cation trapping property is not lowered after the heat curing as compared with the case before the heat curing. Accordingly, in the manufacture of the semiconductor device, it has more sufficient ion trapping property after passing through the thermal history.

The 5% weight loss temperature of the die-bonded film 3 is preferably 200 ° C or more, more preferably 250 ° C or more, and still more preferably 300 ° C or more. When the 5% weight loss temperature of the die-bonded film 3 is 200 ° C or more, the heat-resistant property of the entire solid crystal film 3 is excellent. The measurement method of the 5% weight loss temperature was carried out by the method described in the examples. The 5% weight reduction temperature of the solid crystal film 3 can be selected by the resin, the additive, the filler, or the like constituting the solid crystal film 3, or the manufacturing conditions when the solid crystal film 3 is formed (for example, the drying temperature after coating the film or Drying time) adjustment.

The solid crystal film 3 will be thermally hardened at 175 ° C for 5 hours. The solid crystal film 3 having a weight of 2.5 g is immersed in 50 ml of an aqueous solution having 10 ppm of copper ions, and the pH in the aqueous solution after standing at 120 ° C for 2 hours is preferably in the range of 4 to 6, more preferably in the range of 4.2 to 5.8. Within, it is better in the range of 4.4~5.5. Inorganic ion scavengers typically capture cations by ion exchange. Therefore, cation capture is affected by pH. Specifically, when the pH is too acidic, the cation trapping property may be lowered. Therefore, the cation trapping property can be further improved by setting the pH to a range of 4 to 6. The method of setting the pH to a range of 4 to 6 is exemplified by a method of using the inorganic ion-trapping agent described below. When an inorganic two-ion trapping agent is used, pH can be suppressed to be excessively acidic, and high ion trapping property can be maintained.

(Cutting slice)

The diced sheet 11 has a structure in which the adhesive layer 2 is laminated on the substrate 1.

The substrate 1 is strong as a solid crystal film 10 with a dicing sheet The mother of the body. The substrate 1 preferably has ultraviolet ray permeability. The substrate 1 is exemplified by, for example, low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymerized polypropylene, block copolymerized polypropylene, homopolypropylene. Polyolefins such as polybutene and polymethylpentene, ethylene-vinyl acetate copolymer, ionic polymer resin, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate (random, alternating Copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, polyurethane, polyethylene terephthalate, polyethylene naphthalate, polyester, polycarbonate, poly Yttrium, polyetheretherketone, polyimide, polyether Imine, polyamine, wholly aromatic polyamine, polyphenyl sulfide, polyarylamine (paper), glass, glass cloth, fluororesin, polyvinyl chloride, polyvinylidene chloride, cellulose resin, Polyoxygen resin, metal (foil), paper, and the like.

And as the material of the substrate 1 is listed as the cross-linking of the aforementioned resin a polymer such as a body. The plastic film may be used without extension, and may be applied by a single-axis or two-axis extension as needed. When the resin sheet capable of imparting heat shrinkability by stretching treatment or the like is used, the bonding area of the adhesive layer 2 and the solid crystal film 3 can be reduced by heat-shrinking the substrate 1 after dicing, and semiconductor wafer recovery can be realized. Easy to use.

The surface of the substrate 1 is to improve adhesion to the adjacent layer Sex, retention, etc., may be applied to conventional surface treatments, for example, chromic acid treatment, ozone exposure, flame exposure, high voltage electric shock exposure, ionizing radiation treatment, etc., chemical or physical treatment, using a primer (for example, described later) Coating treatment of adhesive substance). The substrate 1 may be appropriately selected from the same species or different species, and may be blended using several types as needed.

The thickness of the substrate 1 can be appropriately determined without particular limitation, but one Generally, it is about 5~200μm.

The adhesive used for the formation of the adhesive layer 2 is not particularly limited. For the production, a general pressure-sensitive adhesive such as an acrylic adhesive or a rubber-based adhesive can be used. The pressure-sensitive adhesive is preferably made of an acrylic polymer from the viewpoint of not requiring purification of electronic components such as semiconductor wafers or glass by using an organic solvent such as ultrapure water or alcohol. Acrylic adhesive for base polymer.

The aforementioned acrylic polymer is exemplified by (meth) Alkyl acrylate (eg, methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, second butyl ester, tert-butyl ester, amyl ester, isoamyl ester, hexyl ester, heptyl ester, octyl) Ester, 2-ethylhexyl ester, isooctyl ester, decyl ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester, tridecyl ester, tetradecyl ester, cetyl ester, eighteen An alkyl group such as an alkyl ester or an eicosyl ester having a carbon number of 1 to 30, particularly a linear or branched alkyl ester having 4 to 18 carbon atoms, and a cycloalkyl (meth)acrylate (for example, cyclopentane) One or two or more kinds of acrylic polymers to be used as a monomer component, such as an ester or a cyclohexyl ester. Further, the term "(meth)acrylate" means acrylate and/or methacrylate, and all (meth) of the present invention have the same meaning.

The aforementioned acrylic polymer is modified to have cohesive force and heat resistance The nature and the like may also be included in a unit corresponding to other monomer components copolymerizable with the aforementioned alkyl (meth) acrylate or cycloalkyl ester. The monomer component is exemplified by a carboxyl group such as acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid or the like. Monomer; anhydride monomer such as maleic anhydride or itaconic anhydride; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (A) 6-hydroxyhexyl acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (meth)acrylic acid (4- Hydroxyl-containing monomer such as hydroxymethylcyclohexyl)methyl ester; styrenesulfonic acid, allylsulfonic acid, 2-(methyl)acrylamido-2-methylpropanesulfonic acid, (meth)acrylic acid a sulfonic acid group-containing monomer such as an amine propane sulfonic acid, a sulfopropyl (meth) acrylate or a (meth) propylene phthaloxy naphthalene sulfonic acid; a phosphate group-containing monomer such as 2-hydroxyethyl acryloyl phosphate; acrylamide or acrylonitrile. One or two or more kinds of these copolymerizable monomer components can be used. The amount of the copolymerizable monomers used is preferably 40% by weight or less based on the total of the monomer components.

Further, the acrylic polymer may also contain a crosslinking agent. A polyfunctional monomer or the like is used as a monomer component for copolymerization as needed. Such polyfunctional monomers are exemplified by, for example, hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl Alcohol 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) acrylate, and the like. These polyfunctional monomers may be used alone or in combination of two or more. The amount of the polyfunctional monomer to be used is preferably 30% by weight or less based on the total adhesion of the monomer component.

The aforementioned acrylic polymer is made by making a single monomer or 2 The above monomer mixture is obtained by polymerization. The polymerization can be carried out by any one of solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and the like. The content of the low molecular weight substance is less preferred from the viewpoint of preventing contamination of the clean adherend. Based on this, the number average molecular weight of the acrylic polymer is preferably 100,000 or more, more preferably 200,000 to 3,000,000, and most preferably 300,000 to 1,000,000.

In addition, external crosslinking may be suitably employed in the aforementioned adhesive. The agent is used to increase the number average molecular weight of the acrylic polymer or the like of the base polymer. A specific means of the external crosslinking method is 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 an external crosslinking agent is used, the amount thereof is determined according to the balance with the base polymer to be crosslinked, and is appropriately determined depending on the use as the adhesive. Generally, it is preferably formulated in an amount of about 5 parts by weight or less, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the base polymer. Further, as the adhesive, if necessary, additives such as various adhesion-imparting agents and anti-aging agents conventionally used may be used.

The adhesive layer 2 can be formed by a radiation hardening type adhesive to make. The radiation hardening type adhesive can increase the degree of crosslinking by irradiation with radiation such as ultraviolet rays, can easily reduce the adhesion, and can be attached only to the workpiece of the adhesive layer 2 shown in FIG. The partially corresponding portion 2a is irradiated with radiation to provide a difference in adhesion to the other portion 2b.

Further, by making a spoke together with the die bonding film 3' shown in FIG. The ray hardening type adhesive layer 2 is hardened, and the adhesion portion can be remarkably lowered to easily form the aforementioned portion 2a. In order to bond the solid crystal foil film 3' to the portion 2a which is cured and has a reduced adhesive force, the interface between the aforementioned portion 2a of the adhesive layer 2 and the die-bonded film 3' has a property of being easily peeled off at the time of picking up. On the other hand, the portion where the radiation is not irradiated has a sufficient adhesive force to form the aforementioned portion 2b. Further, the irradiation of the adhesive layer with radiation may be performed after dicing and before picking up.

As described above, the solid crystal film with the dicing sheet shown in FIG. 10 in the adhesive layer 2, by uncured radiation curing adhesive The formed portion 2b is adhered to the die-bonding film 3 to ensure the holding force at the time of crystal cutting. Such a radiation hardening adhesive can be followed. The die-bonding film 3 for fixing a wafer-like workpiece (a semiconductor wafer or the like) to an adherend such as a substrate is supported by the peeling balance. In the adhesive layer 2 of the die-bonded film 11 with a dicing sheet shown in Fig. 2, the aforementioned portion 2b can fix the wafer ring.

The radiation hardening type adhesive can be used without any limitation A radiation-hardening functional group having a carbon-carbon double bond or the like, and exhibiting adhesion. The radiation-curable adhesive is exemplified by the addition of a radiation-hardening monomer component or an oligomer component to a general pressure-sensitive adhesive such as an acrylic pressure-sensitive adhesive or a rubber-based pressure-sensitive adhesive. Line hardening adhesive.

The monomer composition of the radiation hardening property is exemplified as an example Such as urethane oligomer, urethane (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, pentaerythritol three (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxy penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butanediol di(methyl) Acrylate and the like. Further, examples of the radiation curable oligomer component include various oligomers such as a urethane type, a polyether type, a polyester type, a polycarbonate type, and a polybutadiene type, and the molecular weight thereof is about 100 to 30,000. The scope is more appropriate. The amount of the radiation curable monomer component or the oligomer component can be appropriately determined depending on the kind of the above-mentioned adhesive layer, and the amount of adhesion of the adhesive layer can be appropriately reduced. In general, it is, for example, 5 to 500 parts by weight based on 100 parts by weight of the base polymer of the acrylic polymer or the like constituting the adhesive. It is preferably about 40 to 150 parts by weight.

In addition, as a radiation hardening type adhesive, in addition to the foregoing In addition to the radiation-curing type adhesive described as an additive type, an intrinsic type radiation-curing type adhesive which uses a polymer side chain or a main chain or a carbon-carbon double bond at the end of the main chain as a base polymer is exemplified. The intrinsic radiation curing adhesive does not necessarily have a low molecular component oligomer component or the like, or is mostly not contained, so that the oligomer component does not move over the adhesive over time, and a stable composition can be formed. The adhesive layer of the layer construction is preferred.

The foregoing base polymer having a carbon-carbon double bond is not particularly limited Those having carbon-carbon double bonds and having adhesiveness are used in the system. The base polymer is preferably an acrylic polymer as a basic skeleton. The basic skeleton of the acrylic polymer is exemplified by the acrylic polymer exemplified above.

Introduction of a carbon-carbon double bond into the aforementioned acrylic polymer The method is not particularly limited, and various methods can be employed, but the carbon-carbon double bond is easier to introduce into the polymer side chain from the viewpoint of molecular design. For example, after copolymerizing a monomer having a functional group with an acrylic polymer in advance, a compound having a functional group capable of reacting with the functional group and a carbon-carbon double bond is used to maintain a carbon-carbon double bond radiation. A method of performing a condensation or addition reaction in a state of hardenability.

Examples of combinations of such functional groups are carboxylic acid groups and epoxy groups. a group, a carboxylic acid group and an aziridine group, a hydroxyl group and an isocyanate group. In the combination of these functional groups, in terms of easy reaction tracking, a combination of a hydroxyl group and an isocyanate group is preferred. Further, by the combination of the functional groups, if a combination of acrylic polymers having the aforementioned carbon-carbon double bond is formed, the functional group may be The acrylic polymer and the side of any of the above compounds, but it is preferred that the acrylic polymer has a hydroxyl group, and the compound has an isocyanate group. In this case, the isocyanate compound having a carbon-carbon double bond is exemplified by, for example, methacrylonitrile isocyanate, 2-methacryloxyethyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl. Isocyanate, etc. Further, as the acrylic polymer, a hydroxyl group-containing monomer or an ether compound of 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether or diethylene glycol monovinyl ether is used. Aggregated.

The aforementioned intrinsic type of radiation hardening type adhesive can be used alone The base polymer (especially an acrylic polymer) having a carbon-carbon double bond is used, but the radiation curable monomer component or oligomer component may be blended to such an extent that the properties are not deteriorated. The radiation curable oligomer component is usually in the range of 30 parts by weight, preferably 0 to 10 parts by weight, per 100 parts by weight of the base polymer.

The radiation hardening type adhesive is hardened by ultraviolet rays or the like It contains a photopolymerization initiator. The photopolymerization initiator is exemplified by, for example, 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)one, α-hydroxy-α,α-dimethylacetophenone, 2-methyl An α-ketal compound such as benzyl-2-hydroxypropiophenone or 1-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2, Acetophenone-based compound such as 2-diethoxyacetophenone or 2-methyl-1-[4-(methylthio)-phenyl]-2-morpholinopropane-1; benzoin ethyl a benzoin ether compound such as ether, benzoin isopropyl ether or anisoin methyl ether; an acetal compound such as benzyl dimethyl acetal; or an aromatic sulfonate such as 2-naphthalene sulfonium chloride Strontium chloride compound; 1-benzophenone-1,1-propanedione-2-(o-B a photoactive lanthanide compound such as oxycarbonyl) oxime; a benzophenone compound such as benzophenone, benzhydrylbenzoic acid or 3,3'-dimethyl-4-methoxybenzophenone Thiaxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone a thioxanthone compound such as 2,4-diethylthioxanthone or 2,4-diisopropylthioxanthone; camphorquinone; a halogenated ketone; a mercaptophosphine oxide; a decylphosphonate Wait. The amount of the photopolymerization initiator to be added is, for example, about 0.05 to 20 parts by weight based on 100 parts by weight of the base polymer of the acrylic polymer or the like constituting the pressure-sensitive adhesive.

And the radiation hardening type adhesive is exemplified as, for example, Japanese special open A photopolymerizable compound containing an addition polymerizable compound having two or more unsaturated bonds, an alkoxysilane having an epoxy group, and a carbonyl compound, an organic sulfur compound, and the like disclosed in Japanese Patent Publication No. 60-196956 A rubber-based adhesive or an acrylic adhesive such as a photopolymerization initiator such as an oxide, an amine or a phosphonium salt compound.

In the aforementioned radiation hardening type adhesive layer 2, it is also visible It is desirable to have a compound that is colored by irradiation with radiation. Since the adhesive layer 2 contains a compound colored by irradiation with radiation, only the portion irradiated with the radiation can be colored. That is, the portion 2a corresponding to the workpiece attaching portion 3a shown in Fig. 1 can be colored. According to this, it is possible to directly judge whether or not the adhesive layer 2 is irradiated to the radiation by visual observation, so that the workpiece attaching portion 3a can be easily recognized, and the workpiece can be easily attached. When the semiconductor wafer is detected by a photo sensor or the like, the detection accuracy can be improved, and malfunction can be prevented when the semiconductor wafer is picked up.

a compound colored by radiation irradiation is irradiated It is colorless or light before irradiation, but it becomes a colored compound by irradiation with radiation. A preferred specific example of the compound is exemplified by a leuco dye. As the leuco dye, a conventional triphenylmethane, anthraquinone, phenothiazine, auramine or spiropyran is preferably used. Specifically, it is 3-[N-(p-tolylamino)]-7-anilinofluoran, 3-[N-(p-tolyl)-N-methylamino]-7-anilinylfluorene Alkane, 3-[N-(p-tolyl)-N-ethylamino]-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, crystal violet Crystal violet lactone, 4,4',4"-dimethylaminotriphenylmethanol, 4,4',4"-dimethylaminotriphenylmethane, and the like.

List of developers that are preferably used together with these leuco dyes It is an electron acceptor such as an initial polymer of a phenol formaldehyde resin used in the past, an aromatic carboxylic acid derivative, or an activated clay, and further, various color developing agents can be used in combination with a color tone.

This kind of compound colored by radiation irradiation can be temporarily It is dissolved in an organic solvent or the like and then contained in a radiation curable adhesive, and may be contained in the adhesive in a powder form. The ratio of use of the compound in the adhesive layer 2 is 10% by weight or less, preferably 0.01 to 10% by weight, more preferably 0.5 to 5% by weight. When the ratio of the compound exceeds 10% by weight, the radiation applied to the adhesive layer 2 is excessively absorbed by the compound, so that the hardening of the portion 2a of the adhesive layer 2 is insufficient, and the adhesion is not sufficiently lowered. . On the other hand, in order to sufficiently color, the ratio of the compound is preferably 0.01% by weight or more.

When the adhesive layer 2 is formed by a radiation-curable adhesive, It is also possible to irradiate one portion of the adhesive layer 2 to the adhesion of the aforementioned portion 2a in the adhesive layer 2 to the adhesion of the other portion 2b.

Method for forming the aforementioned portion 2a in the above adhesive layer 2 As a method of forming the radiation-curable adhesive layer 2 on the support substrate 1, the portion 2a is irradiated with radiation to be hardened. Part of the radiation irradiation can be performed through a photomask formed with a pattern corresponding to the portion 3b or the like other than the workpiece attaching portion 3a. Further, a method of hardening by ultraviolet rays and a method of hardening is exemplified. The formation of the radiation-curable adhesive layer 2 can be carried out by transferring the film provided on the support substrate 1 to the support substrate 1. Part of the radiation hardening can also be performed on the radiation-curable adhesive layer 2 provided on the separator.

In addition, the adhesive layer 2 is formed by a radiation hardening adhesive. At this time, all or a part of the portion other than the portion of the support substrate 1 corresponding to the portion to which the workpiece is attached 3a is shielded may be used, and the radiation-curable adhesive layer 2 may be formed thereon to irradiate the radiation. The portion corresponding to the workpiece attaching portion 3a is hardened to form the aforementioned portion 2a whose adhesive force is lowered. As for the light-shielding material, it can be formed as a photomask by printing or vapor deposition on the support film. According to this manufacturing method, the die-cut film 10 with the dicing sheet of the present invention can be efficiently produced.

Also, when the radiation is irradiated, it is hardened by oxygen. The surface of the radiation hardening type adhesive layer 2 is preferably blocked from oxygen (air) by any means. For example, a method of coating the surface of the pressure-sensitive adhesive layer 2 with a separator or irradiating with ultraviolet rays or the like in a nitrogen atmosphere is exemplified. Method and so on.

The thickness of the adhesive layer 2 is not particularly limited, but is prevented The defect of the cut surface of the wafer or the compatibility of the adhesion maintaining layer is preferably about 1 to 50 μm. It is preferably 2 to 30 μm, more preferably 5 to 25 μm.

(Manufacturing method of solid crystal film with dicing sheet)

The die-bonding film 10 with a dicing sheet is produced, for example, as follows.

First, the substrate 1 can be formed into a film by a conventional film forming method. The film forming method is exemplified by, for example, a calender film forming method, a casting method in an organic solvent, a blow molding method in a closed system, a T die extrusion method, a coextrusion method, a dry layer method, and the like.

Next, a solution of the adhesive composition is applied to the substrate 1 After the film is applied, the coating film is dried under specific conditions (crosslinking if necessary) to form the adhesive layer 2. The coating method is not particularly limited, and examples thereof include roll coating, screen coating, gravure coating, and the like. Further, the drying conditions are carried out, for example, at a drying temperature of 80 to 150 ° C and a drying time of 0.5 to 5 minutes. Further, after the adhesive composition is applied onto the separator to form a coating film, the coating film is dried under the drying conditions to form the adhesive layer 2. Subsequently, the adhesive layer 2 is attached to the substrate 1 together with the separator. Thereby, the crystal cut sheet 11 is produced.

The die bonding film 3 is produced, for example, as follows.

First, a resin composition solution of a material for forming the solid crystal film 3 is produced. The foregoing resin composition solution can be appropriately captured by arranging An ion additive, a thermosetting resin, a thermoplastic resin, a filler, and the like are placed in a container, and are obtained by stirring in a uniform manner in an organic solvent.

The organic solvent may be formed as long as it can constitute the solid crystal film 3 The components which are uniformly dissolved, kneaded or dispersed are not particularly limited, and those skilled in the past can be used. Such a solvent is exemplified by a ketone solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, acetone, methyl ethyl ketone or cyclohexanone, toluene or xylene. Methyl ethyl ketone, cyclohexanone and the like are preferably used in terms of rapid drying speed and availability.

Next, the resin composition is formed in a specific thickness. The solution is applied onto a substrate separator to form a coating film, and then the coating film is dried under specific conditions to form an adhesive layer (solid crystal film 3). The coating method is not particularly limited, and examples thereof include roll coating, screen coating, gravure coating, and the like. The drying conditions are carried out, for example, at a drying temperature of 70 to 160 ° C and a drying time of 1 to 5 minutes. Further, after the resin composition solution is applied onto the separator to form a coating film, the coating film is dried under the drying conditions to form a solid crystal film 3. Subsequently, the die-bonded film 3 is attached to the substrate separator together with the separator.

Next, the self-cut wafer 11 and the solid crystal film 3 are peeled off, respectively. The separator is bonded to each other such that the die bond film 3 and the adhesive layer 2 are bonded to each other. The bonding can be carried out, for example, by pressing. In this case, the lamination temperature is not particularly limited, and is preferably, for example, 30 to 50 ° C, more preferably 35 to 45 ° C. Further, the linear pressure is not particularly limited, and is preferably 0.1 to 20 kgf/cm, more preferably 1 to 10 kgf/cm. Next, the substrate separator on the solid crystal film 3 is peeled off to obtain the actual A die-bonding film 10 with a dicing sheet attached thereto.

(Method of Manufacturing Semiconductor Device)

The method for producing a semiconductor device of the present embodiment (hereinafter also referred to as a first embodiment) includes a step of preparing the thermosetting type solid crystal film, and a semiconductor wafer is fixed to be adhered by permeating the thermosetting type solid crystal film. The solid crystal step on the body.

Further, the method for manufacturing a semiconductor device of the present embodiment (hereinafter also referred to as a second embodiment) may be a step of preparing a die-cut film having the above-described dicing sheet, and preparing the dicing film. a step of bonding a thermosetting type solid crystal film of a solid crystal film of a sheet to a back surface of a semiconductor wafer, and dicing the semiconductor wafer together with the thermosetting type solid crystal film to form a wafer-shaped semiconductor wafer a step of picking up the semiconductor wafer and the thermosetting solid crystal film together with the solid crystal film attached to the dicing sheet, and crystallizing the semiconductor wafer on the adherend through the thermosetting type solid crystal film The solid crystal step.

In the method of manufacturing a semiconductor device according to the first embodiment, a solid crystal film having a dicing sheet is used in the method of manufacturing a semiconductor device according to the second embodiment, and in the method for manufacturing a semiconductor device according to the first embodiment, a solid crystal is used as a single body. The aspects of the film are different, and other aspects are common. In the method of manufacturing a semiconductor device according to the first embodiment, after the solid crystal film is prepared, The step of bonding the film to the die bonding film can be subsequently carried out in the same manner as the method of manufacturing the semiconductor device of the second embodiment. Therefore, the method of manufacturing the semiconductor device of the second embodiment will be described below.

In the method of manufacturing a semiconductor device of the present embodiment, the first First, a solid crystal film with a diced sheet is prepared (preparation step). The die-bonding film 10 with a dicing sheet is suitably peeled off from the separator provided on the die-bonding film 3, and is used as follows. Hereinafter, a case where the die-bonded film 10 with a dicing sheet is used will be described with reference to Fig. 3 as an example.

First, the semiconductor wafer 4 is pressed against the attached crystal wafer. The semiconductor wafer attaching portion 3a of the die-bonded film 3 in the die-bonded film 10 is held and fixed (bonding step). This step is performed by pressing with a pressing means such as a pressure roller. The temperature at which the attachment is applied is not particularly limited, and is preferably in the range of, for example, 40 to 90 °C.

Next, dicing the semiconductor wafer 4 (cutting step) Step). Thereby, the semiconductor wafer 4 is cut into a specific size and singulated to manufacture the semiconductor wafer 5. The dicing method is not particularly limited, for example, from the circuit side of the semiconductor wafer 4 according to a usual method. Further, in this step, for example, a cutting method called a complete cutting in which the solid crystalline film 10 cut into the dicing sheet is cut can be used. The crystal cutting device used in this step is not particularly limited, and conventional ones can be used. Further, since the semiconductor wafer is subsequently fixed by the die-bonding film 10 with the dicing sheet, it is possible to suppress wafer defects or wafer flying out, and to suppress breakage of the semiconductor wafer 4.

Next, in order to peel off and then fix it to the solidified sheet Semiconductor wafer of crystalline film 10, and picking up semiconductor wafer 5 (pickup step). The picking method is not particularly limited, and various methods conventionally known can be employed. For example, a method in which the respective semiconductor wafers 5 are lifted up by the side of the solid crystal film 10 on which the needle-attached dicing sheet is attached, and the semiconductor wafer 5 which is lifted up by the pickup device is picked up.

The picking condition is to prevent the chipping, and it is preferable to set the needle jacking speed to 5 to 100 mm/sec, and more preferably 5 to 10 mm/sec.

When the adhesive layer 2 is of an ultraviolet curing type, the pickup is performed by irradiating the adhesive layer 2 with ultraviolet rays. Thereby, the adhesion of the adhesive layer 2 to the die-bonding film 3 is lowered, and the peeling of the semiconductor wafer 5 is facilitated. As a result, pickup can be performed without damaging the semiconductor wafer 5. The conditions such as the irradiation intensity and the irradiation time at the time of ultraviolet irradiation are not particularly limited, and may be appropriately set as needed. Further, the light source used for ultraviolet irradiation can use the aforementioned one. Further, when the adhesive layer is previously irradiated with ultraviolet rays to be hardened, and the cured adhesive layer and the solid crystal film are bonded together, ultraviolet irradiation is not required here.

Next, the picked-up semiconductor wafer 5 is subsequently fixed to the adherend 6 through the die-bonding film 3 (solid phase step). The adherend 6 is exemplified by a lead frame, a TAB film, a substrate, or a separately fabricated semiconductor wafer or the like. The adherend 6 may be, for example, a deformed adherend that is easily deformed, or a non-deformable adherend (semiconductor wafer or the like) that is not easily deformed.

The aforementioned substrate can be used by conventional practitioners. Further, the lead frame may be a metal lead frame such as a Cu lead frame or a 42 Alloy lead frame, or an organic substrate made of glass epoxy resin, BT (double-maleimide-triazine), polyimine or the like. However, the invention is not limited thereto and also includes a mounting half A conductor chip, a circuit board that can be electrically connected to a semiconductor chip.

Then, since the die-bonded film 3 is a thermosetting type, the semiconductor wafer 5 is subsequently fixed to the adherend 6 by thermal curing, and the heat resistance is improved (thermal curing step). The heating temperature can be carried out at 80 to 200 ° C, preferably at 100 to 175 ° C, more preferably at 100 to 140 ° C. Further, the heating time may be from 0.1 to 24 hours, preferably from 0.1 to 3 hours, more preferably from 0.2 to 1 hour. Moreover, thermal hardening can also be carried out under pressurized conditions. The pressurization condition is preferably in the range of 1 to 20 kg/cm ² , more preferably in the range of 3 to 15 kg/cm ² . Thermal hardening under pressure can be carried out, for example, in a chamber filled with an inert gas. Further, the semiconductor wafer 5 is subsequently fixed to a substrate or the like through the die-bonding film 3, and can be supplied to the reflow step.

The shearing adhesion force of the solid crystal film 3 after heat hardening is relative to The adherend 6 is preferably 0.2 MPa or more, more preferably 0.2 to 10 MPa. When the shearing force of the die-bonding film 3 is at least 0.2 MPa or more, the solid crystal film 3 and the semiconductor wafer 5 or the adherend 6 are caused by ultrasonic vibration or heating in the step in the wire bonding step. There will be no sliding deformation on the next side. That is, the semiconductor wafer is not moved by the ultrasonic vibration at the time of wire bonding, thereby preventing the wire breaking success rate from being lowered.

Next, as shown in Figure 3, as shown in Figure 3, to wire the wire 7 The front end of the terminal portion (internal lead) of the adherend 6 and the electrode pad (not shown) on the semiconductor wafer 5 are electrically connected (wire bonding step). The wire bonding wire 7 is made of, for example, a gold wire, an aluminum wire, or a copper wire. The temperature at the time of wire bonding is 80 to 250 ° C, preferably 80 to 220 ° C. Moreover, the heating time is performed for several seconds to several minutes. The junction line becomes the aforementioned temperature range The state of being heated in the surrounding area is performed by using the vibration energy of the ultrasonic wave in combination with the pressing force by applying pressure. This step can be carried out without performing thermal hardening of the die bonding film 3. Further, in the process of this step, the semiconductor wafer 5 and the adherend 6 are not fixed by the die bonding film 3.

Next, as shown in Figure 3, as shown in Figure 3, the sealing resin is 8 The semiconductor wafer 5 is sealed (sealing step). This step is performed to protect the semiconductor wafer 5 or the bonding wire 7 mounted on the adherend 6. This step can be carried out by molding a resin for sealing with a mold. For the sealing resin 8, for example, an epoxy resin is used. The heating temperature at the time of resin sealing is usually carried out at 175 ° C for 60 to 90 seconds, but the present invention is not limited thereto, and for example, it may be hardened at 165 to 180 ° C for several minutes. Thereby, the semiconductor wafer 5 and the adherend 6 are fixed to the solid crystal film 3 while the sealing resin is cured. In other words, in the present invention, even if the post-hardening step described later is not performed, the solid film 3 can be fixed in this step, which contributes to a reduction in the number of manufacturing steps and a shortening of the manufacturing period of the semiconductor device. In addition, in the sealing step, a method of embedding the semiconductor wafer 5 in the sheet-like sealing sheet may be employed (see, for example, JP-A-2013-7028).

Then, heating is performed as needed to make the aforementioned sealing step The hardening insufficient sealing resin 8 is completely hardened (post-hardening step). In the sealing step, even if the die-bonding film 3 is not completely thermally cured, the die-bonding film 3 can be completely thermally hardened together with the sealing resin 8 in this step. The heating temperature in this step varies depending on the type of the sealing resin, but is, for example, in the range of 165 to 185 ° C, and the heating time is about 0.5 to 8 hours.

Thereby, the semiconductor device shown in FIG. 3 is obtained. So Since the semiconductor device has a die-bonded film 3 containing an inorganic ion scavenger treated with a decane coupling treatment, it can be made thin and has sufficient ion trapping property.

Moreover, the method of manufacturing the semiconductor device of the present embodiment is also After the temporary fixation by the die-bonding step, the wire can be wire-bonded without undergoing the heat-hardening step of the heat treatment of the solid crystal film 3, and the semiconductor wafer 5 can be sealed with a sealing resin to cure the resin (post-hardening). In this case, the shearing adhesion force at the time of temporary fixation of the die-bonded film 3 is preferably 0.2 MPa or more, more preferably 0.2 to 10 MPa, with respect to the adherend 6 . When the shearing force at the time of temporarily fixing the solid crystal film 3 is at least 0.2 MPa or more, even if the wire bonding step is not performed by the heating step, the solid crystal film is not caused by the ultrasonic vibration or heating in the step. 3, sliding deformation occurs with the semiconductor wafer 5 or the adhesion surface of the adherend 6. That is, the semiconductor wafer is not moved by the ultrasonic vibration during the wire bonding, thereby preventing the success rate of the wire from being lowered. In addition, the temporary fixation means that the solid crystal thin film is cured (in a semi-hardened state) to the extent that the hardening reaction of the thermosetting type solid crystal film is not completed, and the semiconductor is fixed without hindrance in the subsequent step. The state of the wafer 5. Further, when the wire is not subjected to the heat hardening step of the heat treatment of the solid crystal film, the step of post-hardening corresponds to the heat hardening step in the present specification.

Moreover, the solid crystal film with the dicing sheet of the present invention can also be compared It is used in a case where a plurality of semiconductor wafers are laminated to form a three-dimensional installation. In this case, a solid crystal film and a separator may be laminated between the semiconductor wafers, or a separator may not be laminated, and a solid crystal film may be laminated only between the semiconductor wafers, and may be Manufacturing conditions, uses, etc. are appropriately changed.

The above embodiments are directed to the semiconductor device of the present invention. The case where the resin film is a die-bonded film will be described. However, the resin film for a semiconductor device of the present invention is not limited to this example, and may be a flip-chip type semiconductor for forming a back surface of a flip-chip bonded semiconductor element on an adherend. The film for the back surface may also be a sealing film for sealing a semiconductor element.

[Examples]

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

The components used in the examples are explained.

Acrylic copolymer: TEISAN resin SG-P3 made by NAGASE CHEMTEX (weight average molecular weight: 850,000, glass transition temperature: 12 ° C)

Phenol resin: MEH-7851SS (a phenol resin having a biphenyl aralkyl skeleton, softening point of 67 ° C, hydroxyl equivalent of 203 g / eq.) manufactured by Minghe Chemical Co., Ltd.

Epoxy resin: YDCN-700-2 made of Nippon Steel Chemical Co., Ltd. (o-cresol novolak type epoxy resin, epoxy equivalent 200, softening point 61 ° C)

Inorganic filler: SO-E2 (molten spherical cerium oxide, average particle size 0.5 μm) manufactured by ADMATECHS

Inorganic ion scavenger: IXEPLAS-A1 manufactured by East Asia Synthetic Co., Ltd. (3 components of magnesium, aluminum and zirconium oxide hydrate, average particle size 0.5 μm)

Inorganic ion trapping agent: IXE-100 (Zirconium Oxide Hydrate, average particle size 1.0 μm) manufactured by East Asia Synthetic Co., Ltd.

Further, the inorganic ion scavengers of Example 1, Example 2, and Example 3 were subjected to surface treatment in advance. The surface treatment was carried out by a dry method and treated with a decane coupling agent in an amount shown in Table 1 (amount of decane coupling agent treatment). As a decane coupling agent, KBM503 (3-methacryloxypropyltriethoxydecane) of Shin-Etsu Chemical Co., Ltd. was used.

On the other hand, the inorganic ion scavenger of Comparative Example 1 was not subjected to surface treatment.

[Examples and Comparative Examples]

According to the blending ratio described in Table 1, each component was dissolved in methyl ethyl ketone as an organic solvent, and a resin composition solution having a concentration of 20% by weight was obtained by dispersion. This resin composition was applied onto a release-treated film of polyethylene terephthalate having a thickness of 38 μm which was subjected to polyfluorene stripping treatment, and then dried at 110 ° C for 5 minutes. Thereby, a resin film of the thickness shown in Table 1 was obtained. At this time, the presence or absence of aggregation of the inorganic ion scavenger was visually observed. The results are shown in Table 1.

(calculation of copper ion capture rate B, and calculation of ratio B/A) [1. Calculation of copper ion capture rate A of resin film before thermal hardening]

Each of the resin films (thickness: 25 μm) was cut into 2.5 g, and was bent into a cylindrical closed 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 was added thereto. (CuCl ₂ aqueous solution) 50 ml. Subsequently, it was allowed to stand at 120 ° C for 20 hours in a constant temperature dryer (ESPEC, PV-231). Subsequently, it was cooled to room temperature. After the film was taken out, the copper ion concentration (copper ion concentration X) in the aqueous solution was measured using ICP-AES (manufactured by SII Nanotechnology, SPS-1700HVR).

Subsequently, the copper ion trapping rate A of the resin film before thermal curing is calculated by the 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 Thermal Hardening]

Each of the resin films (thickness: 25 μm) was cut out so that the weight after peeling off the release-treated film was 2.5 g, and after bending, it was thermally cured at 175 ° C for 5 hours. Next, the release-treated film was peeled off, and a cylindrical closed-type Teflon (registered trademark) container having a diameter of 58 mm and a height of 37 mm was placed, and 50 ml of a copper (II) ion aqueous solution (CuCl ₂ aqueous solution) of 10 ppm was added. Subsequently, it was allowed to stand at 120 ° C for 20 hours in a constant temperature dryer (ESPEC, PV-231). Subsequently, it was cooled to room temperature. After the film was taken out, the copper ion concentration (copper ion concentration Y) in the aqueous solution was measured using ICP-AES (SII Nanotechnology, SPS-1700HVR).

Subsequently, the copper ion trapping rate B of the resin film after thermal curing is calculated by the 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, calculate the ratio B/A. The results are shown in Table 1.

(Measurement of 5% weight reduction temperature)

A sample of 10 mg was weighed and measured by a differential heat balance (TG-DTA (manufactured by RIGAKU Co., Ltd.) in an air atmosphere, and measured at a temperature increase rate of 10 ° C / min at 40 to 550 ° C. When the reading weight was reduced by 5% The temperature.

(pH of aqueous solution after copper ion capture)

The aqueous solution obtained by the above-mentioned "2. Calculation of the copper ion capture rate B of the resin film after thermosetting" was measured using a KASTANY ACT pH meter (D-51, manufactured by Horiba, Ltd.) (when the copper ion concentration Y was measured) Aqueous solution). The results are shown in Table 1.

Further, the pH of the 10 ppm copper (II) ion aqueous solution before the resin film was impregnated was 5.6.

1‧‧‧Substrate

2‧‧‧Adhesive layer

2a‧‧‧ Attached part

2b‧‧‧Other parts

3‧‧‧Crystalline film

3a‧‧‧Working part attachment

3b‧‧‧Parts other than the attached part of the workpiece

4‧‧‧Semiconductor wafer

10‧‧‧Crystal film with dicing flakes

11‧‧‧Cleaved thin slices

Claims (8)

A resin film for a semiconductor device characterized by containing an inorganic ion scavenger treated by a decane coupling treatment. The resin film for a semiconductor device according to claim 1, wherein the inorganic ion scavenger has an average particle diameter of 0.6 μm or less. The resin film for a semiconductor device according to claim 1, wherein the inorganic ion scavenger is an inorganic two ion scavenger that captures a cation and an anion. The resin film for a semiconductor device according to claim 1, wherein the content of the inorganic ion scavenger is from 1 to 30% by weight. The resin film for a semiconductor device according to claim 1, wherein a resin film for a semiconductor device having a weight of 2.5 g after heat-hardening at 175 ° C for 5 hours is immersed in 50 ml of an aqueous solution having 10 ppm of copper ions, and placed at 120 ° C. When the copper ion concentration (ppm) in the aqueous solution after the hour is Y, the copper ion trapping rate B calculated by the following formula (2) is 10% or more: Formula (2): [(10-Y)/10] ×100 (%). The resin film for a semiconductor device according to claim 1, wherein a resin film for a semiconductor device having a weight of 2.5 g before thermosetting is immersed in 50 ml of an aqueous solution having 10 ppm of copper ions, and placed in the aqueous solution after being left at 120 ° C for 20 hours. The copper ion concentration (ppm) was set to X, and a resin film for a semiconductor device having a weight of 2.5 g after heat-hardening at 175 ° C for 5 hours was immersed in 50 ml of an aqueous solution having 10 ppm of copper ions, and placed at 120 ° C. Copper ion concentration in the aforementioned aqueous solution after hours When (ppm) is set to Y, the ratio B/A of the copper ion trapping ratio A calculated by the following formula (1) to the copper ion trapping ratio B calculated by the following formula (2) is 1 or more, and the formula (1): (10-X)/10] × 100 (%) Formula (2): [(10-Y)/10] × 100 (%). The resin film for a semiconductor device according to claim 1 has a thickness of from 1 to 40 μm. A method of fabricating a semiconductor device, comprising the steps of: preparing a solid crystal film according to any one of claims 1 to 7, and crystallizing the semiconductor wafer on the adherend through the solid crystal film; Solid crystal step.