TW201305306A - Next piece and its use - Google Patents

Abstract

The present invention provides an adhesive sheet for manufacturing a semiconductor device which has chemical stability and is easy to control physical properties while suppressing cracking or chipping of a semiconductor wafer or the like. An adhesive sheet for manufacturing a semiconductor device, comprising: a thermoplastic resin having a carboxyl group and having no epoxy group; a thermosetting resin; and a complex forming organic compound, the complex forming organic compound including Two or more benzene rings of a phenolic hydroxyl group, and capable of forming a complex with a cation.

Description

Next piece and its use

The invention relates to an adhesive sheet and its use.

In recent years, a stacked MCP (Multi Chip Package) in which a memory package chip for a mobile phone or a portable audio device is stacked in a plurality of stages has been widely used. In addition, with the versatility of image processing technology and mobile phones, the density, high integration, and thinness of packaging are being promoted. As a method of fixing a semiconductor wafer to a substrate or the like, a method of using a thermosetting paste resin, and a method of using a bonding sheet using a combination of a thermoplastic and a thermosetting resin have been proposed.

On the other hand, in the process of semiconductor manufacturing, a cation (for example, copper ions or iron ions) is mixed into the crystal substrate of the wafer from the outside, and when the cation reaches the circuit forming surface formed on the wafer, the electricity is generated. The characteristics are declining In addition, there is a problem that cations are generated from a circuit or a metal wire during use of the article, and electrical characteristics are degraded.

In response to the above problems, attempts have been made in the past to process a back surface of a wafer to form a fracture layer (strain), and to capture and remove cations via the fracture layer (External Gettering (hereinafter also referred to as "EG") or An oxygen precipitation induced defect (acid precipitation defect) is formed in the crystal substrate of the wafer, and an internal enthalpy (Intrinsic Gettering, hereinafter also referred to as "IG") is captured by the oxygen precipitation induced defect.

However, with the thinning of wafers in recent years, the effect of IG is reduced, and the back strain causing cracking or warpage of the wafer is also removed, thereby The effect of EG is also not obtained, and there is a problem that the effect of removing the sputum is insufficient.

Therefore, various schemes for supplementing the defamation effect have been proposed. Patent Document 1 describes a film-form adhesive including a copper ion-adsorbing layer including a resin having a skeleton capable of forming a complex with copper ions. Further, it is described that the inside of the resin which can chemically adsorb copper ions to the copper ion adsorption layer can significantly reduce the influence of copper ions generated from a member made of copper as a material. Further, in Patent Documents 2 and 3, an adhesive adhesive composition including an ion scavenger is described, and it is disclosed that the ion trapping agent has an effect of trapping chlorine ions or the like. Further, Patent Document 4 describes a film-like adhesive including an ion trapping agent, and describes that the ion trapping agent captures a halogen element. Further, Patent Document 5 describes an adhesive sheet including an anion exchanger. Further, Patent Document 6 describes a sheet-like adhesive comprising a chelate-modified epoxy resin and capable of trapping internal ion impurities.

Prior art literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2011-52109

Patent Document 2: JP-A-2009-203337

Patent Document 3: Japanese Laid-Open Patent Publication No. 2009-203338

Patent Document 4: Japanese Laid-Open Patent Publication No. 2010-116453

Patent Document 5: Japanese Laid-Open Patent Publication No. 2009-256630

Patent Document 6: Japanese Laid-Open Patent Publication No. 2011-105875

However, even if you use the above-mentioned complementary technology to remove the effect, it will be produced. The following questions were raised.

The first problem is that the technique of capturing cations via the film-like adhesives of Patent Documents 2 to 5 or the like is not disclosed. Therefore, if only chloride ions are trapped, it is difficult to prevent a decrease in electrical characteristics based on cations. Further, the ion trapping agent, the ion trapping agent, and the anion exchanger disclosed in Patent Documents 2 to 5 are inorganic compounds. Therefore, there is a problem in that the inorganic compound is brought into contact with the wafer to cause wafer breakage or defect due to a dispersion in the state of dispersion in the resin such as a film-like adhesive or in adhesion to the wafer. In particular, in recent years, there has been a demand for thinning of a bonding sheet, and therefore it is necessary to suppress cracking or chipping of a wafer due to an inorganic compound.

Further, according to the film-like adhesive of Patent Document 1, or the sheet-like adhesive of Patent Document 6, copper ions can be trapped. Further, since the resin has a skeleton capable of forming a complex with copper ions, it is difficult to cause the inorganic compound to come into contact with the wafer to cause cracking or chipping of the wafer. However, the skeleton which can form a complex with copper ions in the resin may react with other resins constituting a film-like adhesive or the like. Therefore, there is a problem in that chemical stability of a film-like adhesive or the like is lowered, or physical properties such as a film-like adhesive are difficult to control, and desired characteristics are not obtained.

Therefore, an adhesive sheet for manufacturing a semiconductor device which has chemical stability and is easy to control physical properties while suppressing cracking or chipping of a semiconductor wafer or the like, a semiconductor device having the succeeding film for manufacturing the semiconductor device, and a semiconductor device using the same are being sought. A method of manufacturing a semiconductor device using a sheet for device fabrication.

The second problem is that when the size of the semiconductor package is standardized in order to increase the capacity of the semiconductor device described above, not only the thickness of the wafer is required, but also the film-like adhesive for fixing the semiconductor wafer needs to be thinned. In general, when a film-like adhesive includes a filler for securing an elastic modulus at a high temperature, the thinner the film-like adhesive is, the thinning or cracking of the semiconductor wafer due to the coarse filler contained in the film-like adhesive. The frequency will increase. With the reduction in thickness in recent years, the strength of the semiconductor wafer itself is also declining, and thus the occurrence of mechanical damage such as defect or crack of the semiconductor wafer tends to be conspicuous. In addition, in the case where the film-like adhesive includes a substance that traps ions, the ion trapping efficiency of the entire film-like adhesive is also lowered in the progress of thinning of the film-like adhesive, and therefore, more effective ion trapping is required. set. In the above-described prior art (for example, Patent Document 1), although trapping ions can be carried out to some extent, since the skeleton portion capable of forming a complex compound exists only at the resin end, the contact frequency with copper ions is lowered, and the difference is made. The formation of the object is also insufficient, so there is still room for improvement.

For this reason, a film-like adhesive which can prevent the electrical characteristics of the manufactured semiconductor device from being lowered, thereby improving the reliability of the product, and preventing mechanical damage to the wafer or the semiconductor wafer even if the thickness is reduced can be sought.

The third problem is that when the ion-trapping adhesive sheet is combined with the dicing film and used as a dicing/wafer bonding film, it is found that the ion trapping property of the subsequent film may be lowered.

Therefore, it is sought to prevent the ion trapping property of the adhesive sheet from being lowered even if an ion-trapping adhesive sheet is used, and it can be captured in a semiconductor package. In the manufacturing process, the metal ion of the semiconductor wafer is mixed to prevent the dicing/wafer bonding film from deteriorating the electrical characteristics of the semiconductor device.

As a result of intensive studies, the inventors of the present invention have found that the above-described conventional problems can be solved by adopting the following configuration, and the present invention has been completed.

That is, the adhesive sheet for manufacturing a semiconductor device of the present invention includes: a thermoplastic resin having a carboxyl group and having no epoxy group; a thermosetting resin; and a complex forming organic compound, the The complex-forming organic compound includes a benzene ring having two or more phenolic hydroxyl groups, and is capable of forming a complex with a cation.

According to the above configuration, since the complex organic compound capable of forming a complex with a cation is included, it is possible to capture cations which are mixed from the outside in various steps in the production of the semiconductor device. As a result, it is difficult for the cations mixed from the outside to reach the circuit formation surface formed on the wafer, and it is possible to suppress the deterioration of the electrical characteristics, thereby improving the reliability of the product. Further, since it is a complex-forming organic compound, it is possible to suppress cracking or chipping of the wafer even if it is brought into contact with a semiconductor wafer or the like at the subsequent time.

Further, when the semiconductor wafer is subsequently attached to the adherend via the adhesive sheet, generally, irregularities are present on the adherend, so that air bubbles are mixed. This bubble is usually diffused into a sealing resin or the like via pressure or the like at the time of resin sealing, so that the influence thereof is weakened. However, when a compound including a benzene ring having two or more phenolic hydroxyl groups is used as the complex-forming organic compound, when an epoxy group is present in the thermoplastic resin, heat in a process such as wire bonding before sealing with a resin History, the curing reaction will be carried out violently, thus sealing the resin The bubbles cannot be diffused into the sealing resin in the sequence. As a result, peeling caused by the bubble is generated at the subsequent interface. In particular, in the case where a plurality of semiconductor wafers are stacked in a plurality of layers, the heat history is increased, and the influence of the bubbles on the peeling is remarkable. According to the invention, since the thermoplastic resin does not have an epoxy group, the reaction with a complex organic compound including a benzene ring having two or more phenolic hydroxyl groups can be suppressed. Therefore, the chemical stability of the adhesive sheet can be improved. Further, since the reaction with the complex-forming organic compound including the benzene ring having two or more phenolic hydroxyl groups is suppressed, it is possible to suppress the curing reaction from being vigorously performed before the molding step, and it is possible to diffuse the bubbles at the interface interface to the sealing. Resin and the like. Thereby, peeling at the subsequent interface can be prevented.

Further, according to the above configuration, since the thermoplastic resin has a carboxyl group, the thermoplastic resin is crosslinked to some extent, for example, via a post-cure step after resin sealing, and peeling at the subsequent interface can be prevented.

That is, according to the above configuration, the thermoplastic resin has a carboxyl group and does not have an epoxy group; a thermosetting resin; and a complex-forming organic compound including two or more complex organic compounds. Since the benzene ring of a phenolic hydroxyl group can form a complex with a cation, the reliability of the product of the semiconductor device manufactured using the adhesive sheet for manufacture of this semiconductor device can be improved.

In the above configuration, it is preferable to include 5 to 95 parts by weight of the thermoplastic resin, 5 to 50 parts by weight of the thermosetting resin, 0 to 60 parts by weight of the filler, and 100 parts by weight of the total amount of the sheet for manufacturing the semiconductor device. 0.1 to 5 parts by weight of the complex-forming organic compound. By setting the respective components within the numerical range, it is possible to further suppress semiconductor wafers and the like. It is broken or defective, and chemical stability can be further improved, and physical properties can be more easily controlled.

In the above configuration, it is preferable that the copper sheet having a weight of 2.5 g for immersing the sheet for the production of a semiconductor device in a 50 ml aqueous solution containing 10 ppm of copper ions and allowed to stand at 120 ° C for 20 hours has a copper ion concentration of 0 to 9.9 ppm. . According to the above configuration, it is possible to further capture copper ions mixed from the outside in various steps of manufacturing the semiconductor device. As a result, copper ions mixed from the outside are more difficult to reach the circuit formation surface formed on the wafer.

Moreover, the semiconductor device of the present invention is characterized in that it has the underlying sheet for manufacturing the semiconductor device described above. According to the above configuration, since the semiconductor sheet for manufacturing a semiconductor device described above is provided, a semiconductor device with improved product reliability can be obtained.

Moreover, the method of manufacturing a semiconductor device according to the present invention includes the step of adhering a semiconductor wafer to an adherend via a bonding sheet for manufacturing a semiconductor device described above. According to the above configuration, the semiconductor device having the succeeding film for manufacturing the semiconductor device described above can be manufactured, and thus the semiconductor device with improved product reliability can be obtained.

In the present invention, as one embodiment, a film-like adhesive comprising an ion-trapping organic compound free from a resin skeleton, an inorganic filler having an average particle diameter of 500 nm or less, and an adhesive resin are also included.

In the film-like adhesive agent, since the average particle diameter of the inorganic filler is set to 500 nm or less, the ratio of the average particle diameter of the inorganic filler to the thickness of the film-form adhesive can be reduced. As a result, even if the thickness of the thin film adhesive is reduced in order to cope with the increase in the capacity of the semiconductor device, To prevent mechanical damage to semiconductor wafers and the like. In addition, the ion-trapping organic compound is in a state in which all the resin skeletons (including the above-mentioned adhesive resin) included in the adhesive film are free (the state in which it is not bonded to the resin skeleton), and thus the degree of freedom is high, and the contact frequency with the metal ions is also High, which can improve ion trapping. Further, since the ion-trapping organic compound itself is an organic substance, compatibility or affinity with the resin component is also good. Thereby, since the film-like adhesive can be uniformly present as a whole, the ion trapping efficiency can be improved even if the thickness is reduced. In the present specification, the "resin skeleton" is explained in the meaning generally used in the field of resin or polymer. For example, when the resin is composed of one or more repeating units, it means a structure in which these repeating units are connected. The method for measuring the average particle diameter of the inorganic filler is based on the description of the examples.

The thickness of the film-like adhesive can be appropriately reduced to 3 to 15 μm.

The adhesive resin is specifically one or more selected from the group consisting of an acrylic resin, an epoxy resin, and a phenol resin.

The content of the inorganic filler in the film-like adhesive is preferably from 1 to 30% by weight. Thereby, the elastic modulus at a high temperature (for example, 175 to 260 ° C) can be ensured, and mechanical damage of the inorganic filler to the semiconductor wafer can be prevented.

When the film-like adhesive is cured at 175 ° C for 1 hour and the tensile storage elastic modulus at 175 ° C is 0.5 to 500 MPa, the film-like adhesive can be appropriately prevented from being irradiated from the semiconductor wafer even after high-temperature treatment such as a sealing step. Stripped on.

When the film-like adhesive is cured at 175 ° C for 1 hour and the shearing force at 175 ° C is 0.01 to 50 MPa, the shear due to ultrasonic vibration in the wire bonding process can be prevented while maintaining good adhesion. The deformation is cut, so that the manufacturing yield can be improved.

In the film-like adhesive, it is preferable to include 1 to 10 parts by weight of the ion-trapping organic compound per 100 parts by weight of the adhesive resin. By setting the content of the ion-trapping organic compound to the above range, metal ions can be efficiently trapped and excessive ion-trapping organic compounds can be prevented from causing a change in the subsequent characteristics.

In the film-like adhesive, the ratio of the content of the inorganic filler to the content of the ion-trapping organic compound is set to 1.1 to 80 based on the weight, whereby the inorganic filler can be prevented from being caused by the ion-trapping organic compound. The elastic modulus or the subsequent force is lowered, and mechanical damage of the inorganic filler to the semiconductor wafer can be prevented.

In the present invention, as another embodiment, a cutting/wafer bonding film is further provided, comprising: a dicing film having a substrate and an adhesive layer laminated on the substrate; and laminating on the adhesive a backing sheet on the agent layer, the backing sheet comprising an ion trapping agent capable of capturing metal ions, and the storage elastic modulus of the adhesive layer at 26 ° C is 1.0 × 10 ⁴ Pa or more and 1.0 × 10 ⁷ Pa the following.

In the dicing/wafer bonding film, the adhesive layer has a storage elastic modulus of 1.0 × 10 ⁴ Pa or more and 1.0 × 10 ⁷ Pa or less, and thus an appropriate crosslinked structure is formed in the adhesive layer. Thereby, the transfer of the ion scavenger from the adhesive sheet to the adhesive layer can be restricted, and as a result, the decrease in the ion trapping property of the adhesive sheet can be suppressed. Further, since the underlying sheet includes an ion trapping agent capable of trapping metal ions (hereinafter sometimes simply referred to as "ion trapping agent"), it is possible to effectively capture metal ions mixed in the semiconductor wafer in the semiconductor manufacturing process, thereby preventing the obtained semiconductor Deterioration of the electrical characteristics of the device. In addition, since the ion trapping property of the adhesive sheet can be maintained by restricting the transfer of the ion scavenger from the adhesive sheet to the adhesive layer, etc., it is possible to cope with further reduction in thickness of the adhesive sheet accompanying the increase in capacity of the semiconductor device.

According to the dicing/wafer bonding film, the ion scavenger is an organic compound capable of forming a complex with a metal ion, so that the ion can be appropriately suppressed even when it has affinity with a constituent material of the adhesive layer. Transfer of the capture agent, etc.

With respect to the dicing/wafer bonding film, it is preferred that the sample having a weight of 2.5 g taken from the sheet is immersed in a 50 ml aqueous solution containing 10 ppm of copper ions and allowed to stand at 120 ° C for 20 hours, and the copper ion concentration in the aqueous solution is 0~9.8ppm. By having such a copper ion trapping property of the adhesive sheet, it is possible to capture metal ions mixed in a semiconductor wafer or the like in the semiconductor device manufacturing process. As a result, it is difficult for metal ions mixed from the outside to reach the circuit formation surface formed on the wafer, so that deterioration of electrical characteristics can be suppressed, and product reliability can be improved.

In the dicing/wafer bonding film, the adhesive layer preferably includes an acrylic resin having a weight average molecular weight of 300,000 or more. Further, the acrylic resin preferably has a hydroxyl group-containing acrylic monomer as a constituent monomer. Further, the adhesive layer preferably includes an isocyanate-based crosslinking agent, and includes 1 to 5 parts by weight of isocyanate per 100 parts by weight of the acrylic resin. Class of crosslinkers. By using such a configuration singly or in combination, a crosslinked structure capable of restricting the transfer of the ion scavenger or the like can be appropriately formed in the adhesive layer.

In the dicing/wafer bonding film, the adhesive layer may be of a radiation curing type. At this time, the storage elastic modulus of the adhesive layer at 26 ° C before the irradiation of the radiation needs to be 1.0 × 10 ⁴ Pa or more and 1.0 × 10 ⁷ Pa or less.

As described above, the dicing/wafer bonding film can prevent deterioration of the ion trapping property of the bonding sheet, so that the thickness of the bonding sheet can be reduced to 3 μm or more and 150 μm or less.

<First embodiment>

The adhesive sheet for manufacturing a semiconductor device of the present embodiment (hereinafter also simply referred to as "adhesive sheet") includes a thermoplastic resin having a carboxyl group and having no epoxy group; a thermosetting resin; and a complex forming organic A compound, the complex-forming organic compound includes a benzene ring having two or more phenolic hydroxyl groups, and is capable of forming a complex with a cation.

Since the adhesive sheet includes a complex-forming organic compound capable of forming a complex with a cation, it is possible to capture cations which are mixed from the outside in various steps in the production of a semiconductor device. As a result, it is difficult for the cations mixed from the outside to reach the circuit formation surface formed on the wafer, and the deterioration of the electrical characteristics can be suppressed, thereby improving the reliability of the product. Further, since it is a complex-forming organic compound, cracking or chipping can be suppressed even if it is brought into contact with a semiconductor wafer or the like at the subsequent time.

In addition, the thermoplastic resin does not have an epoxy group, so it can be suppressed with the package. A reaction of a compound having a benzene ring having two or more phenolic hydroxyl groups. Therefore, the chemical stability of the adhesive sheet can be improved. Further, since the reaction with the compound including the benzene ring having two or more phenolic hydroxyl groups is suppressed, it is possible to suppress the curing reaction from being vigorously performed before the molding step, and it is possible to diffuse the bubbles at the interface interface into the sealing resin or the like. Thereby, peeling at the subsequent interface can be prevented.

Further, since the thermoplastic resin has a carboxyl group, the thermoplastic resin is crosslinked to some extent, for example, via a post-cure step after resin sealing, and peeling at the subsequent interface can be prevented.

That is, according to the adhesive sheet, comprising: a thermoplastic resin having a carboxyl group and having no epoxy group; a thermosetting resin; and a complex forming organic compound, the complex forming organic compound including two Since the benzene ring of the above phenolic hydroxyl group can form a complex with a cation, the reliability of the product of the semiconductor device manufactured using the adhesive sheet for manufacturing the semiconductor device can be improved.

The complex-forming organic compound is preferably soluble in an organic solvent. When the complex-forming organic compound is soluble in an organic solvent, it can be easily and appropriately dispersed in the resin. In the present invention, the organic compound-soluble organic compound is soluble in the organic solvent, and for example, 1 part by weight of the complex-forming organic compound does not cause suspension or the like with respect to 100 parts by weight of methyl ethyl ketone as the organic solvent. Dissolved.

In the present invention, the cation which forms a complex with the complex-forming organic compound is not particularly limited as long as it is a cation, and examples thereof include Na, K, Ni, Cu, Cr, Co, Hf, Pt, and Ca. , Ba, Sr, Ions such as Fe, Al, Ti, Zn, Mo, Mn, and V.

(Compound forming organic compound)

The complex-forming organic compound is not particularly limited as long as it is a compound including a benzene ring having two phenolic hydroxyl groups and capable of forming a complex with a cation, from which a cation can be appropriately captured and suppressed with the thermoplastic resin From the viewpoint of the reaction of the carboxyl group, a tannin, a tannin derivative (gallic acid, methyl gallate, pyrogallol) or the like can be mentioned. These compounds may be used singly or in combination of two or more. The complex organic compound is preferably a finely powdered organic solvent which is soluble in an organic solvent or in a liquid state.

The adhesive sheet includes a thermoplastic resin having a carboxyl group and having no epoxy group, and a thermosetting resin. Examples of the thermosetting resin include a phenol resin, an amino resin, an unsaturated polyester resin, an epoxy resin, a polyurethane resin, a polyoxyalkylene resin, or a thermosetting polyimide resin. These resins may be used singly or in combination of two or more. In particular, at least any one of an epoxy resin and a phenol resin is preferably used. In particular, when an epoxy resin is used, a high adhesion force at a high temperature (for example, 175 to 260 ° C) can be obtained. Therefore, by using a complex-forming organic compound in combination with an epoxy resin, a sheet having a high adhesion force at a high temperature can be obtained.

The epoxy resin is not particularly limited as long as it is usually used as an adhesive composition, and for example, a bisphenol A type, a bisphenol F type, a bisphenol S type, or a brominated bisphenol A type can be used. Hydrogenated bisphenol A type, bisphenol AF type, biphenyl type, naphthalene type, anthraquinone type, phenol novolac type, o-cresol novolac type, tris(hydroxyphenyl)methane type, tetrakis (hydroxyphenyl)ethane Type An epoxy resin such as a bifunctional epoxy resin or a polyfunctional epoxy resin, or a carbendazim type, an isocyanuric acid triglycidyl ester type or a glycidylamine type. These epoxy resins 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 tris(hydroxyphenyl)methane type epoxy resin or a tetrakis (hydroxyphenyl)ethane type epoxy resin is particularly preferable. This is because these epoxy resins have good reactivity with a phenol resin as a curing agent, and are excellent in heat resistance and the like.

Further, the phenol resin acts as a curing agent for the epoxy resin, and examples thereof include a phenol novolak resin, a phenol aralkyl resin, a cresol novolak resin, a t-butylphenol novolak resin, and a nonylphenol. A novolac type phenol resin such as a novolak resin, a resol type phenol resin, or a polyhydroxy styrene such as polyparaxyl styrene. These phenol resins may be used singly or in combination of two or more. Among these phenol resins, a phenol novolak resin and a phenol aralkyl resin are particularly preferable. This is because the connection reliability of the semiconductor device can be improved.

The mixing ratio of the epoxy resin to the phenol resin is suitably carried out, for example, in an amount of 0.5 to 2.0 equivalents based on 1 equivalent of the hydroxyl group in the phenol resin in the epoxy group. Further, it is more suitably 0.8 to 1.2 equivalents. That is, this is because when the mixing ratio of the two is outside the above range, a sufficient curing reaction cannot be performed, and the properties of the cured epoxy resin are likely to deteriorate.

The thermoplastic resin is not particularly limited as long as it is a thermoplastic resin having a carboxyl group and no epoxy group, and examples thereof include butyl rubber, isoprene rubber, chloroprene rubber, and ethylene-vinyl acetate copolymer. Ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, polybutadiene resin, polycarbonate resin, thermoplastic polyimide resin, polyamide resin, phenoxy resin, acrylic resin, PET and PBT A polyester resin, a polyamidamine resin, or a fluorine-containing resin. These thermoplastic resins may be used singly or in combination of two or more. Among these thermoplastic resins, an acrylic resin having less ionic impurities, high heat resistance, and reliability of a semiconductor element can be preferable.

The acrylic resin is not particularly limited as long as it has a carboxyl group and does not have an epoxy group, and examples thereof include a linear chain having a carbon number of 30 or less, particularly a carbon number of 4 to 18. A copolymer of an alkyl acrylate or methacrylate ester with a carboxyl group-containing monomer. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a t-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, and a cyclohexyl group. 2-ethylhexyl, octyl, isooctyl, decyl, isodecyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, tetradecyl, stearyl , octadecyl or dodecyl and the like. Further, examples of the monomer including a carboxyl group include a vinyl carboxylate, a vinyl acetate, and the like.

In the above-mentioned sheet, it is preferable to include 5 to 95 parts by weight (more preferably 10 to 90 parts by weight) of the thermoplastic resin, and 5 to 55 parts by weight (more preferably 10 to 50 parts by weight) based on 100 parts by weight of the total amount of the sheet. The thermosetting resin, 0 to 60 parts by weight (more preferably 0 to 50 parts by weight) of the filler, and 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, of the complex-forming organic compound. By setting the respective components within the numerical range, cracking or defect of the semiconductor wafer or the like can be further suppressed, and further mention can be made High chemical stability and easier control of physical properties.

With respect to the above-mentioned sheet, after the 2.5 g weight of the back sheet was immersed in a 50 ml aqueous solution containing 10 ppm of copper ions and left at 120 ° C for 20 hours, the copper ion concentration in the aqueous solution was preferably 0 to 9.9 ppm, more preferably 0. ~9.5 ppm, further preferably 0-8 ppm. With respect to the above-mentioned sheet, a 2.5 g weight of the back sheet was immersed in a 50 ml aqueous solution containing 10 ppm of copper ions and left at 120 ° C for 20 hours, and the copper ion concentration in the aqueous solution was 0 to 9.9 ppm, which was more easily trapped in the semiconductor. A cation that is mixed from the outside in various processes in the manufacture of the device. As a result, it is difficult for the cations mixed from the outside to reach the circuit formation surface formed on the wafer, and it is possible to suppress the deterioration of the electrical characteristics, thereby improving the reliability of the product.

When the above-mentioned sheet is crosslinked to some extent in advance, a polyfunctional compound which reacts with a functional group at the end of the molecular chain of the polymer or the like may be added as a crosslinking agent. Thereby, the adhesion property at a high temperature can be improved, and heat resistance can be improved.

As the crosslinking agent, a conventionally known crosslinking agent can be used. In particular, a polyisocyanate compound such as toluene 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 0.05 to 7 parts by weight based on 100 parts by weight of the polymer. When the amount of the crosslinking agent exceeds 7 parts by weight, the adhesive force decreases, which is not preferable. On the other hand, when it is less than 0.05 part by weight, the cohesive force is insufficient, which is not preferable. Further, while including such a polyisocyanate compound, other polyfunctional compounds such as an epoxy resin may be included together as needed.

Further, in the above-mentioned sheet, the filler may be appropriately blended depending on the use thereof. The blending of the filler can impart conductivity to the backsheet or improve thermal conductivity, adjust elastic modulus, and the like. Examples of the filler include an inorganic filler and an organic filler, and an inorganic filler is preferred from the viewpoint of improving workability, improving thermoelectric conductivity, adjusting melt viscosity, and imparting characteristics such as thixotropy. 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 boric acid. Aluminum whiskers, boron nitride, crystalline cerium oxide, amorphous cerium oxide, and the like. These fillers may be used singly 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 preferable. Further, from the viewpoint of a good balance of the above characteristics, crystalline ceria or amorphous ceria is preferred. Further, a conductive material (conductive filler) may be used as the inorganic filler for the purpose of imparting conductivity, improving thermal conductivity, and the like. Examples of the conductive filler include metal powder obtained by forming silver, aluminum, gold, copper, nickel, a conductive alloy, or the like into a spherical shape, a needle shape, or a sheet shape, a metal oxide such as alumina, amorphous carbon black, and graphite.

The average particle diameter of the filler may be set to 0.001 to 1 μm. By setting the average particle diameter of the filler to 0.001 μm or more, the wettability and adhesion to the adherend can be improved. In addition, by setting it to 1 μm or less, the effect of the filler added to impart the above-described respective characteristics can be sufficiently exhibited, 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 above-mentioned sheet, in addition to the complex-forming organic compound, other additives may be appropriately blended as needed. Examples of other additives include an anion scavenger, a dispersant, an antioxidant, a decane coupling agent, a curing accelerator, and the like. These additives may be used singly or in combination of two or more.

The manufacturing method of the adhesive composition for forming the adhesive sheet is not particularly limited, and, for example, the thermosetting resin, the thermoplastic resin, and the complex-forming organic compound and other additives as needed It is put into a container, dissolved in an organic solvent, and stirred to be uniform, whereby it can be obtained as a solution of an adhesive composition.

The organic solvent is not particularly limited as long as it can uniformly dissolve, knead or disperse the components constituting the back sheet, and a conventionally known organic solvent can be used. Examples of such a solvent include ketone solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, acetone, methyl ethyl ketone, and cyclohexanone, toluene, xylene, and the like. Methyl ethyl ketone, cyclohexanone or the like is preferably used from the viewpoint of fast drying speed and inexpensive availability. Among them, methyl ethyl ketone which can dissolve the complex-forming organic compound is more preferable.

The adhesive sheet of the present embodiment can be produced, for example, as follows. First, the adhesive composition solution is prepared. Then, the adhesive composition solution is applied onto the substrate separator to a predetermined thickness to form a coating film, which is then dried under predetermined conditions. As the substrate separator, polyethylene terephthalate (PET), polyethylene, polypropylene, or a release agent such as a fluorine-containing release agent or a long-chain alkyl acrylate release agent can be used. Plastic film or paper after surface coating. In addition, the coating method is not particularly limited, and examples thereof include roll coating, screen coating, and gravure coating. Further, the drying conditions can be carried out, for example, at a drying temperature of 70 to 160 ° C and a drying time of 1 to 5 minutes. Thereby, the adhesive sheet of this embodiment can be obtained.

(Method of Manufacturing Semiconductor Device)

Hereinafter, an embodiment of a method of manufacturing a semiconductor device when the above-mentioned succeeding film is used as a die bond film will be described. In the following, a method of manufacturing a semiconductor device in which a dicing/wafer bonding film 10 of the bonding sheet 3 of the present embodiment (hereinafter also referred to as a wafer bonding film 3) is laminated on a conventionally known dicing film will be described. The dicing film of the present embodiment has a structure in which the adhesive layer 2 is laminated on the substrate 1. Fig. 1 is a schematic cross-sectional view showing a dicing/wafer bonding film of the present embodiment. 2 is a schematic cross-sectional view showing an example in which a semiconductor wafer is mounted via a wafer bonding film in the dicing/wafer bonding film.

First, as shown in FIG. 1, the semiconductor wafer 4 is pressure-bonded to the semiconductor wafer pasting portion 3a of the wafer bonding film 3 in the dicing/wafer bonding film 10, and is then held and fixed (mounting process). This step is carried out by extrusion using a pressing means such as a pressure roller.

Then, the dicing of the semiconductor wafer 4 is performed. Thereby, the semiconductor wafer 4 is cut into a predetermined size and diced, and the semiconductor wafer 5 is produced. The dicing is performed from the circuit surface side of the semiconductor wafer 4, for example, in accordance with a conventional method. Further, in this step, for example, a cutting method called full cutting which is cut into the dicing/wafer bonding film 10 may be employed. The cut used in this process The cutting device is not particularly limited, and a conventionally known cutting device can be employed. Further, since the semiconductor wafer is subsequently fixed by the dicing/wafer bonding film 10, wafer defects or wafer scattering can be suppressed, and breakage of the semiconductor wafer 4 can be suppressed.

In order to peel off the semiconductor wafer which is subsequently fixed by the dicing/wafer bonding film 10, picking up of the semiconductor wafer 5 is performed. The picking method is not particularly limited, and various conventionally known methods can be employed. For example, a method in which each semiconductor wafer 5 is pushed up from the dicing/wafer bonding film 10 side by a needle, and the push-up semiconductor wafer 5 is picked up by a pick-up device can be cited.

Here, when the adhesive layer 2 is of an ultraviolet curing type, the adhesive layer 2 is irradiated with ultraviolet rays and then picked up. Thereby, the adhesive force of the adhesive layer 2 to the wafer bonding film 3 is lowered, and the semiconductor wafer 5 is easily peeled off. As a result, pickup can be performed without damaging the semiconductor wafer 5.

Then, as shown in FIG. 2, the semiconductor wafer 5 formed by the dicing is wafer-bonded to the adherend 6 via the wafer bonding film 3. Wafer bonding is performed via crimping. The conditions for wafer bonding are not particularly limited and may be appropriately set as needed. Specifically, for example, it can be carried out at a wafer bonding temperature of 80 to 160 ° C, a wafer bonding pressure of 5 N to 15 N, and a wafer bonding time of 1 to 10 seconds.

Then, a wire bonding step of electrically connecting the tip end of the terminal portion (internal lead) of the adherend 6 to the electrode pad (not shown) on the semiconductor wafer 5 by the bonding wire 7 is performed. As the bonding wire 7, for example, a gold wire, an aluminum wire, a copper wire, or the like can be used. The temperature at the time of wire bonding is carried out in the range of 80 to 250 ° C, preferably 80 to 220 ° C. In addition, its heating time can be carried out for a few seconds ~ a few minutes. The wiring is performed in a state where it is heated to the temperature range by a combination of ultrasonic vibration energy and pressure application.

Further, the wire bonding process can be performed without thermally curing the wafer bonding film 3 without heat treatment. At this time, the shear bonding force of the wafer bonding film 3 to the adherend at 25 ° C is preferably 0.2 MPa or more, more preferably 0.2 to 10 MPa. By adjusting the shearing force to 0.2 MPa or more, the wire bonding process is performed without thermally curing the wafer bonding film 3, and the wafer bonding film 3 is not caused by ultrasonic vibration or heating in the process. Shear deformation occurs on the subsequent surface of the semiconductor wafer 5 or the adherend 6. That is, the semiconductor element does not move due to the ultrasonic vibration at the time of wire bonding, whereby the wire bonding success rate can be prevented from being lowered.

The wafer bonding film 3 includes a thermoplastic resin having a carboxyl group and having no epoxy group, a thermosetting resin, and a compound including a benzene ring having two or more phenolic hydroxyl groups and capable of forming a complex compound with a cation. . Therefore, even if subjected to the thermal history of the wire bonding process, the thermoplastic resin having no epoxy group hardly reacts with the complex-forming organic compound. As a result, it is possible to suppress the wafer bonding film 3 from undergoing a violent curing reaction.

Next, a sealing step of sealing the semiconductor wafer 5 with the sealing resin 8 is performed. This step is performed to protect the semiconductor wafer 5 or the bonding wires 7 mounted on the adherend 6. This step is carried out by molding a resin for sealing with a mold. As the sealing resin 8, for example, an epoxy resin can be used. The heating temperature during resin sealing is usually 175 ° C, and it takes 60 to 90 seconds. However, the embodiment is not limited thereto, and for example, it may be cured at 165 to 185 ° C for several minutes. Even in the case where the wafer bonding film 3 is not thermally cured in the subsequent post-cure step, the wafer bonding film 3 may be thermally cured and then fixed while the sealing resin 8 is cured in this step.

In the mounting process, generally, fine irregularities are present on the semiconductor wafer 4, so that bubbles are mixed into the interface between the semiconductor 4 and the wafer bonding film 3. In the sealing step, the bubble is diffused into the sealing resin 8 or the like by the pressure at the time of resin sealing, and the influence thereof is weakened. Further, as described above, the severe curing reaction of the wafer bonding film 3 due to the heat history in the wire bonding process is suppressed. As a result, the bubbles can be easily diffused in the sealing process, so that peeling at the subsequent interface due to the bubbles can be prevented.

Then, in the post-curing step, the sealing resin 8 which is insufficiently cured in the sealing step is completely cured. Even if the wafer bonding film 3 is not thermally cured in the sealing step, the wafer bonding film 3 can be thermally cured and then fixed while the sealing resin 8 is cured in this step. The heating temperature in this step varies depending on the type of the sealing resin. For example, in the range of 165 to 185 ° C, the heating time is from about 0.5 hours to about 8 hours.

Further, the bonding sheet (wafer bonding film) may be suitably used in the case where a plurality of semiconductor wafers are stacked and three-dimensionally mounted as shown in FIG. 3 is a schematic cross-sectional view showing an example in which a semiconductor wafer is three-dimensionally mounted via a wafer bonding film. In the case of the three-dimensional mounting shown in FIG. 3, first, at least one wafer bonding film 3 wafer cut into the same size as the semiconductor wafer is pasted on the adherend 6, and then, via the wafer bonding film. 3 The semiconductor wafer 5 is pasted with its wire bonding surface as the upper side. Then, the wafer bonding film 13 is pasted away from the electrode pad portion of the semiconductor wafer 5. Further, another semiconductor wafer 15 is wafer-bonded to the wafer bonding film 13 with its wire bonding surface as the upper side.

Then, a wire bonding process is performed. Thereby, the electrode pads of the semiconductor wafer 5 and the other semiconductor wafer 15 are electrically connected to the adherend 6 by the bonding wires 7. Further, this step can be carried out without passing through the heating process of the wafer bonding films 3 and 13.

Next, a sealing step of sealing the semiconductor wafer 5 or the like is performed by the sealing resin 8, and the sealing resin is cured. Then, in the post-curing step, the sealing resin 8 which is insufficiently cured in the sealing step is completely cured.

When a semiconductor wafer is laminated in a plurality of layers, the heat history of the wire bonding process or the like is large, and the influence of the bubbles existing at the interface between the wafer bonding film and the semiconductor wafer on the peeling is large. However, the thermoplastic resin having no epoxy group hardly reacts with the complex-forming organic compound. As a result, it is possible to suppress the wafer bonding films 3, 13 from undergoing a violent curing reaction. Therefore, the bubbles can be easily diffused in the sealing process, and peeling at the subsequent interface due to the bubbles can be prevented.

In the above embodiment, the case where the adhesive sheet is a wafer bonding film has been described. However, the adhesive sheet is not particularly limited as long as it can be used for the production of a semiconductor device. The protective film for protecting the back surface of the semiconductor wafer of the flip chip type semiconductor device, and the sealing sheet for sealing the front surface of the semiconductor wafer of the flip chip type semiconductor device and the adherend may be used. The adhesive sheet can be used to include a via A method of manufacturing a semiconductor device in which a semiconductor wafer is adhered to an adherend by a bonding sheet. The process of adhering the semiconductor wafer to the adherend via the adhesive sheet can be carried out by a conventionally known pasting process. Further, the semiconductor device manufactured through the method of manufacturing the semiconductor device is a semiconductor device having the underlying sheet.

<Second Embodiment>

Hereinafter, differences between the first embodiment and the first embodiment will be described. The adhesive sheet of the present embodiment can exhibit the same characteristics as those of the adhesive sheet of the first embodiment, except for characteristics described in particular in the items of the present embodiment.

[film-like adhesive]

The film-like adhesive includes an ion-trapping organic compound free from a resin skeleton, an inorganic filler having an average particle diameter of 500 nm or less, and an adhesive resin.

In the film-like adhesive agent, since the average particle diameter of the inorganic filler is 500 nm or less, the size of the inorganic filler relative to the thickness of the film-like adhesive can be reduced. As a result, even if the thickness of the thin film-form adhesive is reduced in order to cope with the increase in the capacity of the semiconductor device, mechanical damage to the semiconductor wafer or the like can be prevented. Further, since the ion-trapping organic compound is in a state of being free from all the resin skeletons included in the adhesive film, the degree of freedom is high, and the contact frequency with the metal ions is also high, so that the ion trapping property can be improved. Further, since an ion-trapping organic compound as an organic substance is used, it is possible to exhibit good compatibility or affinity with a resin component, and it can be uniformly present in the entire film-form adhesive, so that even Thinning can also improve ion capture efficiency.

The thickness of the adhesive sheet is not particularly limited, and since the average particle diameter of the inorganic filler contained in the adhesive sheet is 500 nm, it is possible to easily achieve a reduction in thickness in order to increase the capacity of the semiconductor device. The thickness of the sheet is preferably as thin as 3 to 15 μm, more preferably 3.5 to 13 μm, and further preferably thinned to 3 to 10 μm.

The water absorption rate when the film-like adhesive is allowed to stand in an atmosphere of 85 ° C and 85% RH for 120 hours is preferably 3% by weight or less, more preferably 2% by weight or less, still more preferably 1% by weight or less. When the water absorption is 3% by weight or less, the movement of metal ions in the film-like adhesive is suppressed in the semiconductor package, and the cation can be more appropriately captured.

After the film-like adhesive is thermally cured at 175 ° C for 1 hour, the shearing force against the ruthenium wafer is preferably 0.01 MPa or more and 50 MPa or less, more preferably 0.02 MPa or more and 30 MPa or less, more preferably 0.02 MPa or more and 30 MPa or less. 0.05 MPa or more and 25 MPa or less. When the shearing force is 0.01 MPa or more under the condition of 175 ° C, metal ions are easily diffused from a supporting member (for example, a wafer) to a film-like adhesive in a semiconductor package, so that metal ions can be more appropriately captured. . In addition, shear deformation due to ultrasonic vibration during wire bonding can be prevented, so that the success rate of wire bonding can be improved.

For the film-like adhesive, a film-like adhesive having a weight of 2.5 g is immersed in 50 mL of an aqueous solution containing 10 ppm of copper ions and allowed to stand at 120 ° C for 20 hours, and the copper ion concentration in the aqueous solution is preferably 0. 9.9 ppm, more preferably 0 to 9.5 ppm, further preferably 0 to 9.0 ppm. through The film-like adhesive has such copper ion trapping property, and it is possible to capture metal ions mixed in a semiconductor wafer or the like in the manufacturing process of the semiconductor device. As a result, it is difficult for metal ions mixed from the outside to reach the circuit formation surface formed on the wafer, and deterioration of electrical characteristics can be suppressed, so that product reliability can be improved. In the present invention, as a method of causing the copper ion concentration after capturing copper ions to be 0 to 9.9 ppm, as described above, a method of including an ion-trapping organic compound in a film-form adhesive and a resin component to be used can be used. A method of introducing a functional group capable of trapping a metal ion such as a carboxylic acid group, a method of ion-implanting boron or an n-type dopant, and the like are introduced.

(ion trapping organic compound)

When the film-like adhesive includes an ion-trapping organic compound capable of trapping metal ions, it is possible to more appropriately capture metal ions that are mixed from the outside or can be mixed into a semiconductor wafer or a semiconductor wafer in various steps of manufacturing a semiconductor device. The ion-trapping organic compound exists in a state free from the resin skeleton in the film-like adhesive agent including the skeleton of the adhesive resin, and thus the degree of freedom of diffusion or migration is high, so that metal ions can be efficiently captured.

In the present invention, the metal ions captured by the ion-trapping organic compound are not particularly limited as long as they are metal ions, and examples thereof include Na, K, Ni, Cu, Cr, Co, Hf, Pt, Ca, and Ba. , ions such as Sr, Fe, Al, Ti, Zn, Mo, Mn, V, and the like.

The ion-trapping organic compound is not particularly limited as long as it is a compound capable of forming a complex with a metal ion, and is preferably selected from a nitrogen-containing compound, from the viewpoint of appropriately capturing metal ions. One or more of the group consisting of a hydroxy compound and a carboxyl group-containing compound.

(nitrogen-containing compounds)

As the nitrogen-containing compound, a fine powdery, easily soluble in organic solvent or liquid nitrogen-containing compound is preferred. As such a nitrogen-containing compound, a heterocyclic compound having a tertiary nitrogen atom is preferred from the viewpoint of more appropriately capturing metal ions, and examples thereof include a triazole compound, a tetrazole compound, and a bipyridine compound. From the viewpoint of stability of a complex formed between copper ions, a triazole compound is more preferable. These may be used singly or in combination of two or more.

The triazole compound is not particularly limited, and examples thereof include 1,2,3-benzotriazole, 1-{N,N-bis(2-ethylhexyl)aminomethyl}benzotriazole, and a carboxyl group. Benzotriazole, 2-{2'-hydroxy-5'-methylphenyl}benzotriazole, 2-{2'-hydroxy-3',5'-di-tert-butylphenyl}-5- Chlorobenzotriazole, 2-{2'-hydroxy-3'-tert-butyl-5'-methylphenyl}-5-chlorobenzotriazole, 2-{2'-hydroxy-3',5 '-Di-tert-amylphenyl}benzotriazole, 2-{2'-hydroxy-5'-tert-octylphenyl}benzotriazole, 6-(2-benzotriazolyl)-4- Tert-octyl-6'-tert-butyl-4'-methyl-2,2'-methylene bisphenol, 1-(2',3'-hydroxypropyl)benzotriazole, 1-(1 ',2'-Dicarboxydiethyl)benzotriazole, 1-(2-ethylhexylaminomethyl)benzotriazole, 2,4-di-tert-amyl-6-{(H-benzo Triazol-1-yl)methyl}phenol, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, 3-(2H-benzotriazol-2-yl)- 5-(1,1-dimethylethyl)-4-hydroxy, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2- Phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl] Acid ester, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl ) Phenol, 2-(2H-benzotriazol-2-yl)-4-tert-butylphenol, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2' -hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole, 2 -{2'-hydroxy-3',5'-di-tert-amylphenyl}benzotriazole, 2-{2'-hydroxy-3',5'-di-tert-butylphenyl}-5-chloro Benzotriazole, 2-[2'-hydroxy-3,5-di(1,1-dimethylbenzyl)phenyl]-2H-benzotriazole, 2,2'-methylene double [ 6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], (2-[2-hydroxy-3,5-bis(α ,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl) Methyl propionate and the like.

The commercial product of the triazole compound is not particularly limited, and examples thereof include: BT-120, BT-LX, CBT-1, JF-77, JF-78, and JF- manufactured by Chengbei Chemical Co., Ltd. 79, JF-80, JF83, JAST-500, BT-GL, BT-M, BT-260, BT-365; trade names manufactured by BASF: TINUVIN PS, TINUVIN P, TINUVIN PFL, TINUVIN 99-2, TINUVIN 109, TINUVIN 900, TINUVIN 928, TINUVIN 234, TINUVIN 329, TINUVIN 329 FL, TINUVIN 326, TINUVIN 326 FL, TINUVIN 571, TINUVIN 213; Taiwan's Yongguang Chemical Company's trade name: EVERSORB 81, EVERSORB 109, EVERSORB 70, EVERSORB 71, EVERSORB 72, EVERSORB 73, EVERSORB 74, EVERSORB 75, EVERSORB 76, EVERSORB 78, EVERSORB 80, and the like. The triazole compound can also be used as a rust inhibitor.

The tetrazole compound is not particularly limited, and examples thereof include 5-amino-1H-tetrazole.

The bipyridine compound is not particularly limited, and examples thereof include 2,2'-bipyridine and 1,10-phenanthroline.

(hydroxyl-containing compound)

The hydroxyl group-containing compound is not particularly limited, and is preferably a fine powdery, easily soluble in an organic solvent or a liquid hydroxyl group-containing compound. As such a hydroxyl group-containing compound, a compound having two or more hydroxyl groups on one aromatic ring is preferable from the viewpoint of more appropriately capturing metal ions, and specifically, a benzenediol compound, a hydroxyquinone compound or a polyphenol compound may be mentioned. From the viewpoint of stability of a complex formed between copper ions, a polyphenol compound is more preferable. These may be used singly or in combination of two or more. In addition, the aromatic ring refers to a conjugated ring structure in which the π-electron system is delocalized, and includes not only an uncondensed aromatic ring (for example, a benzene ring) but also a condensed aromatic ring (for example, a naphthalene ring, an anthracene ring, a phenanthrene ring, And tetraphenyl ring, pentacene ring, anthracene ring, etc.), anthracene ring and the like.

The benzenediol compound is not particularly limited, and examples thereof include 1,2-benzenediol and the like.

The hydroxy hydrazine compound is not particularly limited, and is a halogen, a 1,5-dihydroxyindole or the like.

The polyphenol compound is not particularly limited, and examples thereof include tannins and tannin derivatives (gallic acid and alkyl gallate). Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, etc., pyrogallol) Wait.

(carboxyl-containing compound)

The carboxyl group-containing compound is not particularly limited, and examples thereof include a carboxyl group-containing aromatic compound and a carboxyl group-containing aliphatic compound.

The carboxyl group-containing aromatic compound is not particularly limited, and examples thereof include phthalic acid, picolinic acid, and pyrrole-2-carboxylic acid.

The carboxyl group-containing aliphatic compound is not particularly limited, and examples thereof include a higher fatty acid and a carboxylic acid type chelating agent.

The commercial product of the carboxylic acid-type chelating agent is not particularly limited, and may be, for example, Chelest A, Chelest 110, Chelest B, Chelest 200, Chelest C, Chelest D, Chelest 400, and the like. Chelest 40, Chelest 0D, Chelest NTA, Chelest 700, Chelest PA, Chelest HA, Chelest MZ-2, Chellet MZ-4A, Chelest MZ-8, and the like.

The content of the ion-trapping organic compound is preferably 1 to 10 parts by weight, more preferably 2 to 8 parts by weight, even more preferably 3 to 5 parts by weight, per 100 parts by weight of the resin component constituting the adhesive sheet. By setting it as 1 part by weight or more, it is possible to effectively capture cations (especially copper ions), and by setting it to 10 parts by weight or less, it is possible to suppress a decrease in heat resistance or an increase in cost, and it is possible to prevent an excessive ion-trapping organic compound from being caused. The subsequent characteristic changes.

(inorganic filler)

The film-like adhesive includes an inorganic filler having an average particle diameter of 500 nm or less. The average particle diameter of the inorganic filler is 500 nm or less, and There is a particular limitation, and it is preferably 500 nm to 1 nm, more preferably 450 nm to 2 nm, still more preferably 400 nm to 5 nm. By setting the average particle diameter of the inorganic filler to 500 nm or less, mechanical damage to the semiconductor wafer can be prevented, and a decrease in the elastic modulus or the subsequent amount at a high temperature can be prevented.

As the inorganic filler, the inorganic filler in the first embodiment can be suitably used.

The inorganic filler is particularly limited to any one of a spherical shape, an ellipsoidal shape, a flat shape, a rod shape, a column shape, a layer shape, a chain shape, a scale shape, a ring shape (doughnut shape), and an indefinite shape. Further, the shape is any shape, but the average particle diameter is obtained based on the diameter of the ball when the target inorganic filler is assumed to be spherical.

The content of the inorganic filler in the film-like adhesive is not particularly limited as long as it can prevent mechanical damage to the semiconductor wafer, and is preferably 1 to 50% by weight, more preferably 3 to 45% by weight, still more preferably 5 to 40% by weight. . Thereby, the elastic modulus at a high temperature can be ensured while preventing mechanical damage of the inorganic filler to the semiconductor wafer.

In the film-form adhesive, the ratio of the content of the inorganic filler to the content of the ion-trapping organic compound based on the weight may be appropriately selected in consideration of ion trapping property, wafer damage prevention property, adhesion force, and the like. It is preferably 1.1 to 80, more preferably 1.5 to 70, still more preferably 2.0 to 60. By setting the weight ratio within the range, the inorganic filler can be prevented from deteriorating the elastic modulus or the adhesion force caused by the ion-trapping organic compound, and mechanical damage of the inorganic filler to the semiconductor wafer can be prevented.

(adhesive resin)

The film-like adhesive includes an adhesive resin. As the adhesive resin, a conventionally known resin having an adhesive property can be used, and a thermoplastic resin or a thermosetting resin can be suitably used.

(thermoplastic resin)

The film-like adhesive preferably includes a thermoplastic resin. As the thermoplastic resin, natural rubber and the resins exemplified in the first embodiment can be suitably used. However, unlike the first embodiment, the limitation of the epoxy group and the carboxyl group is not included, and one of them may be included, or both of them may be included.

In the film-like adhesive, it is preferred that the thermoplastic component and a thermosetting component to be described later can be cross-linked to each other. When the thermoplastic component and the thermosetting component are crosslinked, the adhesion at a high temperature (for example, 175 to 260 ° C) is higher, and peeling in the reflow process or the like can be prevented, and as a result, the yield of the semiconductor device can be improved. As means for allowing the thermoplastic component and the thermosetting component to crosslink each other, for example, a functional group which can be cross-linked to each other can be introduced into the two components. Examples of the combination of the functional groups which can be crosslinked with each other include an epoxy group and a hydroxyl group, an epoxy group and a carboxyl group, an epoxy group, and an amino group. The thermoplastic component and the thermosetting component can be cross-linked to each other by introducing one of the combinations of these functional groups into the thermoplastic component and introducing the other functional group into the thermosetting component.

In order to crosslink the thermoplastic component and the thermosetting component, when the thermoplastic component specifically has an epoxy group or a carboxyl group, it may be appropriately crosslinked with a thermosetting component. Thermoplastic component with epoxy In the case of the above, the adhesive sheet preferably includes a phenol resin as a thermosetting component. Further, in the case where the thermoplastic component has a carboxyl group, the adhesive sheet preferably includes an epoxy resin as a thermosetting component. The crosslinking reaction can be suitably carried out between the epoxy group of the thermoplastic component and the hydroxyl group of the phenol resin of the thermosetting component, or between the hydroxyl group of the thermoplastic component and the epoxy group of the epoxy resin of the thermosetting component. In order to introduce an epoxy group into the thermoplastic component, a monomer including an epoxy group may be employed as a constituent monomer of the acrylic copolymer. The monomer including the epoxy group is not particularly limited as long as it has an epoxy group, and examples thereof include glycidyl acrylate and glycidyl methacrylate. Further, in order to introduce a carboxyl group into the thermoplastic component, a monomer including a carboxyl group may be employed as a constituent monomer of the acrylic copolymer. The monomer including a carboxyl group is not particularly limited as long as it has a carboxyl group, and examples thereof include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like. .

Among the acrylic resins, an acrylic resin having an acid value of 5 to 150 is preferable, an acrylic resin having an acid value of 10 to 145 is more preferable, and an acrylic resin having an acid value of 20 to 140 is more preferable, and an acid value is particularly preferable. 20~40 acrylic resin. When the film-like adhesive includes an acrylic resin having an acid value of 5 to 150, the carboxyl group of the acrylic resin contributes to the formation of a complex compound and promotes the capturing effect of the ion-trapping organic compound. With such a synergistic effect, Metal ions can be captured more well. The acid value of the acrylic resin in the present invention means the number of mg of potassium hydroxide required to neutralize free fatty acid, resin acid, and the like per 1 g of the sample.

In addition, as other monomers forming the polymer, there is no particular limitation. The preparation may, for example, be an acid anhydride monomer such as maleic anhydride or itaconic anhydride; or a hydroxyl group-containing monomer such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, (A) Base) acrylate 12-hydroxylauryl ester, (meth)acrylic acid (4-hydroxymethylcyclohexyl) methyl ester, etc.; sulfonic acid group-containing monomer, such as styrenesulfonic acid, allylsulfonic acid, 2-(A Acrylamide-2-methylpropanesulfonic acid, (meth)acrylamide, propanesulfonic acid, sulfopropyl (meth)acrylate or (meth)acrylonaphthalenesulfonic acid; or A monomer such as 2-hydroxyethyl acrylate or the like. These monomers may be used singly or in combination of two or more.

(thermosetting resin)

Further, the film-like adhesive preferably includes a thermosetting resin while including the thermoplastic resin. As the thermosetting resin, the thermosetting resin described in the first embodiment can be suitably used.

The mixing ratio of the epoxy resin to the phenol resin is suitably carried out, for example, in an amount of 0.5 to 2.0 equivalents based on 1 equivalent of the hydroxyl group in the phenol resin in the epoxy group. Further, it is more suitably 0.8 to 1.2 equivalents. That is, this is because when the mixing ratio of the two is outside the above range, a sufficient curing reaction cannot be performed, and the properties of the cured epoxy resin are likely to deteriorate.

The blending ratio of the thermosetting resin is not particularly limited as long as it functions as a thermosetting film-like adhesive when the film-like adhesive is heated under predetermined conditions, and the weight of the film-like adhesive is not particularly limited. It is preferably 0 to 90% by weight, more preferably 5 to 85% by weight.

In particular, the adhesive resin is preferably one or more selected from the group consisting of an acrylic resin, an epoxy resin, and a phenol resin, from the viewpoint of the adhesiveness at a low temperature and the elastic modulus at a high temperature. In particular, the adhesive resin includes an epoxy resin, a phenol resin, and an acrylic resin, and the total amount of the epoxy resin and the phenol resin is preferably 10 to 2000 parts by weight, more preferably 10%, based on 100 parts by weight of the acrylic resin. 1500 parts by weight, further preferably 10 to 1000 parts by weight. By setting the total amount of the epoxy resin and the phenol resin to 100 parts by weight or more based on 100 parts by weight of the acrylic resin, the adhesive effect can be obtained by curing, and peeling can be suppressed, and the film can be suppressed by setting it to 2000 parts by weight or less. Brittle and workability is degraded.

(crosslinking agent)

When the film-like adhesive is crosslinked to some extent in advance, a polyfunctional compound that reacts with a functional group at the end of the molecular chain of the polymer or the like may be added as a crosslinking agent. Thereby, the adhesive property at a high temperature can be improved and the heat resistance can be improved. As the crosslinking agent, the crosslinking agent described in the first embodiment can be suitably used.

(other additives)

Further, in the film-like adhesive agent, other additives may be appropriately blended as needed in addition to the above components. As the other additives, the additives described in the first embodiment can be suitably used.

In the above embodiment, the thermosetting resin or the thermoplastic resin used as the adhesive resin is used as the adhesive agent contained in the film-like adhesive. In the present invention, the main component of the adhesive contained in the film-form adhesive may include inorganic components such as ceramics, cement, and solder in addition to the above-mentioned thermosetting resin or thermoplastic resin. .

[Method for Producing Film-Type Adhesive]

The film-form adhesive of the present embodiment is produced, for example, by the following method. First, an adhesive composition as a precursor of a film-like adhesive is prepared. The preparation method is not particularly limited. For example, an ion-trapping organic compound and, if necessary, a thermosetting resin, a thermoplastic resin, and other additives are put into a container, dissolved in an organic solvent, and stirred until uniform, whereby an adhesive composition can be used. The form of the solution is obtained. The program in the first embodiment can be suitably employed in the subsequent programs.

The use of the film-like adhesive is not particularly limited, and can be suitably used for the production of a semiconductor device, and for example, it can be used as a wafer bonding film for fixing a semiconductor wafer to an adherend such as a lead frame for protection. A protective film on the back surface of the semiconductor wafer of the flip chip type semiconductor device and a sealing sheet for sealing the semiconductor wafer are used.

The tensile storage elastic modulus at 60 ° C of the film-form adhesive is preferably 0.01 MPa or more and 1000 MPa or less, more preferably 0.05 MPa or more and 100 MPa or less, and further preferably 0.1 MPa or more and 50 MPa or less. By adjusting the tensile storage elastic modulus at 60 ° C before heat curing to 0.01 MPa or more, the shape of the film can be maintained, and good workability can be imparted. Further, by adjusting the tensile storage elastic modulus at 60 ° C before heat curing to 1000 MPa or less, it is possible to impart good wettability to the adherend.

[semiconductor device]

A semiconductor device of the present embodiment will be described with reference to Fig. 2 . The semiconductor device includes an adherend 6 , the film-like adhesive 3 laminated on the adherend 6 , and a semiconductor wafer 5 disposed on the film-like adhesive 3 . The adherend 6 may be a substrate or other semiconductor wafer. In Fig. 2, a substrate is used as an adherend. In the semiconductor device shown in FIG. 2, the semiconductor wafer 5 is adhered to the end of the terminal portion (internal lead) of the adherend 6 so as to be connected to the electrode pad (not shown) on the semiconductor wafer 5. The bonding wire 7 to which the object 6 is electrically connected, including the bonding wire 7, is covered with the sealing resin 8.

In the semiconductor device of the present embodiment, when the semiconductor wafer is fixed to the adherend, the film-like adhesive is used. Therefore, even after the high-temperature treatment such as the sealing step or the reflow step, the film-like adhesive and the semiconductor wafer can be held. Adhesiveness effectively captures metal ions mixed in the manufacturing process, and as a result, excellent product reliability can be ensured.

[Method of Manufacturing Semiconductor Device]

Hereinafter, an embodiment of a method of manufacturing a semiconductor device in the case where the above film-form adhesive is used as a die bond film will be described.

(cutting/wafer bonding film)

In the following, a method of manufacturing a semiconductor device using the dicing/wafer bonding film 10 in which the film-like adhesive 3 (hereinafter also referred to as the wafer bonding film 3) of the present embodiment is laminated on a conventionally known dicing film will be described. In addition, the dicing film of the present embodiment is formed by laminating on the substrate 1 The structure of the agent layer 2.

(Method of Manufacturing Semiconductor Device)

As a method of manufacturing the semiconductor device of the present embodiment, the manufacturing method described in the first embodiment can be suitably employed.

<Third embodiment>

As shown in FIG. 1, the dicing/wafer bonding film of the present embodiment has a structure in which a bonding sheet 3 is laminated on a dicing film in which an adhesive layer 2 is laminated on a substrate 1. The sheet 3 is then laminated on the adhesive layer 2. Further, as a form of forming the adhesive sheet, as shown in Fig. 4, a configuration in which the adhesive sheet 3' is formed only in the semiconductor wafer pasting portion 3a (refer to Fig. 1).

[cut film]

As the dicing film, for example, a dicing film in which the adhesive layer 2 is laminated on the substrate 1 can be mentioned.

(substrate)

The substrate 1 serves as a strength matrix for the dicing/wafer bonding films 10, 11. For example, low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, block copolymer polypropylene, homopoly polypropylene, polybutene, Polyolefin such as polymethylpentene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate (random, alternating) copolymer, ethylene -butene copolymer, ethylene-hexene copolymer, polyurethane, polyethylene terephthalate, polyethylene naphthalate, etc., polyester, polycarbonate, polyimide, polyether ether ketone , polyimine, polyether phthalimide, polyamine, fully aromatic polyamine, polyphenylene sulfide, aromatic polyamine (paper), glass, glass cloth, fluorine-containing resin, polyvinyl chloride, polyvinylidene chloride, cellulose resin, polyoxyalkylene resin, metal (foil), paper, and the like. When the adhesive layer 2 is an ultraviolet curing type, it is preferable that the substrate 1 is transmissive to ultraviolet rays.

In addition, as a material of the base material 1, a polymer such as a crosslinked body of the above resin may be mentioned. The plastic film may be used without stretching, or may be used after uniaxial or biaxial stretching treatment as needed. By using a resin sheet to which heat shrinkability is imparted by a stretching treatment or the like, by thermally shrinking the substrate 1 after dicing, the adhesion area of the adhesive layer 2 and the adhesive sheet 3 can be reduced, so that the semiconductor wafer can be easily recovered. .

In order to improve the adhesion to the adjacent layer, retention, and the like, the surface of the substrate 1 may be subjected to a conventional surface treatment such as chromic acid treatment, ozone exposure, flame exposure, high voltage electric shock exposure, ionizing radiation treatment, or the like. A coating treatment using a primer (for example, an adhesive described later) is used.

The substrate 1 may be appropriately selected from the same or different kinds of materials, and a material obtained by blending several materials may be used as needed. Further, in order to impart antistatic properties to the substrate 1, a vapor deposition layer containing a conductive material having a thickness of from about 30 Å to about 500 Å such as a metal, an alloy, or an oxide thereof may be provided on the substrate 1. The substrate 1 may be a single layer or a multilayer of two or more.

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

Further, in the substrate 1, various additives (for example, coloring agents, fillers, plasticizing) may be included within a range that does not impair the effects of the present embodiment. Agents, anti-aging agents, antioxidants, surfactants, flame retardants, etc.).

(adhesive layer)

The storage elastic modulus of the adhesive layer 2 at 26 ° C was 1.0 × 10 ⁴ Pa or more and 1.0 × 10 ⁷ Pa or less. By having the storage elastic modulus of the range of the adhesive layer 2, a moderate crosslinked structure can be formed in the adhesive layer. Thereby, the transfer of the ion scavenger from the adhesive sheet to the adhesive layer can be restricted, and as a result, the decrease in the ion trapping property of the adhesive sheet can be suppressed.

The adhesive used in the formation of the adhesive layer 2 is not particularly limited as long as it exhibits a predetermined storage elastic modulus after the formation of the adhesive layer, and can control the adhesive of the adhesive sheet 3 in a peelable manner. For example, a general pressure-sensitive adhesive such as an acrylic adhesive or a rubber-based adhesive can be used. As the pressure-sensitive adhesive, it is preferable to use an acrylic polymer as a base polymer from the viewpoint of cleaning and washing property of an organic solvent such as an ultrapure water or an alcohol, such as a semiconductor wafer or glass. Acrylic adhesive.

As the acrylic polymer, an acrylic polymer using acrylate as a main monomer component can be mentioned. As the acrylate, for example, an alkyl (meth)acrylate (for example, methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, sec-butyl ester, tert-butyl ester, or the like) may be used. Amyl, isoamyl, hexyl, heptyl, octyl, 2-ethylhexyl, isooctyl, decyl, decyl, isodecyl, undecyl, dodecyl, tridecane a linear or branched alkyl ester having an alkyl group having 1 to 30 carbon atoms, particularly a carbon number of 4 to 18, such as an ester, a myristyl ester, a hexadecane ester, an octadecyl ester or an eicosyl ester. And cycloalkyl (meth)acrylate (eg, cyclopentyl ester, cyclohexyl ester, etc.) One or two or more kinds of acrylic polymers or the like as a monomer component. Further, (meth) acrylate means acrylate and/or methacrylate, and (meth) of the present invention all means the same meaning.

In order to improve cohesive force, heat resistance, and the like, the acrylic polymer may include a unit corresponding to another monomer component copolymerizable with the alkyl (meth)acrylate or the cycloalkyl ester, as needed. As such a monomer component, for example, a carboxyl group-containing monomer such as acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, and rich may be mentioned. Acidic acid, crotonic acid, etc.; anhydride monomers such as maleic anhydride, itaconic anhydride, etc.; hydroxyl-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate , 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, ( Methyl)acrylic acid-12-hydroxylauryl ester, (meth)acrylic acid (4-hydroxymethylcyclohexyl) methyl ester, etc.; sulfonic acid group-containing monomer, such as styrenesulfonic acid, allylsulfonic acid, 2-( Methyl)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid, sulfopropyl (meth)acrylate, (meth)acrylonaphthalenesulfonic acid, etc.; A phosphate group monomer such as 2-hydroxyethyl acrylate or the like; acrylamide, acrylonitrile or the like. These copolymerizable monomer components may be used alone or in combination of two or more. The amount of these copolymerizable monomers used is preferably 40% by weight or less based on the total of the monomer components.

Further, the acrylic polymer may include a polyfunctional monomer or the like as a monomer component for copolymerization as needed in order to carry out crosslinking. Examples of such a polyfunctional monomer include hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, and (poly)propylene glycol di(methyl). Acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol Methyl) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, and the like. These polyfunctional monomers may also be used alone or in combination of two or more. The amount of use of the polyfunctional monomer is preferably 30% by weight or less based on the total of the monomer components from the viewpoint of adhesion characteristics and the like.

The acrylic polymer can be obtained by polymerizing a single monomer or a mixture of two or more monomers. The polymerization can be carried out by any means such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, or the like. The content of the low molecular weight substance is preferably small from the viewpoint of preventing contamination of the clean adherend, and the weight average molecular weight of the acrylic polymer is preferably about from the viewpoint of exhibiting a predetermined storage elastic modulus of the adhesive layer. More than 300,000, more preferably about 400,000 to about 3 million.

The glass transition temperature (Tg) of the acrylic polymer is preferably -70 ° C or more from the viewpoint of peeling adhesion. More preferably, it is -60 ° C or more. Further, the glass transition temperature is preferably -40 to 15 °C. Therefore, it is suitable that the glass transition temperature of the homopolymer is -70 ° C or more for the main monomer for forming the acrylic polymer. The method for measuring the glass transition temperature (Tg) of the acrylic polymer is based on the description of the examples.

The iodine value of the acrylic polymer is preferably in the range of 5 to 10, more preferably in the range of 5.5 to 9. When the iodine value is less than 5, the effect of reducing the adhesion after irradiation of the radiation layer in the case where the adhesive layer 2 is irradiated is insufficient. On the other hand, when the iodine value exceeds 10, the cut film is next The adhesion of the sheet is increased and sometimes it is difficult to pick up. Further, the numerical value range of the iodine value is a value measured based on JIS K 0070-1992, and the details of the measurement procedure are based on the description of the examples.

The hydroxyl value of the acrylic polymer is preferably in the range of from 7 to 30, more preferably in the range of from 10 to 25. When the hydroxyl value is less than 7, the effect of lowering the adhesion after irradiation of the radiation layer in the case where the adhesive layer 2 is irradiated is insufficient. On the other hand, when the hydroxyl value exceeds 30, the adhesion of the dicing film to the wafer bonding film is increased, and it is sometimes difficult to pick up. Further, the numerical value range of the hydroxyl value is a value measured by an acetylation method based on JIS K 0070-1992, and the details of the measurement procedure are based on the description of the examples.

Further, in order to increase the weight average molecular weight of the acrylic polymer or the like as the base polymer, an external crosslinking agent may be suitably used in the adhesive. Specific examples of the external crosslinking method include a method of adding a so-called crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound or a melamine crosslinking agent, and reacting the same. When an external crosslinking agent is used, the amount thereof to be used is appropriately determined depending on the balance with the base polymer to be crosslinked and the use as an adhesive. In general, it is preferably blended 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. In addition, from the viewpoint of imparting a predetermined storage elastic modulus to the adhesive layer, it is preferable to include 1 to 5 parts by weight of an isocyanate crosslinking agent per 100 parts by weight of the acrylic resin. Further, if necessary, in addition to the above-described components, additives such as various conventionally known tackifiers and anti-aging agents may be used in the adhesive.

The adhesive layer 2 can be formed of a radiation curable adhesive. At this time, the storage elastic modulus of the adhesive layer at 26 ° C before the irradiation of the radiation needs to be 1.0 × 10 ⁴ Pa or more and 1.0 × 10 ⁷ Pa or less. The radiation-curable adhesive can easily reduce the adhesion by increasing the degree of crosslinking by irradiation with radiation such as ultraviolet rays. For example, in the adhesive layer 2 shown in Fig. 1, by irradiating only the portion 2a corresponding to the wafer adhering portion 3a with radiation, it is possible to provide a difference in adhesion to the portion 2b other than the portion 2a.

Further, by curing the radiation-curable adhesive layer 2 in accordance with the adhesive sheet 3', the portion 2a in which the adhesive strength is remarkably lowered can be easily formed. Since the adhesive sheet 3' is adhered to the portion 2a which is cured and has a lowered adhesive force, the interface between the portion 2a and the adhesive sheet 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 portion 2b.

As described above, in the adhesive layer 2 of the dicing/wafer bonding film 10 shown in Fig. 1, the portion 2b formed of the uncured radiation-curable adhesive adheres to the adhesive sheet 3, and the retention at the time of cutting can be ensured. force. Thus, the radiation-curable adhesive can support the adhesive sheet 3 for fixing the semiconductor wafer to an adherend such as a substrate with a good adhesion-peel balance. In the adhesive layer 2 of the dicing/wafer bonding film 11 shown in Fig. 4, the portion 2b can fix a wafer ring.

The radiation-curable adhesive can be a radiation-curable adhesive which exhibits an adhesive having a radiation-curable functional group such as a carbon-carbon double bond without any particular limitation. As a radiation-curable adhesive, for example, a radiation-curable monomer component or an oligomer component is blended in a general pressure-sensitive adhesive such as an acrylic adhesive or a rubber-based adhesive. Addition type radiation curing adhesive.

Examples of the radiation curable monomer component to be blended include a urethane oligomer, a urethane (meth) acrylate, a trimethylolpropane tri(meth) acrylate, and a tetrahydroxy group. Methyl methane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxy penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , 1,4-butanediol di(meth)acrylate, and the like. Further, examples of the radiation curable oligomer component include various oligomers such as urethanes, polyethers, polyesters, polycarbonates, and polybutadienes, and the weight average molecular weight thereof is from about 100 to about A range of 30000 is appropriate. The blending amount of the radiation curable monomer component or the oligomer component can be appropriately determined according to the type of the adhesive layer to reduce the adhesion of the adhesive layer. In general, it is, for example, about 5 parts by weight to about 500 parts by weight, preferably about 40 parts by weight to about 150 parts by weight, per 100 parts by weight of the base polymer such as an acrylic polymer constituting the pressure-sensitive adhesive.

Further, as the radiation-curable adhesive, in addition to the above-described additive-type radiation-curable adhesive, polymerization using a carbon-carbon double bond in a polymer side chain or a main chain or at a main chain terminal may be mentioned. An intrinsic radiation curing adhesive that acts as a base polymer. The intrinsic type radiation-curable adhesive does not need to include or contain a large amount of an oligomer component as a low molecular weight component, and therefore the oligomer component or the like does not move in the adhesive over time, and can form a stable layer structure adhesion. The agent layer is therefore preferred.

As the base polymer having a carbon-carbon double bond, a polymer having a carbon-carbon double bond and having adhesiveness can be used without particular limitation. As such a base polymer, a polymer having an acrylic polymer as a basic skeleton is preferable. The basic skeleton of the acrylic polymer may, for example, be an acrylic polymer exemplified above.

The method of introducing the carbon-carbon double bond in the acrylic polymer is not particularly limited, and various methods can be employed, but introducing a carbon-carbon double bond into the polymer side chain is relatively easy in molecular design. For example, a monomer having a functional group is copolymerized into an acrylic polymer, and then a compound having a functional group capable of reacting with the functional group and a carbon-carbon double bond is used to maintain the radiation curability of the carbon-carbon double bond. A method of carrying out a condensation or addition reaction.

Examples of the combination of these functional groups include a carboxyl group, an epoxy group, a carboxyl group and an aziridine group, a hydroxyl group and an isocyanate group. Among the combinations of these functional groups, a combination of a hydroxyl group and an isocyanate group is preferred from the viewpoint of easiness of reaction tracking. Further, if a combination of the acrylic polymers having a carbon-carbon double bond is formed by a combination of these functional groups, the functional group may be on either of the acrylic polymer and the compound, in the preferred combination Among them, it is preferred 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 methacryl oxime isocyanate, 2-methacryl oxirane ethyl isocyanate, m-isopropenyl-α, α-dimethylbiphenyl hydrazine. Isocyanate, etc. Further, as the acrylic polymer, a hydroxyl group-containing monomer or 2-hydroxyethyl group exemplified above may be used. A polymer such as an ether compound of vinyl ether, 4-hydroxybutyl vinyl ether or diethylene glycol monovinyl ether.

The intrinsic radiation-curable adhesive may use the base polymer (especially an acrylic polymer) having a carbon-carbon double bond alone, or may blend the radiation curability in a range that does not impair the properties. Monomer component or oligomer component. The radiation curable oligomer component or the like 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 curable adhesive may include a photopolymerization initiator when cured via ultraviolet rays or the like. The photopolymerization initiator may, for example, be an α-keto alcohol compound such as 4-(2-hydroxyethoxy)phenyl (2-hydroxy-2-propyl) ketone or α-hydroxy-α, α'. - dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, 1-hydroxycyclohexyl phenyl ketone, etc.; acetophenones such as methoxyacetophenone, 2,2-dimethoxy 2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1- Ketones; benzoin ether compounds, such as benzoin ethyl ether, benzoin isopropyl ether, fennel aceton methyl ether, etc.; ketal compounds, such as biphenyl dimethyl ketal; aromatic sulfonate a chlorine-based compound such as 2-naphthalenesulfonium chloride; a photoactive terpenoid such as 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)anthracene; Ketones such as benzophenone, benzamidine benzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, etc.; thioxanthone compounds such as thioxanthone, 2-chloro Thioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone 2,4-diisopropylthioxanthone ; Camphor quinone; halogenated ketones; acyl phosphine oxide; acyl Phosphonate and the like. The amount of the photopolymerization initiator to be added is, for example, about 0.05 part by weight to about 20 parts by weight based on 100 parts by weight of the base polymer such as the acrylic polymer constituting the pressure-sensitive adhesive.

In the case where the adhesive layer 2 is formed by the radiation-curable adhesive, it is preferable to irradiate a part of the adhesive layer 2 with radiation so that the adhesive force of the portion 2a < the adhesion of the portion 2b. In the dicing/wafer bonding film of Fig. 1, for example, the relationship of the adhesion force of the portion 2a < the portion 2b to the SUS304 plate (#2000 polishing) as the adherend is the adhesion.

As a method of forming the portion 2a in the adhesive layer 2, after the radiation-curable adhesive layer 2 is formed on the substrate 1, the portion 2a is partially irradiated with radiation to be cured. method. The local radiation irradiation can be performed via a photomask formed with a pattern corresponding to the portion 3b or the like other than the semiconductor wafer pasting portion 3a. Further, a method of curing by spot irradiation with ultraviolet rays or the like can be mentioned. The formation of the radiation curable adhesive layer 2 can be carried out by transferring the radiation curable adhesive layer provided on the separator to the substrate 1. Localized radiation exposure can also be performed on the radiation curable adhesive layer 2 disposed on the separator.

Further, when the adhesive layer 2 is formed by the radiation-curable adhesive, it is possible to use light-shielding of all or part of a portion other than the portion corresponding to the semiconductor wafer adhering portion 3a on at least one side of the substrate 1. In the substrate, the radiation-curable adhesive layer 2 is formed on the substrate, and then irradiated with radiation to cure a portion corresponding to the semiconductor wafer adhering portion 3a, thereby forming the portion 2a in which the adhesive force is lowered. As a light-shielding material, it can be printed or vapor-deposited on a support film to be a photomask. Material to make. The dicing/wafer bonding film 10 of the present embodiment can be efficiently manufactured through the manufacturing method.

Further, when curing failure occurs due to oxygen at the time of radiation irradiation, it is preferable to isolate oxygen (air) from the surface of the radiation-curable adhesive layer 2 by any method. For example, a method of covering the surface of the adhesive layer 2 with a separator or a method of irradiating radiation such as ultraviolet rays in a nitrogen atmosphere may be mentioned.

The thickness of the adhesive layer 2 is not particularly limited, and is preferably from about 1 μm to about 50 μm from the viewpoint of simultaneously preventing the chip cut surface defect and the adhesion maintaining of the adhesive layer. It is preferably 2 μm to 30 μm, and more preferably 5 μm to 25 μm.

Further, in the adhesive layer 2, various additives (for example, a coloring agent, a thickener, a bulking agent, a filler, a tackifier, a plasticizer, and an anti-wear agent) may be included within a range not impairing the effects of the embodiment. Aging agents, antioxidants, surfactants, crosslinkers, etc.).

[Next film]

Next, the sheets 3, 3' (hereinafter sometimes referred to as "the succeeding sheet 3") include an ion trapping agent capable of trapping metal ions, and suitably include a thermoplastic resin and a thermosetting resin, and may further include other components. As the adhesive sheets 3, 3', the adhesive sheet of the above-described embodiment can be suitably used.

The thickness of the sheet 3 is not particularly limited, and since the transfer of the ion scavenger from the adhesive sheet 3 to the adhesive layer can be suppressed, it is possible to easily reduce the thickness of the semiconductor device in order to increase the capacity of the semiconductor device. The thickness of the sheet is preferably thinner in a range of 3 μm or more and 150 μm or less, and more preferably in a range of 4 μm or more and 120 μm or less. More preferably, it is the range of 5 micrometers or more and 100 micrometers or less.

For the succeeding sheet 3, after the 2.5 g weight of the back sheet was immersed in 50 mL of an aqueous solution containing 10 ppm of copper ions and left at 120 ° C for 20 hours, the copper ion concentration in the aqueous solution was preferably 0 to 9.8 ppm, more preferably It is 0 to 9.5 ppm, and more preferably 0 to 9.0 ppm. By having such copper ion trapping property through the adhesive sheet, it is possible to capture metal ions that are mixed into the semiconductor wafer or the like from the outside in the manufacturing process of the semiconductor device. As a result, it is difficult for metal ions mixed from the outside to reach the circuit formation surface formed on the wafer, and deterioration of electrical characteristics can be suppressed, so that product reliability can be improved. In the present embodiment, as a method of causing the copper ion concentration after capturing copper ions to be 0 to 9.8 ppm, in addition to the method of including the ion scavenger in the underlayer as described above, it is also possible to introduce the resin component to be used. A method of capturing a functional group of a metal ion such as a carboxylic acid group, a method of ion-implanting boron or an n-type dopant, or the like.

The tensile storage elastic modulus at 60 ° C of the adhesive sheet before heat curing is preferably 0.01 MPa or more and 1000 MPa or less, more preferably 0.05 MPa or more and 100 MPa or less, further preferably 0.1 MPa or more and 50 MPa or less. By adjusting the tensile storage elastic modulus at 60 ° C before heat curing to 0.01 MPa or more, the shape of the film can be maintained, and good workability can be imparted. Further, by adjusting the tensile storage elastic modulus at 60 ° C before heat curing to 1000 MPa or less, it is possible to impart good wettability to the adherend.

[Method of Manufacturing Cutting/Wafer Bonding Film]

The dicing/wafer bonding films 10 and 11 of the present embodiment can be, for example, It is produced by separately making a cut film and a back sheet, and finally sticking them. Specifically, it can be produced in accordance with the following procedure.

First, the substrate 1 can be formed into a film by a conventionally known film forming method. Examples of the film forming method include 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 co-extrusion method, and a dry lamination method. Wait.

Next, an adhesive composition for forming an adhesive layer was prepared. A resin, an additive, and the like described in the adhesive layer item are blended in the adhesive composition. The prepared adhesive composition is coated on the substrate 1 to form a coating film, and then the coating film is dried (heat-crosslinked as needed) under predetermined conditions to form an adhesive layer 2. The coating method is not particularly limited, and examples thereof include roll coating, screen coating, and gravure coating. 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. Alternatively, the coating film may be formed by applying an adhesive composition to the separator, and then drying the coating film under the drying conditions to form the adhesive layer 2. Thereafter, the adhesive layer 2 is adhered to the substrate 1 together with the separator. Thus, a dicing film having the substrate 1 and the adhesive layer 2 was produced. Further, the dicing film may have at least a base material and an adhesive layer, and is also referred to as a dicing film when it has other elements such as a separator.

The adhesive sheet of the present embodiment is produced, for example, by the following method. First, for example, an ion trapping agent and, if necessary, a thermosetting resin, a thermoplastic resin, and other additives are put into a container, dissolved in an organic solvent, and stirred to be uniform, thereby being obtained as a solution of the adhesive composition.

As the organic solvent, as long as it is a component which can constitute a sheet The organic solvent which is uniformly dissolved, kneaded or dispersed is not limited, and a conventionally known organic solvent can be used. Examples of such a solvent include ketone solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, acetone, methyl ethyl ketone, and cyclohexanone, toluene, xylene, and the like. Methyl ethyl ketone, cyclohexanone or the like is preferably used from the viewpoint of fast drying speed and inexpensive availability.

The adhesive composition solution prepared above is applied onto a substrate separator to a predetermined thickness to form a coating film, which is then dried under predetermined conditions. As the substrate separator, polyethylene terephthalate (PET), polyethylene, polypropylene, or a surface release coating using a release agent such as a fluorine-containing release agent or a long-chain alkyl acrylate release agent can be used. Plastic film or paper, etc. In addition, the coating method is not particularly limited, and examples thereof include roll coating, screen coating, and gravure coating. Further, 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. Thereby, the adhesive sheet of this embodiment can be obtained.

Next, the separator was peeled off from the dicing film, and the adhesive sheet was adhered to the dicing film in such a manner that the adhesive sheet and the adhesive layer were adhered. Adhesion can be carried out, for example, via crimping. At this time, the lamination temperature is not particularly limited, and is, for example, preferably 30 to 50 ° C, more preferably 35 to 45 ° C. Further, the linear pressure is not particularly limited, and is, for example, preferably 0.1 to 20 kgf/cm, more preferably 1 to 10 kgf/cm. Then, the substrate spacer on the film is peeled off to obtain the dicing/wafer bonding film of the present embodiment.

[Semiconductor device and method of manufacturing the same]

As the semiconductor device and the method of manufacturing the same according to the embodiment, it is possible to The semiconductor device and the manufacturing method described in the first embodiment are employed.

Example

Hereinafter, preferred embodiments of the present invention will be specifically described 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 unless otherwise specified. In addition, hereinafter, when it is a part, it means the weight part.

[First Embodiment]

Each of the following embodiments corresponds to the above-described one of the first embodiment.

(Example 1)

The following (a) to (e) were dissolved in methyl ethyl ketone to obtain a solution of an adhesive composition having a concentration of 20% by weight.

Applying the solution of the adhesive composition to release from the polyoxyalkylene After the treated release film having a thickness of 50 μm of a polyethylene terephthalate film, it was dried at 130 ° C for 2 minutes. Thus, the adhesive sheet of Example 1 having a thickness of 20 μm was produced.

(Example 2)

The following (a) to (e) were dissolved in methyl ethyl ketone to obtain a solution of an adhesive composition having a concentration of 20% by weight.

The adhesive composition solution was applied onto a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after demolding with polyoxymethane, and then dried at 130 ° C for 2 minutes. . Thus, the succeeding film of Example 2 having a thickness of 20 μm was produced.

(Example 3)

The following (a) to (e) were dissolved in methyl ethyl ketone to obtain a solution of an adhesive composition having a concentration of 20% by weight.

The adhesive composition solution was applied onto a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after demolding with polyoxymethane, and then dried at 130 ° C for 2 minutes. . Thus, the succeeding film of Example 3 having a thickness of 20 μm was produced.

(Comparative Example 1)

The following (a) to (e) were dissolved in methyl ethyl ketone to obtain a solution of an adhesive composition having a concentration of 20% by weight.

The adhesive composition solution was applied onto a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after demolding with polyoxymethane, and then dried at 130 ° C for 2 minutes. . Thus, a laminate of Comparative Example 1 having a thickness of 20 μm was produced.

(Comparative Example 2)

The following (a) to (e) were dissolved in methyl ethyl ketone to obtain a solution of an adhesive composition having a concentration of 20% by weight.

Applying the solution of the adhesive composition to release from the polyoxyalkylene After the treated release film having a thickness of 50 μm of a polyethylene terephthalate film, it was dried at 130 ° C for 2 minutes. Thus, a laminate of Comparative Example 2 having a thickness of 20 μm was produced.

(Comparative Example 3)

The following (a) to (e) were dissolved in methyl ethyl ketone to obtain a solution of an adhesive composition having a concentration of 20% by weight.

The adhesive composition solution was applied onto a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after demolding with polyoxymethane, and then dried at 130 ° C for 2 minutes. . Thus, a film of Comparative Example 3 having a thickness of 20 μm was produced.

(Comparative Example 4)

The following (a) to (d) were dissolved in methyl ethyl ketone to obtain a solution of an adhesive composition having a concentration of 20% by weight.

The adhesive composition solution was applied onto a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after demolding with polyoxymethane, and then dried at 130 ° C for 2 minutes. . Thus, a laminate of Comparative Example 4 having a thickness of 20 μm was produced.

(Copper ion capture evaluation)

The back sheets (thickness 20 μm) of the examples and the comparative examples were respectively cut into a size of 240 mm × 300 mm (about 2.5 g), and folded five times to obtain a size of 37.5 mm × 60 mm, which was placed to a diameter of 58 mm and a height of 37 mm. In a cylindrical sealed Teflon (registered trademark) container, 50 ml of a 10 ppm copper (II) ion aqueous solution was added. Then, it was allowed to stand at 120 ° C for 20 hours in a constant temperature dryer (PV-231, manufactured by Espec Co., Ltd.). After the film was taken out, the concentration of copper ions in the aqueous solution was measured using ICP-AES (SPS-1700HVR, manufactured by SII NanoTechnology Co., Ltd.). When the concentration of copper ions in the aqueous solution was 0 to 9.8 ppm, it was evaluated as ○, and when it was more than 9.8 ppm, it was evaluated as ×. Result list 1 is shown.

(void disappearance)

The succeeding sheets (thickness: 20 μm) of the examples and the comparative examples were adhered to a semiconductor wafer of 10 mm square at a temperature of 40 ° C, and the semiconductor wafer was mounted on the BGA substrate via each of the succeeding sheets. The installation conditions were a temperature of 120 ° C, a pressure of 0.1 MPa, and 1 second. Then, the BGA substrate on which the semiconductor wafer was mounted was heat-treated at 175 ° C for 30 minutes using a dryer, and then packaged with a sealing resin (GE-100, manufactured by Nitto Denko Corporation). The sealing conditions were: heating temperature 175 ° C, 90 seconds. Next, the sealed semiconductor device was cut with a glass knife, and the cross section was observed using an ultrasonic microscope, and the void area in the adhesion surface of each of the adhesive sheets and the BGA substrate was measured. When the void area was less than 50% with respect to the adhesion area, it was evaluated as ○, and when it was 50% or more, it was evaluated as ×. The results are shown in Table 1 below.

(wet reflow resistance)

The succeeding sheets (thickness: 20 μm) of the examples and the comparative examples were adhered to a semiconductor wafer of 10 mm square at a temperature of 40 ° C, and the semiconductor wafer was mounted on the BGA substrate via each of the succeeding sheets. The installation conditions were a temperature of 120 ° C, a pressure of 0.1 MPa, and 1 second. Then, the BGA substrate on which the semiconductor wafer was mounted was heat-treated at 175 ° C for 30 minutes using a dryer, and then packaged with a sealing resin (GE-100, manufactured by Nitto Denko Corporation). The sealing conditions were: heating temperature 175 ° C, 90 seconds. Then, moisture absorption was performed under conditions of 85 ° C, 60% RH, and time 168 hours, and the BGA substrate on which the semiconductor wafer was mounted was placed on the IR reflow set at 260 ° C or higher for 10 seconds. furnace in. Then, the sealed semiconductor device was cut with a glass knife, and the cross section was observed using an ultrasonic microscope to confirm whether or not peeling occurred at the boundary between each of the thermosetting wafer bonding film and the BGA substrate. When it was confirmed that the semiconductor wafers which were peeled off were three or less, it was evaluated as ○, and when it was four or more, it was evaluated as ×. The results are shown in Table 1 below.

(result)

In the examples, copper ion trapping property, void disappearance, and wet reflow resistance all showed good results. On the other hand, in Comparative Example 1, the dodecyl gallate reacted with the epoxy group of the acrylic resin, and the curing was vigorously performed, and the void disappearability at the time of molding was lowered. Further, in Comparative Example 2, a functional group which reacts with a curable resin or a complex-forming organic compound (including a complex-forming organic compound having a benzene ring having two or more phenolic hydroxyl groups) is not present on the acrylic resin. Therefore, the void disappearance at the time of molding can be ensured. However, the acrylic resin was not crosslinked, and thus could not withstand the reflow test, causing peeling at the subsequent interface, thereby generating voids. Further, in Comparative Example 3, TT-LX did not have an inverse relationship with the resin constituting the adhesive sheet. However, since it acts as a basic catalyst, the reaction of an epoxy group and a carboxyl group, or an epoxy group and a phenol group is accelerated by a heat history, and the void-formability at the time of shaping|molding declines. Further, in Comparative Example 4, since the complex-forming organic compound capable of forming a complex with a cation was not contained, metal ions could not be captured.

[Second Embodiment]

Each of the following embodiments and the like corresponds to the above-described one of the second embodiment.

(Example 1)

The following (a) to (e) were dissolved in methyl ethyl ketone to obtain a solution of an adhesive composition having a concentration of 20% by weight.

Applying the solution of the adhesive composition to a polyethylene terephthalate having a thickness of 50 μm after being released from the polysiloxane by using a release liner After the release-treated film composed of the alcohol ester film, it was dried at 130 ° C for 2 minutes. Thus, a film-like adhesive A having a thickness of 20 μm was produced.

(Example 2)

The following (a) to (e) were dissolved in methyl ethyl ketone to obtain a solution of an adhesive composition having a concentration of 20% by weight.

After applying the solution of the adhesive composition onto a release-treated film comprising a polyethylene terephthalate film having a thickness of 50 μm which has been subjected to release treatment with polysiloxane, as a release liner, Dry at 130 ° C for 2 minutes. Thus, a film-like adhesive B having a thickness of 20 μm was produced.

(Example 3)

The following (a) to (e) were dissolved in methyl ethyl ketone to obtain a solution of an adhesive composition having a concentration of 20% by weight.

(a) Propylene with ethyl acrylate-methyl methacrylate as main component

After applying the solution of the adhesive composition onto a release-treated film comprising a polyethylene terephthalate film having a thickness of 50 μm which has been subjected to release treatment with polysiloxane, as a release liner, Dry at 130 ° C for 2 minutes. Thus, a film-like adhesive C having a thickness of 20 μm was produced.

(Example 4)

The following (a) to (e) were dissolved in methyl ethyl ketone to obtain a solution of an adhesive composition having a concentration of 20% by weight.

After applying the solution of the adhesive composition onto a release-treated film comprising a polyethylene terephthalate film having a thickness of 50 μm which has been subjected to release treatment with polysiloxane, as a release liner, Dry at 130 ° C for 2 minutes. Thus, a film-like adhesive D having a thickness of 20 μm was produced.

(Comparative Example 1)

The following (a) to (d) were dissolved in methyl ethyl ketone to obtain a solution of an adhesive composition having a concentration of 20% by weight.

After applying the solution of the adhesive composition onto a release-treated film comprising a polyethylene terephthalate film having a thickness of 50 μm which has been subjected to release treatment with polysiloxane, as a release liner, Dry at 130 ° C for 2 minutes. Thus, a film-like adhesive E having a thickness of 20 μm was produced.

(Comparative Example 2)

The following (a) to (e) were dissolved in methyl ethyl ketone to obtain a solution of an adhesive composition having a concentration of 20% by weight.

After applying the solution of the adhesive composition onto a release-treated film comprising a polyethylene terephthalate film having a thickness of 50 μm which has been subjected to release treatment with polysiloxane, as a release liner, Dry at 130 ° C for 2 minutes. Thus, a film-like adhesive F having a thickness of 20 μm was produced.

(Measurement of average particle size of inorganic filler)

The average particle diameter of the filler was determined by a photometric particle size distribution meter (manufactured by HORIBA, device name: LA-910). Under the following measurement conditions: laser 89.7%, the distribution pattern is monodisperse, the number of measurements (take 込 The number of times is 10 times.

(Copper ion capture evaluation)

Each of the film-form adhesives A to F of the examples and the comparative examples was cut into a weight of about 2.5 g, laminated to a size of 30 mm × 37.5 mm × 0.32 mm, and the laminated sample was heated at 175 ° C for 5 hours. The heated sample was placed in a cylindrical closed Teflon (registered trademark) container having a diameter of 58 mm and a height of 37 mm, and 50 ml of a 10 ppm copper (II) ion aqueous solution was added thereto. Then, it was allowed to stand at 120 ° C for 20 hours in a constant temperature dryer (PV-231, manufactured by Espec Co., Ltd.). After the film was taken out, the concentration of copper ions in the aqueous solution was measured using ICP-AES (SPS-1700HVR, manufactured by SII NanoTechnology Co., Ltd.). When the concentration of copper ions in the aqueous solution was 0 to 9.8 ppm, it was evaluated as ○, and when it was more than 9.8 ppm, it was evaluated as ×. The results are shown in Table 2. The copper ion concentration (ppm) measured after the test is listed in Table 2.

(Identification of wafer damage during wafer bonding)

The film-like adhesives A to F obtained in the examples and the comparative examples were adhered to a dicing film (DU-300, manufactured by Nitto Denko Corporation) to obtain a film-like adhesive with a dicing film. The wafer having a thickness of 30 μm in which a circuit was formed and a film-like adhesive having a film-like adhesive having a dicing film were adhered at 60° C., and then cut (cutting device: manufactured by DISCO Co., Ltd., DFD6361) to make a paste. A 10 mm × 10 mm wafer of a film-like adhesive. The fabricated wafer wafer with a film-like adhesive was bonded to a lead frame (Alloy 42). The wafer bonding was carried out by applying a load (0.1 MPa) at a temperature of 120 ° C and heating for 1 second using a wafer bonding machine (SPA-300 manufactured by Shinkawa Co., Ltd.). The case where no damage occurred in all of the 50 wafer-bonded wafers was evaluated as ○, even if there was A condition in which a defect such as a defect or a fracture is generated is evaluated as ×. The results are shown in Table 2.

(Determination of tensile storage elastic modulus at 175 ° C after heat curing)

The film-like adhesives of the respective Examples and Comparative Examples were allowed to stand in an oven at 175 ° C for 5 hours, and then tensile heat storage at 175 ° C after heat curing was measured using a viscoelasticity measuring apparatus (RSA-II, manufactured by Rheometric Co., Ltd.). Elastic Modulus. In the measurement, a measurement sample which was cut so as to have a length of 30 mm, a width of 10 mm, and a thickness of 0.20 mm was obtained by adhering a plurality of produced continuous sheets. The tensile storage elastic modulus was measured at a temperature of -40 to 300 ° C at a frequency of 1 Hz, a strain of 0.1%, and a temperature increase rate of 10 ° C / minute. When the tensile storage elastic modulus was 0.1 MPa or more, it was evaluated as ○, and when it was less than 0.1 MPa, it was evaluated as ×. The measured values and results at 175 ° C are listed in Table 2.

(Measurement of shear adhesion at 175 ° C after heat curing)

The wafer-bonded sample in the above wafer damage evaluation was heated at 175 ° C for 1 hour to cure the adhesive sheet. The shearing force of the succeeding film and the wafer wafer was measured using a shear tester (Dage 4000, manufactured by Dage Co., Ltd.). The conditions of the shear test were a measurement speed of 500 μm/s, a measurement gap of 100 μm, and a plateau temperature of 175 °C. The case where the shearing force was 0.01 MPa or more was evaluated as ○, and when it was less than 0.01 MPa, it was evaluated as ×. The measured values at 175 ° C are listed in Table 2 together with the results.

Table 2

As can be seen from the results of Table 2, the copper ion trapping property of the film-like adhesive of the examples, the wafer damage at the time of wafer bonding, the tensile storage elastic modulus at 175 ° C after heat curing, and the heat curing were The shear adhesion at 175 ° C is a good result. On the other hand, the film-form adhesive of Comparative Example 1 did not cause wafer damage, but since the ion-trapping organic compound was not contained, the ion trapping property was hardly exhibited. Further, in the film-form adhesive of Comparative Example 2, although the ion trapping property was good, the wafer was damaged. This is considered to be due to the fact that the inorganic filler has an average particle diameter of up to 5.0 μm, thereby causing the inorganic filler to contact the wafer during wafer bonding.

[Third embodiment]

Each of the following examples and the like corresponds to the dicing/wafer bonding film of the third embodiment.

(Preparation of substrate)

A polyethylene terephthalate film (PET film) having a thickness of 50 μm was prepared as a substrate.

(Preparation of Acrylic Polymer A)

In a reaction vessel having a condenser tube, a nitrogen gas introduction tube, a thermometer, and a stirring device, 4 parts of 2-ethylhexyl acrylate, 3 parts of butyl acrylate, 100 parts of 2-hydroxyethyl acrylate, and 0.2 part of peroxidation were charged. Benzoquinone and 20 parts of acetic acid were subjected to polymerization treatment at 61 ° C for 6 hours in a nitrogen stream to obtain an acrylic polymer A. The acrylic polymer A had a weight average molecular weight Mw of 300,000, a glass transition temperature (Tg) of -16 ° C, an iodine value of 2, and a hydroxyl value (mgKOH/g) of 30.

(Preparation of acrylic polymer B)

In a reaction vessel having a condenser tube, a nitrogen gas introduction tube, a thermometer, and a stirring device, 80 parts of 2-ethylhexyl acrylate, 20 parts of 2-hydroxyethyl acrylate, and 65 parts of toluene were charged in a nitrogen stream at 61 The polymerization treatment was carried out for 6 hours at ° C to obtain an acrylic polymer B. The acrylic polymer B had a weight average molecular weight Mw of 800,000, a glass transition temperature (Tg) of -60 ° C, an iodine value of 6, and a hydroxyl value (mgKOH/g) of 30.

(Preparation of acrylic polymer C)

In a reaction vessel with a condenser, a nitrogen inlet, a thermometer and a stirring device, in 100 parts of butyl acrylate, 5 parts of acrylonitrile and 5 parts of C To 100 parts of the acrylic polymer having a number average molecular weight of about 300,000, which is composed of an olefinic acid, 5 parts of polyisocyanate, 15 parts of pentaerythritol triacrylate, and 1 part of α-hydroxycyclohexyl phenyl ketone are blended to obtain an acrylic polymer C. The acrylic polymer C had a weight average molecular weight Mw of 500,000, a glass transition temperature (Tg) of 10 ° C, an iodine value of 1, and a hydroxyl value (mgKOH/g) of 30. In addition, the measurement method of each evaluation item is as follows.

(Measurement of weight average molecular weight Mw)

The measurement of the weight average molecular weight Mw of the acrylic polymers A to C was carried out by GPC (gel permeation chromatography). The measurement conditions are as follows. Further, the weight average molecular weight is calculated based on polystyrene.

Measuring device: HLC-8120GPC (product name, manufactured by Tosoh Corporation)

Column: TSKgel GMH-H(S)×2 (product number, manufactured by Tosoh Corporation)

Flow rate: 0.5ml/min

Injection volume: 100μl

Column temperature: 40 ° C

Eluent: THF

Injection sample concentration: 0.1% by weight

Detector: Differential Refractometer

(Measurement of glass transition temperature (Tg))

The glass transition temperature (Tg) is determined by the Tg _{1-n of the} homopolymer of each monomer and the weight fraction W _{1-n of} each monomer, using 1/Tg=W ₁ /Tg ₁ +... ...+W _n /Tg _n measured value.

(Measurement of hydroxyl value)

The hydroxyl value of acrylic polymer A~C according to JIS K 0070-1992 (Ethyl acetate method) for evaluation. Namely, 10 ml of an acetamidine reagent was added to about 3 g of each acrylic polymer after drying, and 30 ml of pyridine as a solvent and 30 ml of dimethylformamide were added. This solution was heated in a water bath equipped with a condenser (95 to 100 ° C) for 1.5 hours. Further, 3 ml of water was added, followed by heating for 10 minutes.

Then, it was cooled to room temperature, the condenser was washed with 5 ml of ethanol, and the washing liquid was added to the above solution. A stir bar was placed in the solution, and titration was carried out using a potentiometric titration apparatus with a 0.5 mol/L potassium hydroxide solution while stirring with a magnetic stirrer. When 1 g of the sample was acetonitrile, the number of mg of potassium hydroxide required to neutralize the acetic acid bound to the hydroxyl group was taken as the hydroxyl value.

(Measurement of iodine value)

The acid value of the acrylic polymer A to C was evaluated in accordance with JIS K 0070-1992. That is, 30 ml of chloroform was added to about 3 g of each acrylic polymer after drying to dissolve it. 25 ml of Wijs solution was added thereto and stirred. Then, the lid was closed to be sealed, and left in the dark at 23 ° C for 1 hour. 20 ml of a potassium iodide solution and 100 ml of water were added to the solution, followed by stirring. The solution was titrated with a 0.1 mol/L sodium thiosulfate solution. When the solution turned yellowish, a few drops of the starch solution were added and titrated until the blue color disappeared. When a halogen is reacted with a 100 g sample, the amount of halogen to be converted is converted to the number of g of iodine, and the value obtained is an iodine value.

(Preparation of Adhesive Composition Solutions A~C)

To each of the polymers of the acrylic polymers A to C, 24.1 parts of 2-methylpropenyloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd., hereinafter also referred to as "MOI") was added, and it was carried out at 50 ° C in an air stream. Hourly addition reaction The acrylic polymer A'~C' was obtained by treatment.

Then, 3 parts of a polyisocyanate compound (trade name "Coronate L", manufactured by Nippon Polyurethane Co., Ltd.) and 3 parts of a photopolymerization initiator (trade name "Irgacure 651" were added to 100 parts of each of the acrylic polymers A' to C'. The product was dissolved in toluene to obtain a 20% by weight adhesive composition solution A to C.

(Preparation of dicing film A~C)

The obtained adhesive composition solutions A to C were applied to the prepared substrates, respectively, and dried to form an adhesive layer having a thickness of 30 μm, thereby obtaining cut films A to C.

(following the production of slice A)

The following (a) to (e) were dissolved in methyl ethyl ketone to obtain a solution of an adhesive composition having a concentration of 20% by weight.

Applying the adhesive composition solution to the release liner On a release-treated film comprising a polyethylene terephthalate film having a thickness of 50 μm after the release treatment of polyoxyalkylene, the film was dried at 130 ° C for 2 minutes to prepare a back sheet A having a thickness of 20 μm.

(following the production of slice B)

The following (a) to (e) were dissolved in methyl ethyl ketone to obtain a solution of an adhesive composition having a concentration of 20% by weight.

The adhesive composition solution was applied onto a release-treated film comprising a 50 μm thick polyethylene terephthalate film which was subjected to release treatment with polyoxyalkylene as a release liner, and was carried out at 130 After drying at ° C for 2 minutes, a back sheet B having a thickness of 20 μm was produced.

(Examples 1 to 4)

Each of the dicing films A to C and the succeeding sheets A to B was bonded at room temperature in the combination shown in Table 3, and the dicing/wafer bonding films of Examples 1 to 4 were produced.

(Measurement of storage elastic modulus of the adhesive layer)

Using the adhesive composition solutions A to C, an adhesive layer was formed on a release liner (manufactured by Mitsubishi Chemical Polyester Co., Ltd., MRF38, thickness: 38 μm), and the adhesive layer was prepared to have a layer thickness of 3 mm and a diameter of 8 mm Φ as a layer. Test sample. Then, using a viscoelasticity tester ARES manufactured by Rheometric Co., Ltd., a test piece was sandwiched with a parallel plate (for shear test) having a diameter of 7.9 mm to provide a shear strain at a frequency of 1 Hz at a temperature increase rate of 5 ° C / min. The storage elastic modulus (G': Pa) at 26 ° C was measured. The results are shown in Table 3.

(Evaluation of the rate of change of copper ion capture amount)

The sheets A and B were each cut into a weight of about 2.5 g, and the cut sample was placed in a cylindrical Teflon (registered trademark) container having a diameter of 58 mm and a height of 37 mm, and 10 ppm of Cu(II) ions were added thereto. 50 mL of aqueous solution. Then, it was allowed to stand at 120 ° C for 20 hours in a constant temperature dryer (PV-231, manufactured by Espec Co., Ltd.). After the film was taken out, the copper (II) ion concentration in the aqueous solution was measured using ICP-AES (SPS-1700HVR, manufactured by SII NanoTechnology Co., Ltd.). Thus, the copper ion capture amount X (initial copper ion concentration: 10 ppm - copper ion concentration ppm after the test) of the succeeding sheets A and B before the dicing film was adhered was determined.

Further, after preparing the dicing/wafer bonding films of Examples 1 to 4, they were allowed to stand at room temperature for 30 days. Then, the dicing/wafer bonding film was subjected to ultraviolet irradiation (400 mJ/cm ² ), and the adhesive sheets A' and B' were peeled off from the dicing film. These back sheets A' and B' were used as samples, and the copper ion concentration was measured in the same manner as the above procedure. Thus, each copper ion capturing amount Y (initial copper ion concentration: 10 ppm - copper ion concentration ppm after the test) of the succeeding sheets A' and B' after the adhesion treatment of the dicing film was determined.

From the following formula, the rate of change (%) of the amount of copper ion trapped before and after the film was adhered to the cut film.

{(copper ion capture amount X-copper ion capture amount Y) / copper ion capture amount X}×100 (%)

When the rate of change in the amount of captured copper ions was 5% or less, it was evaluated as ○, and when it was more than 5%, it was evaluated as ×. The results are shown in Table 3.

As can be seen from the results of Table 3, the storage elastic modulus of each of the dicing/wafer bonding films of Examples 1 to 4 was in the range of 1.0 × 10 ⁴ Pa or more and 1.0 × 10 ⁷ Pa or less. Therefore, it is possible to suppress the transfer of the ion scavenger from the adhesive sheet to the adhesive layer of the dicing film, and the ion trapping property of the adhesive sheet can be appropriately exhibited even after being adhered to the dicing film.

1‧‧‧Substrate

2‧‧‧Adhesive layer

2a, 2b, 3b‧‧‧

3‧‧‧Next film, wafer bonding film, film-like adhesive

3’‧‧‧Next film

3a‧‧‧Semiconductor wafer bonding part

4‧‧‧Semiconductor wafer

5, 15‧‧‧ semiconductor wafer

6‧‧‧Adhesive

7‧‧‧welding line

8‧‧‧ Sealing resin

10, 11‧‧‧ cutting/wafer bonding film

13‧‧‧ wafer bonding film

1 is a schematic cross-sectional view showing a dicing/wafer bonding film according to an embodiment of the present invention.

2 is a schematic cross-sectional view showing an example in which a semiconductor wafer is mounted via a wafer bonding film in the dicing/wafer bonding film.

3 is a schematic cross-sectional view showing an example in which a semiconductor wafer is three-dimensionally mounted via a wafer bonding film in the dicing/wafer bonding film.

4 is a schematic cross-sectional view showing a dicing/wafer bonding film according to another embodiment of the present invention.

1‧‧‧Substrate

2‧‧‧Adhesive layer

2a, 2b, 3b‧‧‧

3‧‧‧Next film (wafer bonding film)

3a‧‧‧Semiconductor wafer bonding part

4‧‧‧Semiconductor wafer

10‧‧‧Cutting/wafer bonding film

Claims (5)

An adhesive sheet for manufacturing a semiconductor device, comprising: a thermoplastic resin having a carboxyl group and having no epoxy group; a thermosetting resin; and a complex forming organic compound, said complex formation property The organic compound includes a benzene ring having two or more phenolic hydroxyl groups, and is capable of forming a complex with a cation. The adhesive sheet for manufacturing a semiconductor device according to claim 1, wherein the thermoplastic resin is included in an amount of 5 to 95 parts by weight based on 100 parts by weight of the total of the sheet for manufacturing the semiconductor device. 50 parts by weight of the thermosetting resin, 0 to 60 parts by weight of the filler, and 0.1 to 5 parts by weight of the complex-forming organic compound. The adhesive sheet for manufacturing a semiconductor device according to claim 1 or 2, wherein a weight of 2.5 g of the adhesive sheet for manufacturing the semiconductor device is immersed in a 50 ml aqueous solution containing 10 ppm of copper ions at 120 After standing at ° C for 20 hours, the concentration of copper ions in the aqueous solution was 0 to 9.9 ppm. A semiconductor device comprising the adhesive sheet for manufacturing a semiconductor device according to any one of claims 1 to 3. A method of manufacturing a semiconductor device, comprising: transducing a semiconductor according to any one of claims 1 to 3 The adhesive sheet for manufacturing the body device adheres the semiconductor wafer to the adherend.