TWI614322B - Adhesive sheet and use thereof - Google Patents

Abstract

The present invention provides a bonding sheet for manufacturing a semiconductor device that is chemically stable while suppressing cracks or defects in a semiconductor wafer and the like, and is easy to control physical properties. An adhesive sheet for manufacturing a semiconductor device includes: a thermoplastic resin having an epoxy group and no carboxyl group; a thermosetting resin; and a complex-forming organic compound, the complex-forming organic compound including A tertiary nitrogen atom is a heterocyclic compound that is a ring atom and can form a complex with a cation.

Description

Adhesive film and its use

The present invention relates to adhesive sheets and uses thereof.

In recent years, a stacked MCP (Multi Chip Package) obtained by stacking a plurality of memory package chips (Memory Package Chips) for mobile phones and portable audio devices has become widespread. In addition, with the multi-functionalization of image processing technology and mobile phones, the high-density, high-integration and thinness of packages are being promoted. As a method for fixing a semiconductor wafer to a substrate or the like, a method using a thermosetting paste resin and a method using a bonding sheet using a combination of a thermoplastic and a thermosetting resin have been proposed.

On the other hand, in the semiconductor manufacturing process, cations (for example, copper ions and iron ions) are mixed into the crystal substrate of the wafer from the outside. When the cations reach the circuit formation surface formed on the wafer, electrical characteristics are present. decline. In addition, there is a problem in that cations are generated from a circuit or a metal wire during use of a product, thereby reducing electrical characteristics.

In response to the above problems, an external gettering method (hereinafter also referred to as "EG") that attempts to form a crushed layer (strain) by processing the back surface of the wafer, and captures and removes cations through the crushed layer, or Intrinsic Gettering (hereinafter also referred to as "IG") is a method of forming oxygen-induced defects (acid precipitation defects) in a crystal substrate of a wafer, and capturing and removing cations through the oxygen-induced defects.

However, with the thinning of wafers in recent years, the effect of IG is reduced, and the back strain that causes cracking or warping of the wafer is also removed, so the effect of EG It cannot be obtained, so there is a problem that the removal effect is insufficient.

Therefore, various schemes for supplementing the effect of removing defects have been proposed. Patent Document 1 describes a thin film adhesive having a copper ion adsorption layer including a resin having a skeleton capable of forming a complex with copper ions. In addition, it is described that copper ions can be chemically adsorbed into the resin of the copper ion adsorption layer, and the influence of copper ions generated from a member made of copper as a material can be significantly reduced compared with the past. In addition, Patent Documents 2 and 3 describe an adhesive adhesive composition including an ion trapping agent, and disclose that the ion trapping agent has an effect of capturing chloride ions and the like. In addition, Patent Document 4 describes a film-shaped adhesive including an ion trapping agent, and describes that the ion trapping agent traps a halogen element. In addition, Patent Document 5 describes an adhesive sheet including an anion exchanger. In addition, Patent Document 6 describes a sheet-shaped adhesive including a chelate-modified epoxy resin that can trap ionic impurities inside.

Prior art literature Patent literature

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

Patent Document 2: Japanese Patent Application Laid-Open No. 2009-203337

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

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

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

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

However, even if the above-mentioned supplementary technology of the defect removal effect is used, the following problems arise.

The first problem is that there is no disclosure of a technique for capturing cations through a film-like adhesive or the like of Patent Documents 2 to 5. Therefore, it is difficult to prevent degradation of the electrical characteristics based on cations by simply capturing chloride ions. The ion trapping agents, ion trapping agents, and anion exchangers disclosed in Patent Documents 2 to 5 are inorganic compounds. For this reason, there are problems in that the catchability varies due to the dispersion state in a resin such as a thin film adhesive, or when the inorganic compound comes into contact with the wafer when adhered to the wafer, the wafer is cracked or defective. In particular, in recent years, there has been a demand for thinning of the bonding sheet. Therefore, it is necessary to suppress cracks or defects of the wafer caused by the inorganic compound.

In addition, the film-shaped adhesive of Patent Document 1 or the sheet-shaped adhesive of Patent Document 6 can capture copper ions. In addition, since the resin has a skeleton capable of forming a complex with copper ions, it is difficult to cause the problem that the inorganic compound comes into contact with the wafer and the wafer is cracked or defective. However, the skeleton of the resin capable of forming a complex with copper ions may react with other resins constituting a film-like adhesive. Therefore, there are problems in that the chemical stability of the film-shaped adhesive agent or the like is reduced, or the physical properties of the film-shaped adhesive agent or the like are difficult to control, so that desired characteristics cannot be obtained.

Therefore, there is a need for a bonding pad for manufacturing a semiconductor device that has chemical stability and is easy to control physical properties while suppressing cracks or defects in a semiconductor wafer or the like, a semiconductor device having the bonding pad for manufacturing the semiconductor device, and a semiconductor device using the same. Method for manufacturing a semiconductor device with a wafer for device manufacture.

The second problem is that, for example, even if the adhesive sheet contains a component that adsorbs metal ions, after the adhesive sheet is peeled from the semiconductor wafer, as long as it is a peeled area, the supplementary effect of the defect removal effect is reduced. With the recent years of semiconductor devices For high-capacity packages, if multi-layer stacking of thin semiconductor wafers and adhesive wafers is required for packages with the same specifications, as the stacking progresses, thermal history due to heat treatment is accumulated in the subsequent wafers. As a result, the bonding characteristics of the bonding sheet are degraded, and the bonding sheet may be peeled from the semiconductor wafer when the sealing process or the reflow process is performed, so that the replenishing effect of the defect removing effect may be weakened. Such a peeling phenomenon cannot be solved by the above-mentioned prior art.

Therefore, there is a demand for a bonding sheet that does not cause peeling from a semiconductor wafer even if high-temperature treatment is performed, and can capture metal ions mixed into the semiconductor wafer during the manufacturing process of the semiconductor device, thereby preventing degradation of the electrical characteristics of the semiconductor device.

The third problem is that a thermoplastic resin is added to the conventional adhesive sheet to improve the adhesion in a low temperature range. However, since the thermoplastic resin itself has a low glass transition temperature (Tg), the elastic modulus of the subsequent sheet may decrease at high temperatures, the semiconductor wafer may be displaced during wire bonding after wafer bonding, or it may be used for mounting semiconductor wafers. Peeling occurred during the reflow process. Therefore, measures have been taken to increase the elastic modulus at high temperatures by adding a filler such as silicon dioxide to the adhesive sheet.

However, when a filler is used, a wafer may be damaged due to contact between the semiconductor wafer and the filler, or cracks may occur depending on the situation. In order to increase the capacity of the semiconductor device described above, not only the wafer thickness needs to be reduced, but also the thickness of the wafer used for fixing the semiconductor wafer must be reduced. The frequency will increase. In addition, with the recent reduction in thickness, the strength of the semiconductor wafer itself is also decreasing. Therefore, the occurrence of defects or cracks in the semiconductor wafer tends to become apparent. In addition, since any of the above-mentioned prior arts uses an inorganic filler, this problem cannot be solved. question.

Therefore, there is a demand for a bonding sheet that can prevent the deterioration of the electrical characteristics of the manufactured semiconductor device and improve the reliability of the product, and can prevent mechanical damage to the wafer or semiconductor wafer even if the thickness is reduced.

The fourth problem is that, in the film-shaped adhesive of Patent Document 1, a resin is used as an ion trapping agent, and therefore the ion trapping performance is insufficient. In addition, in Patent Documents 2 to 5, the use of organic low molecular weight compounds capable of forming complexes with metal ions is not studied at all.

The conventional adhesive sheet has the aforementioned problems. In addition, the chemical stability, chemical reactivity, and physical properties of the adhesive sheet are changed due to the ion trapping agent of the complexing agent, and the adhesion to the adherend such as the substrate is reduced. There is still room for improvement.

Therefore, a multilayer adhesive sheet for manufacturing a semiconductor device having high ion trapping properties and high adhesion to an adherend is required.

The fifth problem is that, in the manufacture of a conventional semiconductor device, a semiconductor wafer having a circuit pattern formed thereon is adjusted in thickness by back surface grinding (back surface grinding process), and then cut into semiconductor wafers (cutting process), The semiconductor wafer is fixed to an adherend such as a lead frame with an adhesive (wafer bonding step), and then a wire bonding step is performed.

In order to effectively fix a semiconductor wafer to a lead frame or the like, a dicing / wafer bonding film for holding a semiconductor wafer in a dicing process and also providing an adhesive layer for wafer fixing required for a pick-up process has been proposed. This dicing / wafer bonding film is provided with an adhesive layer on the dicing film in a peelable manner, a semiconductor wafer is cut with the adhesive layer held, and then the dicing film is stretched to form a film. The wafer is peeled off together with the adhesive layer, and each of them is recovered and fixed to an adherend such as a lead frame through the adhesive layer.

However, when a bonding sheet having an ion-trapping property is used as a dicing / wafer bonding film in combination with a dicing film, it is found that the ion-trapping property of the bonding sheet may be reduced.

Therefore, even if an ion-trapping adhesive sheet is used, it is sought to prevent dicing of the adhesive sheet from deteriorating, and to trap metal ions mixed into the semiconductor wafer during the manufacturing process of the semiconductor device, thereby preventing degradation of the electrical characteristics of the semiconductor device. / Wafer bonding film.

The inventors of the present application conducted extensive and intensive studies, and as a result, found that the above-mentioned 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 an epoxy group and no carboxyl group; a thermosetting resin; and a complex-forming organic compound. The compound-forming organic compound includes a heterocyclic compound containing a tertiary nitrogen atom as a ring atom, and is capable of forming a complex with a cation.

According to the configuration described above, since the complex-forming organic compound capable of forming a complex with a cation is included, cations which are externally mixed in various steps of manufacturing a semiconductor device can be captured. As a result, it is difficult for cations mixed in from the outside to reach the circuit formation surface formed on the wafer, and it is possible to suppress the decrease in electrical characteristics, thereby improving product reliability. In addition, since it is a complex-forming organic compound, even if it comes into contact with a semiconductor wafer or the like at the time of bonding, it is possible to suppress the occurrence of cracks or defects on the wafer.

In addition, when a semiconductor wafer is adhered to an adherend via an adhesive sheet, generally there are irregularities in the adherend, and therefore, air bubbles are mixed. These bubbles are generally diffused into the sealing resin or the like by pressure or the like when the resin is sealed, so that its influence is weakened. However, when a heterocyclic compound containing a tertiary nitrogen atom as a ring atom is used as a complex-forming organic compound, when a carboxyl group is present in the thermoplastic resin, the thermal history in a process such as wire bonding before sealing the resin, Since a curing reaction proceeds violently, bubbles cannot be diffused into the sealing resin during the resin sealing step. As a result, peeling caused by bubbles occurs at the adjoining interface. In particular, when semiconductor wafers are stacked in multiple layers, the thermal history increases and the effect of bubbles on peeling is significant. According to the present invention, the thermoplastic resin does not have a carboxyl group, and thus can suppress a reaction with a heterocyclic compound including a tertiary nitrogen atom as a ring atom. Therefore, the chemical stability of the adhesive sheet can be improved. In addition, since the reaction with a heterocyclic compound including a tertiary nitrogen atom as a ring atom is suppressed, it is possible to suppress a rapid curing reaction before the molding step, and it is possible to diffuse bubbles at the interface to the sealing resin or the like. Thereby, peeling at the interface can be prevented.

Moreover, according to the said structure, since a thermoplastic resin has an epoxy group, for example, a thermoplastic resin is bridge | crosslinked to some extent by the post-cure process after resin sealing, and peeling at an interface can be prevented.

That is, according to the foregoing configuration, it includes: a thermoplastic resin having an epoxy group and no carboxyl group; a thermosetting resin; and a complex-forming organic compound including a tertiary nitrogen-containing compound Since the atom is a heterocyclic compound of a ring atom and can form a complex with a cation, the reliability of a semiconductor device manufactured by using the adhesive sheet for manufacturing a semiconductor device can be improved.

In the foregoing configuration, it is preferable that the thermoplastic resin includes 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 filler, and 0.1 to 5 parts by weight of the complex-forming organic compound. By setting the respective components within the numerical range, cracks or defects in semiconductor wafers and the like can be further suppressed, chemical stability can be further improved, and physical properties can be controlled more easily.

In the foregoing configuration, it is preferable that a 2.5 g weight adhesive sheet for manufacturing a semiconductor device is immersed in a 50 ml aqueous solution including 10 ppm copper ions and left at 120 ° C. for 20 hours. The copper ion concentration in the aqueous solution is 0 to 9.9 ppm. . According to the aforementioned configuration, it is possible to further capture copper ions mixed in from outside in various processes of manufacturing a semiconductor device. As a result, it is more difficult for copper ions mixed in from the outside to reach the circuit formation surface formed on the wafer.

The semiconductor device of the present invention includes a bonding sheet for manufacturing a semiconductor device described above. According to the said structure, since the adhesive sheet for semiconductor device manufacture mentioned above is provided, a semiconductor device with improved product reliability can be obtained.

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

In the present invention, as an embodiment, an adhesive sheet is also included, which is composed of an adhesive composition including an ion trapping agent, and has a tensile storage elastic modulus of 0.5 at 260 ° C after being cured at 175 ° C for 5 hours. Above MPa and Below 1000MPa.

The adhesive sheet has a tensile storage elastic modulus at 260 ° C. (hereinafter sometimes referred to simply as “elastic modulus” in this embodiment) after being thermally cured under predetermined conditions, and thus can be 0.5 MPa or more and 1000 MPa or less. Maintaining the elastic modulus at a high temperature (for example, 175 to 260 ° C) can prevent the adhesive sheet from being peeled from the semiconductor wafer during the sealing process or the reflow process. In addition, it is possible to prevent peeling of the adhesive sheet and maintain the adhesion state between the adhesive sheet and the semiconductor wafer. Therefore, it is possible to prevent a reduction in capture efficiency of metal ions mixed into the semiconductor wafer or having a possibility of mixing, and to prevent electrical characteristics of the obtained semiconductor device Degradation. The method for measuring the tensile storage elastic modulus of the adhesive sheet is based on the description in the examples.

The adhesive composition constituting the adhesive sheet preferably further includes a thermoplastic resin and a thermosetting resin. By using two components, the elastic modulus of the adhesive sheet can be appropriately set to a predetermined range.

The thermoplastic resin preferably includes an acrylic resin having a weight average molecular weight of 100,000 or more. Accordingly, the cohesive force can be sufficiently exerted through the acrylic resin, the adhesive force at a low temperature (for example, 60 ° C.) can be obtained, and the decrease in the elastic modulus at a high temperature can be prevented.

In this adhesive sheet, the acrylic resin preferably includes an epoxy group or a carboxyl group. By using an acrylic resin including an epoxy group or an acrylic resin including a carboxyl group, a crosslinking reaction with a thermosetting resin can be performed, and an elastic modulus at a high temperature can be secured.

In this adhesive sheet, the content on a weight basis of the thermoplastic resin in the adhesive composition is preferably 0.5 to 20 times the content on a weight basis of the thermosetting resin. The ratio of the content of the thermoplastic resin to the content of the thermosetting resin When set to such a range, the adhesiveness at low temperature and the elastic modulus at high temperature can be effectively achieved simultaneously.

With regard to the adhesive sheet, it is preferable that a 2.5 g adhesive sheet is immersed in a 50 ml aqueous solution including 10 ppm copper ions and left at 120 ° C. for 20 hours, and the copper ion concentration in the aqueous solution is 0 to 9.9 ppm. The adhesive sheet has such a copper ion trapping property, and can trap metal ions mixed in a semiconductor wafer or the like during the manufacturing process of the semiconductor device. As a result, it is difficult for metal ions mixed in from the outside to reach the circuit formation surface formed on the wafer, it is possible to suppress a decrease in electrical characteristics, and to improve product reliability.

The present invention also includes a dicing / wafer bonding film including: a dicing film having a substrate and an adhesive layer formed on the substrate; and the adhesive film laminated on the adhesive layer.

Thus, this adhesive sheet can be used suitably as a wafer bonding film which comprises a dicing / wafer bonding film.

The present invention also includes a method for manufacturing a semiconductor device, which includes: a step of adhering the bonding sheet of the dicing / wafer bonding film to a semiconductor wafer; a step of cutting the semiconductor wafer to form a semiconductor wafer; and the semiconductor wafer. A step of picking up with the adhesive sheet; a step of fixing the picked-up semiconductor wafer to an adherend via the adhesive sheet; a step of electrically connecting the semiconductor wafer and the adherend via a bonding wire; And a step of sealing the semiconductor wafer via a sealing resin.

By manufacturing the semiconductor device through the dicing / wafer bonding film using the bonding sheet as the wafer bonding film, the bonding sheet can be prevented from being peeled from the semiconductor wafer in the sealing process or the reflow process, so that the finished product of the semiconductor device can be improved. It can efficiently capture metal ions that can be mixed into a semiconductor wafer, thereby manufacturing a semiconductor device with excellent electrical characteristics.

The present invention also includes another embodiment, which is an adhesive sheet including the following components (a) to (c) and composed of only an organic component.

(a) an acrylic resin having a weight average molecular weight of 800,000 or more; (b) at least one of an epoxy resin and a phenol resin; (c) a complexing agent capable of forming a complex with a metal ion.

This adhesive sheet is composed only of organic components. In other words, it does not contain fillers composed of inorganic components such as silicon dioxide, and therefore prevents semiconductor wafers or wafers (hereinafter sometimes referred to as "semiconductor wafers") caused by contact with the fillers. Etc. "). In addition, by using the component (a) and the component (b), it is possible to prevent the glass transition temperature from being lowered. Therefore, even without a filler, the elastic modulus of the adhesive sheet at high temperature can be maintained. As a result, sufficient shear can be obtained at high temperature. Because of the cutting force, the wire bonding process can be performed well, and peeling between the adhesive sheet and the adherend during the reflow process can be suppressed. In addition, since the adhesive sheet includes the component (c), metal ions such as a semiconductor wafer mixed in the manufacturing process of the semiconductor device can be efficiently captured, and a semiconductor device having high product reliability can be manufactured. In addition, the term “consisting of only an organic component” means that an inorganic component is not actively used as a constituent component of the adhesive sheet, and the case where an inorganic component as an impurity is inevitably included in each constituent component is included in the scope of the present invention.

With regard to the adhesive sheet, it is preferable that a 2.5 g adhesive sheet is immersed in a 50 ml aqueous solution including 10 ppm copper ions and left at 120 ° C. for 20 hours, and the copper ion concentration in the aqueous solution is 0 to 9.9 ppm. The adhesive sheet has such a copper ion trapping property, and can be mixed into a semiconductor device during the manufacturing process. Metal ions such as conductor wafers. As a result, it is difficult for metal ions mixed in from the outside to reach the circuit formation surface formed on the wafer, it is possible to suppress a decrease in electrical characteristics, and to improve product reliability.

The tensile storage elastic modulus of the adhesive sheet at 175 ° C after thermal curing at 175 ° C for 1 hour is preferably 0.1 MPa or more and 1000 MPa or less. Thereby, the tensile storage elastic modulus at a high temperature can be secured, and the wire bonding process or the reflow process can be performed favorably.

In this adhesive sheet, it is preferred that the (a) component and the (b) component can be crosslinked with each other. By cross-linking the component (a) and the component (b), the adhesion force at a high temperature (for example, 175 to 260 ° C) is further improved, and peeling and the like in a reflow process can be prevented. As a result, the yield of semiconductor device manufacturing can be improved .

In order to crosslink the (a) component and the (b) component, when the (a) component specifically has an epoxy group, a crosslinking reaction with the (b) component may be appropriately performed.

In this adhesive sheet, the component (c) is preferably at least one of a heterocyclic compound having a tertiary nitrogen atom and a compound having two or more hydroxyl groups on one aromatic ring. By using such an organic complexing agent, the affinity with the resin component which comprises a bonding sheet improves, it can exist in a balance in a bonding sheet, and metal ions can be efficiently captured. In addition, by using a complexing agent having the above-mentioned specific structure, the complex-forming ability can be improved, and metal ions can be captured more effectively.

Since this adhesive sheet is composed of only organic components, the thickness of the adhesive sheet can be reduced to 3 to 20 μm in order to cope with higher capacity of the semiconductor device.

The adhesive sheet preferably contains no filler component. Therefore, mechanical damage to the semiconductor wafer or the like by the filler component can be avoided, and a bonding wafer or a semiconductor wafer can be realized. As a result, the thickness and thickness of the semiconductor device can be increased. The filler may be composed of an organic component and an inorganic component. It is preferred that the adhesive sheet does not include any type of filler.

The present invention also includes a semiconductor device including: an adherend; the adhesive sheet laminated on the adherend; and a semiconductor wafer disposed on the adhesive sheet.

The semiconductor device can be efficiently manufactured by a method for manufacturing a semiconductor device including a step of fixing a semiconductor wafer to an adherend via the adhesive sheet.

The present invention also includes a multilayer adhesive sheet for a semiconductor device according to another embodiment, which includes an ion-trapping layer made of an ion-trapping composition including an organic low-molecular-weight compound capable of forming a complex with a metal ion. Forming; and an adhesive layer formed from the adhesive composition.

The multilayer adhesive sheet includes an ion-trapping layer including an organic low-molecular-weight compound capable of forming a complex with metal ions, and thus can capture a crystalline substrate that can be externally mixed into a wafer in various steps in the manufacture of a semiconductor device. And other metal ions. As a result, it is difficult for metal ions mixed in from the outside to reach the circuit formation surface formed on the wafer, and it is possible to suppress a reduction in electrical characteristics of the manufactured semiconductor device, thereby improving product reliability. In addition, the multilayer adhesive sheet of the present invention has an adhesive layer in addition to the ion-trapping layer, and therefore has excellent adhesion to an adherend such as a substrate.

The organic low molecular weight compound is preferably one or more compounds selected from the group consisting of a nitrogen-containing heterocyclic compound and a compound having two or more hydroxyl groups on one aromatic ring.

The ion-trapping composition and the adhesive composition preferably include an epoxy resin Based thermoplastic resin.

The film thicknesses of the ion-trapping layer and the adhesive layer are each preferably 5 to 100 μm.

The organic low molecular weight compound is preferably 0.1 to 10 parts by weight based on 100 parts by weight of all the components in the ion trapping layer.

The ion-trapping composition includes a thermoplastic resin, a thermosetting resin, and a silica filler. The thermoplastic resin, the thermosetting resin, and the silica filler are 100 parts by weight in total, and the thermoplastic resin is preferably 10 to 99 parts by weight and the thermosetting resin is 1 ~ 30 parts by weight and silica filler is 0 ~ 60 parts by weight.

The present invention also relates to a semiconductor device obtained by laminating a wafer onto an adherend via the multilayer adhesive sheet, and a method for manufacturing a semiconductor device including a step of laminating a wafer onto an adherend via the multilayer adhesive sheet.

The present inventors have conducted extensive and intensive studies in particular to solve the above-mentioned fifth problem, and as a result, have obtained the following findings. That is, after an ion-trapping adhesive sheet and an adhesive layer of a dicing film are laminated to obtain a dicing / wafer bonding film, there is a considerable storage period until it is applied to the manufacture of a semiconductor device. At this time, since the ion-trapping component from the adhesive sheet is transferred or transferred to the adhesive layer, or a chemical reaction between the ion-trapping component and the constituent material of the adhesive layer occurs (hereinafter, these phenomena are referred to as "transfer etc."), As a result, the amount of the ion-trapping component in the adhesive sheet is reduced or the ion-trapping component itself is deteriorated. As a result, the ion-trapping property of the adhesive sheet is reduced. As described above, when the thickness of the adhesive sheet is reduced in order to increase the capacity of the semiconductor device, the absolute amount of the ion-trapping component in the adhesive sheet is reduced, so that the ion-trapping property of the adhesive sheet is further reduced.

Based on the above findings, the present inventors focused on preventing ions in the adhesive film. The structure of the adhesive layer, such as the transfer of the capture agent, was found to reduce the free volume in the adhesive layer by forming a moderate cross-linked structure in the adhesive layer, thereby restricting the ion trapping agent from the adhesive sheet to the adhesive layer. The above-mentioned problem can be solved by the free movement, and the present invention has been completed.

That is, the present invention also includes a dicing / wafer bonding film including: a dicing film having a base material and an adhesive layer laminated on the base material; and an adhesive sheet laminated on the adhesive layer, The adhesive sheet includes 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 or less.

In this dicing / wafer bonding film, since the adhesive layer has a storage elastic modulus of 1.0 × 10 ⁴ Pa or more and 1.0 × 10 ⁷ Pa or less, a moderately crosslinked structure is formed in the adhesive layer. This can restrict the transfer of the ion trapping agent from the adhesive sheet to the adhesive layer, etc. As a result, it is possible to suppress a decrease in the ion trapping property of the adhesive sheet. In addition, since the adhesive sheet includes an ion trapping agent (hereinafter sometimes referred to as an “ion trapping agent”) capable of capturing metal ions, the metal ions mixed into the semiconductor wafer during the semiconductor manufacturing process can be effectively captured, and the obtained semiconductor device can be prevented. Degradation of electrical characteristics. In addition, since the transfer of the ion trapping agent from the adhesive sheet to the adhesive layer can be restricted and the ion trapping property of the adhesive sheet can be maintained, it is also possible to cope with further thinning of the adhesive sheet accompanying the increase in the capacity of the semiconductor device.

According to this dicing / wafer bonding film, the ion trapping agent is an organic compound capable of forming a complex with metal ions, and can suppress ions appropriately even when it has affinity with the constituent material of the adhesive layer. Capture agent transfer, etc.

With regard to the dicing / wafer bonding film, a 2.5 g sample taken from the adhesive was immersed in a 50 ml aqueous solution including 10 ppm copper ions and left at 120 ° C for 20 hours. The copper ion concentration in the aqueous solution was 0. ~ 9.8ppm. The adhesive sheet has such a copper ion trapping property, and can trap metal ions mixed into a semiconductor wafer or the like in a semiconductor manufacturing process. As a result, it is difficult for metal ions mixed in from the outside to reach the circuit formation surface formed on the wafer, it is possible to suppress a decrease in electrical characteristics, and to improve product reliability.

In this dicing / wafer bonding film, the adhesive layer preferably includes an acrylic resin having a weight average molecular weight of 300,000 or more. The acrylic resin preferably contains a hydroxyl-containing acrylic monomer as a constituent monomer. In addition, the adhesive layer preferably includes an isocyanate-based crosslinking agent, and includes 1 to 5 parts by weight of an isocyanate-based crosslinking agent with respect to 100 parts by weight of the acrylic resin. By using such a structure alone or in combination, a crosslinked structure capable of restricting the transfer of an ion trapping agent and the like can be appropriately formed in the adhesive layer.

In the dicing / wafer bonding film, the adhesive layer may be a radiation-curable type. At this time, before the radiation of the adhesive layer, the storage elastic modulus at 26 ° C. 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 the ion trapping property of the adhesive sheet from being deteriorated. Therefore, the thickness of the adhesive sheet can be reduced to 3 μm or more and 150 μm or less.

<First Embodiment>

The adhesive sheet for manufacturing a semiconductor device according to the first embodiment of the present invention (hereinafter also simply referred to as “adhesive sheet”) includes a thermoplastic resin, and the thermoplastic resin Has an epoxy group and does not have a carboxyl group; a thermosetting resin; and a complex-forming organic compound including a heterocyclic compound containing a tertiary nitrogen atom as a ring atom, and capable of forming a complex with a cation组合。 The compound.

The adhesive sheet includes a complex-forming organic compound capable of forming a complex with a cation, and thus can capture cations mixed in from outside in various steps in the manufacture of a semiconductor device. As a result, it is difficult for cations mixed in from the outside to reach the circuit formation surface formed on the wafer, it is possible to suppress a decrease in electrical characteristics, and to improve product reliability. In addition, since it is a complex-forming organic compound, even if it comes into contact with a semiconductor wafer or the like at the time of bonding, cracks or defects can be suppressed.

In addition, since the thermoplastic resin does not have a carboxyl group, the reaction with a heterocyclic compound including a tertiary nitrogen atom as a ring atom can be suppressed. Therefore, the chemical stability of the adhesive sheet can be improved. In addition, since the reaction with a heterocyclic compound including a tertiary nitrogen atom as a ring atom is suppressed, it is possible to suppress the curing reaction from violently proceeding before the molding step, and it is possible to diffuse bubbles at the interface to the sealing resin or the like. Thereby, peeling at the interface can be prevented.

In addition, since the thermoplastic resin has an epoxy group, the thermoplastic resin undergoes a certain degree of cross-linking, for example, through a post-curing step after the resin sealing, so that peeling at the interface can be prevented.

That is, the adhesive sheet includes: a thermoplastic resin having an epoxy group and no carboxyl group; a thermosetting resin; and a complex-forming organic compound, the complex-forming organic compound including As a heterocyclic compound having a ring nitrogen atom and a complex with a cation can be formed, it is possible to improve the reliability of a semiconductor device manufactured using the bonding sheet for manufacturing the semiconductor device.

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 a resin. In addition, in the present embodiment, the term “the complex-forming organic compound is soluble in an organic solvent” means that, for example, 1 part by weight of the complex-forming organic compound is not suspended in 100 parts by weight of methyl ethyl ketone as an organic solvent. Can dissolve.

In this embodiment, the cation forming the 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, Ca, Ba, Sr, Fe, Al, Ti, Zn, Mo, Mn, V and other ions.

(Complex-forming organic compound)

The complex-forming organic compound is not particularly limited as long as it is a heterocyclic compound containing a tertiary nitrogen atom as a ring atom, and a complex capable of forming a complex with a cation. The cation can be appropriately captured and inhibited from reacting with all compounds. From the viewpoint of the reaction of the epoxy group in the thermoplastic resin, a triazole compound, a tetrazole compound, or a bipyridine compound can be mentioned. Among these, a triazole compound is more preferable from the viewpoint of the stability of a complex formed with copper ions. These compounds may be used alone or in combination of two or more. As the complex-forming organic compound, a fine powdery, easily soluble organic solvent, or a liquid organic compound is preferred.

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'-methyl Phenyl} -5-chlorobenzotriazole, 2- {2'-hydroxy-3 ', 5'-di-tert-pentylphenyl} benzotriazole, 2- {2'-hydroxy-5'-tert Octylphenyl} benzotriazole, 6- (2-benzotriazolyl) -4-tert-octyl-6'-tert-butyl-4'-methyl-2,2'-methylenebis Phenol, 1- (2 ', 3'-hydroxypropyl) benzotriazole, 1- (1', 2'-dicarboxydiethyl) benzotriazole, 1- (2-ethylhexylcarbamate Phenyl) benzotriazole, 2,4-di-tert-amyl-6-{(H-benzotriazol-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-yl) phenyl] propionate, 2-ethylhexyl-3- [3-tert-butyl-4- Hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate, 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-pentylphenyl} benzotriazole, 2- {2'-hydroxy-3', 5'-di-tert-butylphenyl} -5-chloro Benzotriazole, 2- [2'-hydroxy-3,5-bis (1,1-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2'-methylenebis [ 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 so on.

The commercially available product of the triazole compound is not particularly limited, and examples thereof include: trade names manufactured by Chengbei Chemical Co., Ltd .: BT-120, BT-LX, CBT-1, JF-77, JF-78, JF- 79, JF-80, JF83, JAST-500, BT-GL, BT-M, BT-260, BT-365, TT-LX; Trade names manufactured by BASF: TINUVIN PS, TINUVIN P, TINUVIN P FL, 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 Yongguang Chemical Company's trade names: EVERSORB 81, EVERSORB 70, EVERSORB 71, EVERSORB 72, EVERSORB 73, EVERSORB 74, EVERSORB 75, EVERSORB 76, EVERSORB 78, EVERSORB 80, and so on. Triazole compounds can also be used as rust inhibitors.

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

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

The adhesive sheet includes a thermoplastic resin having an epoxy group and no carboxyl 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 urethane resin, a polysiloxane resin, or a thermosetting polyimide resin. These resins can be used singly or in combination of two or more kinds. In particular, at least one of an epoxy resin and a phenol resin is preferably used. 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, an adhesive sheet having high adhesive force at high temperature can be obtained.

The epoxy resin is not particularly limited as long as it is an epoxy resin generally used as an adhesive composition, and examples thereof include bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, and the like. Hydrogenated bisphenol A type, bisphenol AF type, biphenyl type, naphthalene type, fluorene type, phenol novolac type, o-cresol novolac type, Bifunctional epoxy resins or polyfunctional epoxy resins such as tris (hydroxyphenyl) methane type and tetras (hydroxyphenyl) ethane type, or hydantoin type, isocyanuric acid triglycidyl type, or glycidol Amine type and other epoxy resins. These epoxy resins can be used alone or in combination of two or more. Among these epoxy resins, novolac-type epoxy resins, biphenyl-type epoxy resins, tris (hydroxyphenyl) methane-type epoxy resins, or tetras (hydroxyphenyl) ethane-type epoxy resins are particularly preferred. 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.

The phenol resin functions as a curing agent for the epoxy resin, and examples thereof include phenol novolac resin, phenol aralkyl resin, cresol novolac resin, tert-butylphenol novolac resin, and nonylphenol. Novolac-type phenolic resins such as novolac resins, resol-type phenolic resins, polyhydroxystyrenes such as polyparahydroxystyrene, and the like. These phenol resins can be used alone 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 blending ratio of the epoxy resin and the phenolic resin is, for example, appropriate to blend 0.5 to 2.0 equivalents of the hydroxyl group in the epoxy resin 1 equivalent of the phenol resin. In addition, it is more suitable to be 0.8 to 1.2 equivalents. That is, when the mixing ratio of the two is outside the above range, a sufficient curing reaction cannot be performed, and the characteristics of the cured epoxy resin are liable to deteriorate.

The thermoplastic resin is not particularly limited as long as it is a thermoplastic resin having an epoxy group and no carboxyl group, and examples thereof include butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, and ethylene. -acrylic acid Copolymer, ethylene-acrylate copolymer, polybutadiene resin, polycarbonate resin, thermoplastic polyimide resin, polyimide resin, phenoxy resin, acrylic resin, saturated polyester resin such as PET or PBT , Polyimide, imine resin, or fluorine-containing resin. These thermoplastic resins can be used alone or in combination of two or more. Among these thermoplastic resins, an acrylic resin having few ionic impurities, high heat resistance, and ensuring the reliability of a semiconductor element is particularly preferred.

The acrylic resin is not particularly limited as long as it is an acrylic resin having an epoxy group and no carboxyl group, and examples thereof include straight or branched chains having 30 or less carbon atoms, particularly 4 to 18 carbon atoms. Copolymers of alkane acrylates or methacrylates with monomers including epoxy groups. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl, pentyl, isopentyl, hexyl, heptyl, cyclohexyl, 2-ethylhexyl, octyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, lauryl, tridecyl, tetradecyl, stearyl, ten Octyl or eicosyl and the like. Examples of the monomer including an epoxy group include glycidyl acrylate, glycidyl methacrylate, and 4-hydroxybutyl acrylate glycidyl ether.

The adhesive sheet preferably contains 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) relative to 100 parts by weight of the total amount of the adhesive sheet. Parts) of the thermosetting resin, 0 to 60 parts by weight (more preferably 0 to 50 parts by weight) of a 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, cracks or defects in semiconductor wafers and the like can be further suppressed, and chemical stability can be further improved, and furthermore, Easy to control physical properties.

Regarding the adhesive sheet, a 2.5 g adhesive sheet was immersed in a 50 ml aqueous solution including 10 ppm 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, and more preferably 0. ~ 9.5 ppm, more preferably 0 to 8 ppm. Regarding the adhesive sheet, a 2.5 g adhesive sheet was immersed in a 50 ml aqueous solution including 10 ppm copper ions and left at 120 ° C for 20 hours. When the copper ion concentration in the aqueous solution was 0 to 9.9 ppm, it was easier to capture the semiconductor Cations mixed from the outside in various steps of manufacturing the device. As a result, it is difficult for cations mixed in from the outside to reach the circuit formation surface formed on the wafer, and it is possible to suppress the decrease in electrical characteristics, thereby improving product reliability.

When the adhesive sheet is previously crosslinked to some extent, a polyfunctional compound that reacts with a functional group at the molecular chain end of the polymer or the like may be added as a crosslinking agent. Thereby, the adhesion characteristics at high temperatures can be improved, and the heat resistance can be improved.

As the crosslinking agent, a conventionally known crosslinking agent can be used. In particular, polyisocyanate compounds such as toluene diisocyanate, diphenylmethane diisocyanate, terephthalic acid diisocyanate, 1,5-naphthalene diisocyanate, and an adduct of a polyol and a diisocyanate are more preferable. The addition amount of the crosslinking agent is usually preferably set to 0.05 to 7 parts by weight based on 100 parts by weight of the polymer. When the amount of the cross-linking agent exceeds 7 parts by weight, the adhesive force decreases, which is not preferable. On the other hand, when the content is less than 0.05 parts by weight, the cohesive force is insufficient, which is not preferable. In addition, while including such a polyisocyanate compound, other polyfunctional compounds such as epoxy resin may be included together as necessary.

Moreover, a filler can be mix | blended with the said adhesive sheet suitably according to the use. The combination of fillers can impart conductivity to the adhesive sheet, improve thermal conductivity, and adjust Modulus of elasticity, etc. Examples of the filler include inorganic fillers and organic fillers, and inorganic fillers are preferred from the viewpoints of improving workability, improving thermal conductivity, adjusting melt viscosity, and imparting thixotropic properties. The inorganic filler is not particularly limited, and examples thereof include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, and boric acid. Aluminum whiskers, boron nitride, crystalline silicon dioxide, amorphous silicon dioxide, etc. These fillers can be used alone or in combination of two or more. From the viewpoint of improving the thermal conductivity, alumina, aluminum nitride, boron nitride, crystalline silicon dioxide, and amorphous silicon dioxide are preferred. In addition, from the viewpoint of a good balance of the above characteristics, crystalline silicon dioxide or amorphous silicon dioxide is preferred. In addition, a conductive substance (conductive filler) may be used as the inorganic filler for the purpose of imparting conductivity and improving thermoelectric conductivity. Examples of the conductive filler include metal powder obtained by forming silver, aluminum, gold, copper, nickel, conductive alloy, and the like into a spherical shape, needle shape, and flake shape, metal oxides 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 the thickness to 1 μm or less, the effects of the filler added to impart the above-mentioned characteristics can be fully exhibited, and heat resistance can be secured. The average particle diameter of the filler is a value obtained by a photometric particle size distribution meter (manufactured by HORIBA, device name: LA-910).

In addition, in the adhesive sheet, in addition to the complex-forming organic compound, other additives may be appropriately blended as necessary. Examples of the other additives include anion trapping agents, dispersants, antioxidants, silane coupling agents, and curing accelerators. These additives can be used alone or in combination of two or more. use.

The method for producing the adhesive composition for forming the adhesive sheet is not particularly limited. For example, the thermosetting resin, the thermoplastic resin, the complex-forming organic compound, and other additives as necessary It can be obtained as an adhesive composition solution by putting it into a container, dissolving it in an organic solvent, and stirring until it is uniform.

The organic solvent is not particularly limited as long as it can dissolve, knead, or disperse the components constituting the adhesive sheet uniformly, and conventionally known organic solvents 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. From the viewpoint of fast drying speed and availability, it is preferable to use methyl ethyl ketone, cyclohexanone, or the like. Among them, methyl ethyl ketone which can dissolve the complex-forming organic compound is more preferable.

The adhesive sheet of this embodiment can be produced, for example, as follows. First, a solution of the adhesive composition is prepared. Then, the adhesive composition solution is applied to a substrate separator to a predetermined thickness to form a coating film, and then the coating film is dried under predetermined conditions. The substrate separator can be surface-coated with a polyethylene terephthalate (PET), polyethylene, polypropylene, or a release agent such as a fluorine-containing release agent or a long-chain alkyl acrylate-based release agent. Plastic film or paper. The coating method is not particularly limited, and examples thereof include roll coating, screen coating, and gravure coating. The drying conditions are performed, for example, in a range of 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.

(Manufacturing method of semiconductor device)

Hereinafter, an embodiment of a method for manufacturing a semiconductor device when the adhesive sheet is used as a wafer bonding film will be described. Hereinafter, a method for manufacturing a semiconductor device using a dicing / wafer bonding film 10 in which a bonding sheet 3 (hereinafter also referred to as a wafer bonding film 3) of the present embodiment is laminated on a conventionally known dicing film will be described. The dicing film of this embodiment has a structure in which an adhesive layer 2 is laminated on a base material 1. FIG. 1 is a schematic cross-sectional view showing a dicing / wafer bonding film according to this embodiment. FIG. 2 is a schematic cross-sectional view showing an example of mounting a semiconductor wafer via a wafer bonding film of the dicing / wafer bonding film.

First, as shown in FIG. 1, the semiconductor wafer 4 is crimped onto the semiconductor wafer bonding portion 3 a of the wafer bonding film 3 in the dicing / wafer bonding film 10, and then held and fixed (mounting step). This step is carried out by pressing using a pressing means such as a crimping roller.

Then, dicing of the semiconductor wafer 4 is performed. Thereby, the semiconductor wafer 4 is cut into a predetermined size and reduced to pieces, and a semiconductor wafer 5 is produced. Dicing is performed from the circuit surface side of the semiconductor wafer 4 according to a conventional method, for example. In addition, in this step, for example, a dicing method called full dicing, which is cut into the dicing / wafer bonding film 10, can be used. The cutting device used in this step is not particularly limited, and a conventionally known cutting device can be used. In addition, since the semiconductor wafer is subsequently fixed by the dicing / wafer bonding film 10, it is possible to suppress wafer defects or wafer scattering, and to suppress damage to the semiconductor wafer 4.

In order to peel off the semiconductor wafer which is subsequently fixed by the dicing / wafer bonding film 10, the semiconductor wafer 5 is picked up. The pickup method is not particularly limited, and various conventionally known methods can be adopted. For example, each semiconductor wafer 5 is pushed up from the dicing / wafer bonding film 10 side with a needle, and picked up by a pick-up device. Method of pushing up the semiconductor wafer 5 and the like.

Here, when the adhesive layer 2 is an ultraviolet curing type, the adhesive layer 2 is picked up after being irradiated with ultraviolet rays. Thereby, the adhesive force of the adhesive layer 2 to the wafer bonding film 3 is reduced, and the semiconductor wafer 5 is easily peeled. 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 dicing is bonded to the adherend 6 via the wafer bonding film 3. Wafer bonding is performed by pressure bonding. The conditions for wafer bonding are not particularly limited, and can be appropriately set as necessary. Specifically, for example, it can be performed in the range of a wafer bonding temperature of 80 to 160 ° C, a wafer bonding pressure of 5N to 15N, and a wafer bonding time of 1 to 10 seconds.

Then, a wire bonding process is performed in which the tip of the terminal portion (internal lead) of the adherend 6 is electrically connected to an electrode pad (not shown) on the semiconductor wafer 5 by the bonding wire 7. As the bonding wire 7, for example, a gold wire, an aluminum wire, or a copper wire can be used. The temperature at the time of wire bonding is performed in the range of 80 to 250 ° C, preferably 80 to 220 ° C. In addition, the heating time can be from several seconds to several minutes. Wiring is performed by using a combination of ultrasonic vibration energy and pressure energy generated by applying pressure in a state heated to the temperature range.

The wire bonding step can be performed without thermally curing the wafer bonding film 3. At this time, the shear adhesion force of the wafer bonding film 3 to the adherend at 25 ° C. is preferably 0.2 MPa or more, and more preferably 0.2 to 10 MPa. By adjusting the shear bonding force to 0.2 MPa or more, even if the wire bonding process is performed without thermally curing the wafer bonding film 3, the wafer bonding film 3 is not caused by the ultrasonic vibration or heating in this process. Shear deformation occurs on the bonding surface with the semiconductor wafer 5 or the adherend 6. That is, semiconductor elements are not affected by It moves by ultrasonic vibration during wire bonding, thereby preventing a decrease in the success rate of wire bonding.

The wafer bonding film 3 includes a thermoplastic resin having an epoxy group and no carboxyl group, a thermosetting resin, and a complex-forming organic compound including a heterocyclic compound containing a tertiary nitrogen atom as a ring atom and capable of forming a complex with a cation. . Therefore, even if subjected to the thermal history of the wire bonding process, the thermoplastic resin having no carboxyl 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 curing reaction violently.

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 wire 7 mounted on the adherend 6. This step is performed by molding a sealing resin with a mold. As the sealing resin 8, for example, an epoxy resin can be used. The heating temperature at the time of resin sealing is usually 175 ° C, and it is performed for 60 to 90 seconds. However, this embodiment is not limited to this. For example, it may be cured at 165 to 185 ° C for several minutes.

In the mounting step, since there are generally minute irregularities on the semiconductor wafer 4, air bubbles are mixed into an interface or the like between the semiconductor wafer 4 and the wafer bonding film 3. In this sealing step, the bubbles are diffused into the sealing resin 8 and the like by the pressure when the resin is sealed, and the influence thereof is reduced. In addition, as described above, the severe curing reaction caused by the thermal history in the wire bonding process of the wafer bonding film 3 is suppressed. As a result, the bubbles can be easily diffused in the sealing step, so that peeling at the bonding interface due to the bubbles can be prevented.

Then, in the post-curing step, the sealing resin 8 that was insufficiently cured in the aforementioned sealing step is completely cured. Even if the wafer bonding film 3 is not thermally cured in the sealing process, the same process as that in which the sealing resin 8 is cured can be performed in this step. The wafer bonding film 3 is then thermally cured and then fixed. 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 about 0.5 to 8 hours.

The adhesive sheet (wafer bonding film) can also be suitably used in a case where a plurality of semiconductor wafers are stacked and three-dimensionally mounted as shown in FIG. 3. 3 is a schematic cross-sectional view showing an example of three-dimensional mounting of a semiconductor wafer via a wafer bonding film. In the case of three-dimensional mounting shown in FIG. 3, first, at least one wafer bonding film 3 diced to the same size as the semiconductor wafer is affixed to the adherend 6, and then the semiconductor wafer 5 is bonded to the substrate 6 via the wafer bonding film 3. The wire bonding surface is adhered with the upper side. Then, the wafer bonding film 13 is adhered while avoiding the electrode pad portion of the semiconductor wafer 5. Furthermore, the other semiconductor wafer 15 is wafer-bonded to the wafer-bonding film 13 so that the wire bonding surface is on the upper side.

Then, a wire bonding process is performed. Accordingly, 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. This step can be carried out without going through the heating step of the wafer bonding films 3 and 13.

Next, a sealing step of sealing the semiconductor wafer 5 or the like is performed with 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 semiconductor wafers are stacked in multiple layers, the thermal history of the wire bonding process and the like is large, and bubbles existing at the interface between the wafer bonding film and the semiconductor wafer have a large effect on peeling. However, the thermoplastic resin having no carboxyl group hardly reacts with the complex-forming organic compound. As a result, the wafer bonding films 3 and 13 can be restrained from undergoing a curing reaction violently. Therefore, during the sealing process, The bubbles are easily diffused, so that peeling at the bonding interface caused by the bubbles can be prevented.

In the above embodiment, the case where the adhesive sheet is a wafer bonding film has been described, but the adhesive sheet is not particularly limited as long as it is an adhesive sheet that can be used in the manufacture of a semiconductor device. It may be a protective film for protecting the back surface of the semiconductor wafer of the flip-chip semiconductor device, or a sealing sheet for sealing between the front surface of the semiconductor wafer of the flip-chip semiconductor device and the adherend. The adhesive sheet can be used in a method for manufacturing a semiconductor device including a step of attaching a semiconductor wafer to an adherend via the adhesive sheet. The step of pasting the semiconductor wafer onto the adherend via the adhesive sheet can be a conventionally known pasting step. The semiconductor device manufactured by the method of manufacturing a semiconductor device is a semiconductor device having the bonding sheet.

<Second Embodiment>

The adhesive sheet of this embodiment is composed of an adhesive composition including an ion trapping agent, and the tensile storage elastic modulus at 260 ° C after curing at 175 ° C for 5 hours is 0.5 MPa or more and 1000 MPa or less. Hereinafter, this embodiment will be described with respect to differences from the first embodiment. The adhesive sheet of this embodiment can exhibit the same characteristics as those of the adhesive sheet of the first embodiment, as characteristics other than those specifically described in the items of this embodiment.

After the adhesive sheet is thermally cured under predetermined conditions, the tensile storage elastic modulus at 260 ° C. is 0.5 MPa or more and 1000 MPa or less, so that the elastic modulus at high temperature can be maintained, and it can be prevented in the sealing process or the rewelder. In the next step, the wafer is peeled from the semiconductor wafer. In addition, peeling of the adhesive sheet can be prevented, and the adhesiveness between the adhesive sheet and the semiconductor wafer can be maintained, so that the semiconductor wafer can be prevented from being mixed in. The capture efficiency of metal ions that can be mixed into semiconductor wafers is reduced.

The film thickness of the adhesive sheet is preferably 3 to 150 μm, more preferably 5 to 120 μm, and still more preferably 5 to 60 μm. By setting the film thickness of the adhesive sheet to 3 μm or more, metal ions can be captured more favorably. On the other hand, by setting the film thickness of the adhesive sheet to 150 μm or less, it is easy to control the film thickness.

The water absorption of the adhesive sheet when left 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, and still more preferably 1% by weight or less. When the water absorption is preferably 3% by weight or less, in the semiconductor package, the movement of metal ions in the subsequent sheet is suppressed, and cations can be captured more appropriately.

The shear adhesive force of the adhesive sheet after thermal curing of the silicon wafer is preferably 0.1 MPa or more and 20 MPa or less, more preferably 0.15 MPa or more and 15 MPa or less, and still more preferably 0.2 MPa or more and 10 MPa or less under the condition of 175 ° C. When the shear bonding force is 0.1 MPa or more under the condition of 175 ° C., in the semiconductor package, metal ions are easily diffused from the supporting member (for example, a wafer) to the bonding sheet, and the metal ions can be captured more appropriately.

[Adhesive composition]

The adhesive composition constituting the adhesive sheet includes an ion trapping agent, preferably includes a thermoplastic or thermosetting resin, and includes other ingredients as necessary.

(Ion trapping agent)

When an ion trapping agent capable of trapping metal ions is included in the adhesive sheet, metal ions that are mixed in from outside or can be mixed into a semiconductor wafer or a semiconductor wafer can be more appropriately captured in various steps of manufacturing a semiconductor device.

Examples of the ion trapping agent include a cation exchanger and a complex. Physical forming compounds. Among them, a cation exchanger is preferred from the viewpoint of excellent heat resistance, and a complex-forming compound is more preferred from the viewpoint of being able to capture metal ions well.

As the cation exchanger, an inorganic cation exchanger is preferred because it can capture metal ions more appropriately.

In this embodiment, examples of the metal ions captured by the ion trapping agent include the cations described in the first embodiment.

(Inorganic cation exchanger)

The inorganic cation exchanger is not particularly limited, and conventionally known inorganic cation exchangers can be used. For example, from the viewpoint of more appropriately capturing metal ions, examples thereof include antimony, bismuth, zirconium, titanium, tin, magnesium, and An oxide hydrate of an element in the group consisting of aluminum. These may be used alone or in combination of two or more. Among these, oxide hydrates of magnesium and aluminum are preferred.

Examples of commercially available products of the inorganic cation exchanger include trade names manufactured by Toa Synthesis Co., Ltd .: IXE-700F, IXE-770, IXE-770D, IXE-2116, IXE-100, IXE-300, IXE- 600, IXE-633, IXE-6107, IXE-6136, etc.

The average particle diameter of the inorganic cation exchanger is preferably 0.05 to 20 μm, and more preferably 0.1 to 10 μm. By setting the average particle diameter of the inorganic cation exchanger to 20 μm or less, a decrease in adhesive force can be suppressed, and by setting it to 0.05 μm or more, dispersibility can be improved.

(Complex-forming compound)

The complex-forming compound is not particularly limited as long as it is a substance capable of forming a complex with a metal ion, and is preferably a complex-forming organic compound. The substance is preferably one or more selected from the group consisting of a nitrogen-containing compound, a hydroxyl-containing compound, and a carboxyl-containing compound from the viewpoint that metal ions can be appropriately captured.

(Nitrogen compounds)

As the nitrogen-containing compound, a fine powdery, easily soluble organic solvent or liquid nitrogen-containing compound is preferred. Examples of such a nitrogen-containing compound include a heterocyclic compound having a tertiary nitrogen atom from the viewpoint that metal ions can be more appropriately captured. As such a heterocyclic compound, the compounds listed in the first embodiment can be appropriately used.

(Hydroxy compounds)

The hydroxyl-containing compound is not particularly limited, and a fine powder, an easily soluble organic solvent, or a liquid hydroxyl-containing compound is preferred. As such a hydroxyl-containing compound, a compound having two or more hydroxyl groups on one aromatic ring is preferred from the viewpoint that metal ions can be more appropriately captured. Specific examples include a hydroquinone compound, a hydroxyanthraquinone compound, or a polyphenol compound. From the viewpoint of the stability of a complex formed with copper ions, a polyphenol compound is more preferred. These may be used alone 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 (such as a benzene ring) but also a condensed aromatic ring (for example, a naphthalene ring, an anthracene ring, a phenanthrene ring, Tetracene ring, pentacene ring, pyrene ring, etc.), anthraquinone ring and the like.

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

The hydroxyanthraquinone compound is not particularly limited, and includes alizarin, 1,5-dihydroxyanthraquinone, and the like.

The polyphenol compound is not particularly limited, and examples thereof include tannin, Tannin derivatives (gallic acid, alkyl gallate (as the alkyl group, for example, methyl, ethyl, propyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl , Undecyl, dodecyl, etc.), pyrogallol) and the like.

(Carboxylic compounds)

The carboxyl-containing compound is not particularly limited, and examples thereof include a carboxyl-containing aromatic compound and a carboxyl-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 higher fatty acids and carboxylic acid-type chelating agents.

The commercially available products of the carboxylic acid-type chelating reagent are not particularly limited, and examples thereof include: Chelest A, Chelest 110, Chelest B, Chelest 200, Chelest C, Chelest D, Chelest 400, Chelest 40, Chelest 0D, Chelest NTA, Chelest 700, Chelest PA, Chelest HA, Chelest MZ-2, Chelest MZ-4A, Chelest MZ-8, etc.

The content of the metal ion capturing additive is preferably 0.1 to 80 parts by weight, more preferably 0.1 to 50 parts by weight, and still more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the resin component constituting the adhesive sheet. By setting it to 0.1 part by weight or more, metal ions (especially copper ions) can be efficiently captured, and by setting it to 80 parts by weight or less, it is possible to suppress a decrease in heat resistance or an increase in cost.

(Thermoplastic resin)

The adhesive composition used in the formation of the adhesive sheet preferably includes a thermoplastic resin. As the thermoplastic resin, in addition to natural rubber, the resins listed in the first embodiment can be appropriately used. However, unlike the first embodiment The difference is that there are no restrictions on epoxy groups and carboxyl groups, either one or both of them can be included, or neither can be included.

In the said adhesive sheet, it is preferable that the said thermoplastic component and the thermosetting component mentioned later can be mutually crosslinked. Through the cross-linking of the thermoplastic component and the thermosetting component, the adhesion force at a high temperature (for example, 175 to 260 ° C.) is higher, and peeling and the like in a reflow process can be prevented. As a result, the yield of semiconductor device manufacturing can be improved. Examples of the means capable of cross-linking the thermoplastic component and the thermosetting component include, for example, introducing a functional group capable of cross-linking into the two components, and the like. Examples of combinations of functional groups that can be crosslinked include epoxy groups and hydroxyl groups, epoxy groups and carboxyl groups, epoxy groups and amino groups, and the like. By introducing one of these functional group combinations into the thermoplastic component and introducing the other functional group into the thermosetting component, the thermoplastic component and the thermosetting component can be crosslinked with each other.

In order to crosslink the thermoplastic component and the thermosetting component with each other, when the thermoplastic component specifically has an epoxy group or a carboxyl group, a crosslinking reaction with the thermosetting component may be appropriately performed. When the thermoplastic component has an epoxy group, the adhesive sheet preferably includes a phenol resin as a thermosetting component. When the thermoplastic component has a carboxyl group, the adhesive sheet preferably includes an epoxy resin as a thermosetting component. The epoxy group of the thermoplastic component and the hydroxyl group of the phenol resin of the thermosetting component or the hydroxyl group of the thermoplastic component and the epoxy group of the epoxy resin of the thermosetting component may be appropriately crosslinked. In order to introduce an epoxy group into the thermoplastic component, a monomer including an epoxy group may be adopted as a constituent monomer of the acrylic copolymer. The monomer including an epoxy group is not particularly limited as long as it has an epoxy group, and examples thereof include glycidyl acrylate and glycidyl methacrylate. Glycerides, etc. In addition, in order to introduce a carboxyl group into the thermoplastic component, a monomer including a carboxyl group may be adopted 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, and crotonic acid. .

In addition, the other monomers forming the polymer are not particularly limited, and examples thereof include: acid anhydride monomers such as maleic anhydride or itaconic anhydride; hydroxyl-containing monomers such as (meth) acrylic acid 2-hydroxyl Ethyl ester, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate , 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, etc .; monomers containing sulfonic acid groups, Such as styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, sulfopropyl (meth) acrylate, or ( (Meth) acrylic acid oxonaphthalene sulfonic acid, etc .; or a phosphate group-containing monomer, such as acrylic acid phosphonium 2-hydroxyethyl ester and the like. These monomers can be used alone or in combination of two or more.

(Thermosetting resin)

In addition, the adhesive composition preferably includes a thermosetting resin together with the thermoplastic resin. As the thermosetting resin, the thermosetting resin described in the first embodiment can be appropriately used.

The blending ratio of the thermosetting resin is not particularly limited as long as it functions as a thermosetting adhesive sheet when the adhesive sheet is heated under predetermined conditions, and is preferably 1 to 80 weight based on the total amount of the adhesive composition. Within the range of%, more preferably within the range of 3 to 70% by weight.

The adhesive composition includes an epoxy resin, a phenol resin, and an acrylic resin. The total amount of the epoxy resin and the phenol resin is preferably 10 to 2000 parts by weight, and more preferably 10 to 100 parts by weight based on 100 parts by weight of the acrylic resin. 1500 parts by weight, and more preferably 10 to 1,000 parts by weight. By setting the total amount of the epoxy resin and the phenol resin to 100 parts by weight of the acrylic resin to 10 parts by weight or more, the adhesive effect can be obtained through curing, and peeling can be suppressed. By setting the weight to 2000 parts by weight or less, the film change can be suppressed It is brittle and the workability is reduced.

In the adhesive sheet, the content of the thermoplastic resin in the adhesive composition is preferably 0.5 to 20 times, and more preferably 1 to 15 times, based on the weight of the thermosetting resin. By setting the ratio of the content of the thermoplastic resin to the thermosetting resin within such a range, the adhesiveness at low temperature and the elastic modulus at high temperature of the adhesive sheet can be effectively achieved simultaneously.

(Crosslinking agent)

When the adhesive sheet produced using the said adhesive composition is previously crosslinked to some extent, you may add the polyfunctional compound which reacts with the functional group etc. of the molecular chain end of a polymer as a crosslinking agent. Thereby, the adhesion characteristics at high temperatures can be improved, and the heat resistance can be improved. As the crosslinking agent, the crosslinking agent described in the first embodiment can be appropriately used.

(filler)

Moreover, the said adhesive composition can mix | blend a filler suitably according to the use. The blending of the filler can impart conductivity to the adhesive sheet obtained from the adhesive composition, increase its thermal conductivity, adjust its elastic modulus, and the like. As the filler, the filler described in the first embodiment can be appropriately used.

(Other additives)

In addition, in addition to the above-mentioned components, other additives may be appropriately blended in the adhesive composition as necessary. As other additives, those described in the first embodiment can be appropriately used.

In the embodiment described above, the case where a thermosetting resin or a thermoplastic resin is used as the main component of the adhesive contained in the adhesive composition has been described. However, in this embodiment, the main component of the adhesive contained in the adhesive composition is used. The component may replace the above-mentioned thermosetting resin, thermoplastic resin, or include inorganic components such as ceramics, cement, and solder in addition to the above-mentioned thermosetting resin and thermoplastic resin.

[Manufacturing method of adhesive sheet]

The adhesive sheet according to the present embodiment can be appropriately produced by the method described in the first embodiment.

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

The tensile storage elastic modulus of the adhesive sheet at 60 ° C. before thermal 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, and still more preferably 0.1 MPa or more and 50 MPa or less. By adjusting the tensile storage elastic modulus at 60 ° C before thermal curing to 0.01 MPa or more, the shape of the film can be maintained, and good workability can be imparted. In addition, the tensile storage elastic modulus at 60 ° C before thermal curing was adjusted to 1000 MPa or less can provide good wettability to the adherend.

[Semiconductor device]

A semiconductor device according to this embodiment will be described with reference to FIG. 2. The semiconductor device includes an adherend 6, the adhesive sheet 3 laminated on the adherend 6, and a semiconductor wafer 5 disposed on the adhesive sheet 3. The adherend 6 may be a substrate or another semiconductor wafer. In FIG. 2, a substrate is used as an adherend. In the semiconductor device shown in FIG. 2, the semiconductor wafer 5 and the substrate to be adhered are further provided so that the tip of the terminal portion (internal lead) of the adherend 6 is connected to an electrode pad (not shown) on the semiconductor wafer 5. The semiconductor wire 5 is covered with the sealing resin 8 including the bonding wire 7 electrically connected to the object 6.

In the semiconductor device according to this embodiment, the bonding sheet is used when fixing the semiconductor wafer to the adherend. Therefore, the adhesiveness between the bonding sheet and the semiconductor wafer can be maintained while maintaining the adhesion between the bonding sheet and the semiconductor wafer even after a high temperature process such as a sealing process or a reflow process. The metal ions mixed in the manufacturing process are effectively captured, and as a result, excellent product reliability can be ensured.

[Manufacturing method of semiconductor device]

Hereinafter, an embodiment of a method for manufacturing a semiconductor device in a case where the above-mentioned adhesive sheet is used as a wafer bonding film will be described. The method of manufacturing a semiconductor device according to this embodiment includes a step of adhering a bonding sheet of a dicing / wafer bonding film to a semiconductor wafer, a step of dicing the semiconductor wafer to form a semiconductor wafer, and bonding the semiconductor wafer to the semiconductor wafer. The step of picking up the next wafer together and the step of fixing the picked-up semiconductor wafer to the adherend via the bonding wafer.

(Cut / Wafer Bonding Film)

Hereinafter, a method for manufacturing a semiconductor device using a dicing / wafer bonding film 10 in which a bonding sheet 3 (hereinafter also referred to as a wafer bonding film 3) of the present embodiment is laminated on a conventionally known dicing film will be described. The dicing film according to this embodiment has a structure in which an adhesive layer 2 is laminated on a substrate 1.

(Manufacturing method of semiconductor device)

As the method of manufacturing the semiconductor device of the present embodiment, the manufacturing method described in the first embodiment can be appropriately adopted.

In addition, the surface of the semiconductor package obtained through the post-curing step after the sealing step may be mounted on a printed wiring board. The surface mounting method includes, for example, reflow soldering in which solder is supplied in advance on a printed wiring board and then heated and melted with warm air or the like. Examples of the heating method include hot air reflow, infrared reflow, and the like. In addition, any one of global heating and local heating may be used. The heating temperature is preferably 240 to 265 ° C, and the heating time is preferably in a range of 1 to 60 seconds.

According to the adhesive sheet, the tensile storage elastic modulus at 260 ° C after curing at 175 ° C for 5 hours is 0.5 MPa or more and 1000 MPa or less, so the elastic modulus at high temperature (for example, 175 to 260 ° C) can be maintained It can prevent the adhesive sheet from peeling off from the semiconductor wafer in the sealing process or the reflow process.

In addition, the adhesive sheet (wafer bonding film) can be suitably applied to a case where a plurality of semiconductor wafers are stacked and three-dimensionally mounted as shown in FIG. 3. For the three-dimensional mounting method of the present embodiment, the method described in the first embodiment can be appropriately adopted. In addition, the finally obtained semiconductor package may be surface-mounted on a printed wiring board after the reflow process described above.

<Third Embodiment>

The adhesive sheet of this embodiment includes the following components (a) to (c), and is composed of only organic components, (a) an acrylic resin having a weight average molecular weight of 800,000 or more; (b) an epoxy resin and a phenol resin At least one of (c) a complexing agent capable of forming a complex with a metal ion.

Hereinafter, this embodiment will be described with respect to differences from the first embodiment. The adhesive sheet of this embodiment can exhibit the same characteristics as those of the adhesive sheet of the above-mentioned embodiment as characteristics other than those specifically described in the item of this embodiment.

This adhesive sheet is comprised only of an organic component. In other words, since a filler component represented by a silicon dioxide filler is not included, mechanical damage such as chipping or cracking of a semiconductor wafer or the like caused by contact with the filler can be prevented. In addition, by using the component (a) and the component (b), it is possible to prevent a decrease in the glass transition temperature. Therefore, even without a filler, the elastic modulus of the adhesive sheet at a high temperature can be maintained, and further, the shear adhesive force can be maintained. The wire bonding process or the reflow process is performed well. In addition, since the adhesive sheet includes the component (c), metal ions such as a semiconductor wafer mixed in the manufacturing process of the semiconductor device can be efficiently captured, and a semiconductor device with high product reliability can be manufactured.

The adhesive sheet is preferably free of fillers. As a result, a dispersed phase that can cause mechanical damage to a semiconductor wafer or the like, such as an inorganic filler or an organic filler, can be eliminated, and thus it is possible to cope with further thinning of the adhesive sheet.

The shear adhesive force of the adhesive sheet after thermal curing of the supporting member (175 ° C. × 1 hour) is preferably 0.05 MPa or more and 1 GPa or less, more preferably 0.1 MPa or more and 0.8 GPa or less, and more preferably 175 ° C. 0.2MPa or more And 0.5GPa or less. When the shear adhesive force is 0.05 MPa or more under the condition of 175 ° C., in a semiconductor package, metal ions are easily diffused from a supporting member (for example, a wafer, etc.) to the bonding sheet, and metal ions can be captured more appropriately.

((a) Ingredient)

The adhesive sheet includes an acrylic resin having a weight average molecular weight of 800,000 or more as a component (a). Acrylic resin is preferable because it has few ionic impurities and high heat resistance, and can ensure the reliability of the semiconductor element. (a) The weight average molecular weight of a component is not specifically limited if it is 800,000 or more, Preferably it is 800,000 or more and 2 million or less, More preferably, 1 million or more and 1.8 million or less, More preferably, 1.2 million or more and 1.5 million or less. By setting the weight-average molecular weight of the component (a) to 800,000 or more, it is possible to prevent a decrease in the elastic modulus at a high temperature while maintaining the adhesiveness at a low temperature of the adhesive sheet. The measuring method of the weight average molecular weight of an acrylic resin is based on the method as described in an Example.

The acrylic resin is not particularly limited, and examples thereof include one of an acrylate or a methacrylate having a linear or branched alkyl group having 30 or less carbon atoms, particularly 4 to 18 carbon atoms, or A polymer (acrylic copolymer) of two or more components. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl, pentyl, isopentyl, hexyl, heptyl, cyclohexyl, 2-ethylhexyl, octyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, lauryl, tridecyl, tetradecyl, stearyl, ten Octyl or eicosyl and the like.

In the adhesive sheet, the component (a) and the component (b) may preferably be crosslinked with each other. By cross-linking the component (a) and the component (b), the adhesion force at a high temperature (for example, 175 to 260 ° C) is further improved, which can prevent the reflow process and the like. As a result, the yield of semiconductor device manufacturing can be improved. Examples of the means capable of cross-linking the (a) component and the (b) component with each other include, for example, introducing a functional group capable of cross-linking into the two components, and the like. Examples of combinations of functional groups that can be crosslinked include epoxy groups and hydroxyl groups, epoxy groups and carboxyl groups, epoxy groups and amino groups, and the like. By introducing one of these functional group combinations into the (a) component and introducing the other functional group into the (b) component, the (a) component and the (b) component can be made to interact with each other. Link.

In order to crosslink the (a) component and the (b) component, when the (a) component specifically has an epoxy group, a crosslinking reaction with the (b) component may be appropriately performed. At this time, the adhesive sheet preferably includes a phenol resin as the component (b). The epoxy group of the component (a) and the hydroxyl group of the phenol resin of the component (b) can be appropriately subjected to a crosslinking reaction. In order to introduce an epoxy group into the component (a), a monomer including an epoxy group may be used as a constituent monomer of the acrylic copolymer. The monomer including an epoxy group is not particularly limited as long as it has an epoxy group, and examples thereof include glycidyl acrylate, glycidyl methacrylate, and 4-hydroxybutyl acrylate glycidyl ether.

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, 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 an acrylic resin having an acid value of 5 to 150 is included in the adhesive sheet, the carboxyl group of the acrylic resin contributes to the formation of the complex and promotes the capture effect of the ion trapping agent. Through such a synergistic effect, the synergy effect can be better. Capture metal ions. The acid value of the acrylic resin in this embodiment refers to neutralization per 1 g of the test The number of mg of potassium hydroxide required for free fatty acids, resin acids, etc. included in the sample.

In addition, as other monomers forming the polymer, other monomers described in the second embodiment can be appropriately used.

((b) Ingredient)

The adhesive sheet includes at least one of an epoxy resin and a phenol resin as a component (b). When an epoxy resin is included as a curing agent, a high bonding force between the bonding sheet and the wafer can be obtained at a high temperature. As a result, it is difficult for water to enter the bonding interface between the bonding sheet and the wafer, and ions are difficult to move. This improves reliability.

As the epoxy resin and the phenol resin, the resin described in the first embodiment can be appropriately used.

The compounding ratio of the component (b) is not particularly limited as long as the adhesive sheet functions as a thermosetting type when heated under predetermined conditions, and it is preferably 1 to 1 in the adhesive composition constituting the adhesive sheet. It is in the range of 50% by weight, and more preferably in the range of 1 to 30% by weight.

The constituents of the adhesive sheet include an acrylic resin having an epoxy group as the component (a) and a phenol resin as the component (b). The total of the component (b) with respect to the components (a) and (b) The amount ratio is preferably 1 to 50% by weight, more preferably 1 to 30% by weight, and still more preferably 1 to 10% by weight. By setting the ratio of the component (b) to the total amount of the components (a) and (b) to 1% by weight or more, a bonding effect can be obtained through curing, peeling can be suppressed, and 50% by weight or less can be suppressed. The film becomes brittle and the workability is reduced.

((c) component)

The adhesive sheet includes a complexing agent capable of forming a complex with a metal as (c) ingredient. When the component (c) is included in the adhesive sheet, metal ions mixed from the outside during various steps of manufacturing a semiconductor device can be efficiently captured.

In this embodiment, the metal ion captured by the complexing agent and the complexing agent can be suitably used as the metal ion and the complex-forming compound described in the second embodiment, respectively.

(Other ingredients)

(Crosslinking agent)

When the adhesive sheet made using the said adhesive composition is previously crosslinked to some extent, the polyfunctional compound which reacts with the functional group etc. of the molecular chain end of a polymer can be added as a crosslinking agent. Thereby, the adhesion characteristics at high temperatures can be improved, and the heat resistance can be improved. As the crosslinking agent, the crosslinking agent described in the first embodiment can be appropriately used.

(Other thermoplastic resins)

Examples of the thermoplastic resin other than the component (a) include natural rubber, butyl rubber, isoprene rubber, neoprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, and ethylene-acrylate copolymer Resins, polybutadiene resins, polycarbonate resins, thermoplastic polyimide resins, polyamide resins such as nylon 6 or nylon 6,6, phenoxy resins, saturated polyester resins such as PET or PBT, and polyamides醯 imine resin or fluororesin. These thermoplastic resins can be used alone or in combination of two or more.

(Other thermosetting resins)

Examples of the thermosetting resin other than the component (b) include amino resins, unsaturated polyester resins, polyurethane resins, polysiloxane resins, and thermosetting polyimide resins. These resins can be used alone or in combination of two or more. use.

(Other additives)

In addition, in the adhesive sheet, in addition to the optional ingredients listed so far, other additives may be appropriately blended as necessary. Examples of the other additives include anion trapping agents, dispersants, antioxidants, silane coupling agents, and curing accelerators. These additives may be used alone or in combination of two or more.

The tensile storage elastic modulus of the adhesive sheet at 60 ° C. before thermal 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, and still more preferably 0.1 MPa or more and 50 MPa or less. In addition, the thermal storage elastic modulus of the adhesive sheet at 260 ° C is preferably 0.01 MPa or more and 500 MPa or less, more preferably 0.03 MPa or more and 500 MPa or less, still more preferably 0.05 MPa or more and 100 MPa or less, further More preferably, it is 0.1 MPa or more and 50 MPa or less. By setting the tensile storage elastic modulus at 60 ° C before thermal curing to 0.01 MPa or more, the shape of the film can be maintained, and good workability can be imparted. In addition, by setting the tensile storage elastic modulus at 60 ° C. before thermal curing to 1000 MPa or less, good wettability to an adherend can be imparted. On the other hand, by setting the tensile storage elastic modulus at 260 ° C after thermal curing to 0.01 MPa or more, the occurrence of reflow cracks can be suppressed. In addition, by setting the tensile storage elastic modulus at 260 ° C. to 500 MPa or less after thermal curing, thermal stress caused by a difference in thermal expansion coefficient between a semiconductor wafer and an interposer as a wiring substrate can be alleviated.

[Manufacturing method of adhesive sheet]

The adhesive sheet of this embodiment can be appropriately described in the first embodiment. Make it clear.

[Manufacturing method of semiconductor device]

As the method of manufacturing the semiconductor device of this embodiment, the manufacturing method described in the second embodiment can be appropriately adopted.

<Fourth Embodiment>

As shown in FIG. 4, the multilayer adhesive sheet 3 for a semiconductor device according to this embodiment is a multilayer sheet including an ion-trapping layer 3A and an adhesive layer 3B. An ion trapping composition of an organic low molecular compound is formed, and the adhesive layer 3B is formed of an adhesive composition. 1 to 3 are shown in the form of a multilayer adhesive sheet 3 in which these ion trapping layers 3A and the adhesive layer 3B are integrated. Hereinafter, this embodiment will be described with respect to differences from the first embodiment. The adhesive sheet of this embodiment can exhibit the same characteristics as those of the adhesive sheet of the above-mentioned embodiment as characteristics other than those specifically described in the items of the embodiment.

[Ion capture layer]

The ion-trapping composition includes an organic low-molecular-weight compound capable of forming a complex with a metal ion (hereinafter sometimes simply referred to as an “organic low-molecular-weight compound”), and the present embodiment includes an ion-trapping layer formed from the composition. The subsequent sheet can capture metal ions mixed in from outside during various processes of manufacturing a semiconductor device. As a result, it is difficult for metal ions mixed in from the outside to reach the circuit formation surface formed on the wafer, it is possible to suppress the decrease in electrical characteristics, and it is possible to improve product reliability.

In this embodiment, the metal ion captured by the organic low molecular weight compound is not particularly limited as long as it is a metal ion, and examples thereof include: Ions of Na, K, Ni, Cu, Cr, Co, Hf, Pt, Ca, Ba, Sr, Fe, Al, Ti, Zn, Mo, Mn, V, etc.

The organic low molecular weight compound capable of forming a complex with a metal ion is different from a resin capable of forming a complex with a metal ion, and its molecular weight is preferably 1,000 or less, and more preferably 500 or less. The lower limit of the molecular weight is not particularly limited, but is usually 50 or more. The resin has a low proportion of functional groups that contribute to the capture of metal ions in the resin, and as a result, it is difficult to form a complex with the metal ions. Therefore, a resin capable of forming a complex with a metal ion is insufficient in terms of ion trapping property. On the other hand, organic low-molecular-weight compounds having a molecular weight of 1,000 or less have a high proportion of functional groups that contribute to the capture of metal ions in one molecule, and therefore easily form complexes with metal ions. As a result, ion trapping properties are high.

The organic low molecular weight compound is not particularly limited as long as it is a compound capable of forming a complex with a metal ion, and the complex-forming compound in the second embodiment can be appropriately used.

The compounding amount of the organic low molecular weight compound capable of forming a complex with metal ions is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, with respect to 100 parts by weight of all the components of the ion-trapping composition, further It is preferably 0.2 to 5 parts by weight, and particularly preferably 0.3 to 3 parts by weight. By setting it to 0.1 part by weight or more, metal ions (especially copper ions) can be efficiently trapped, and by setting it to 10 parts by weight or less, it is possible to suppress a decrease in heat resistance and increase in cost. The compounding amount of the organic low-molecular-weight compound in the multilayer adhesive sheet of the present embodiment with respect to all the components in the ion-trapping layer is the same as the compounding amount of the organic low-molecular-weight compound with respect to all the components in the ion-trapping composition. .

The ion-trapping composition preferably includes a thermoplastic resin, and more preferably includes a thermoplastic resin and a thermosetting resin. As the thermoplastic resin and the thermosetting resin, the resin described in the second embodiment can be appropriately used.

When the ion-trapping composition includes an epoxy resin, a hydroxyl-containing resin or a carboxyl-containing resin is preferably used in combination. From the viewpoint of heat resistance, a phenol resin is preferably used in combination. When the thermoplastic resin having an epoxy group and the like described later are included in the ion-trapping composition, the phenol resin can react with the thermoplastic resin having an epoxy group and the like. As the phenol resin, the phenol resin described in the first embodiment can be appropriately used.

In addition, the blending ratio of the epoxy resin, the thermoplastic resin having an epoxy group, and the hydroxyl-containing or carboxyl-containing resin is not particularly limited. For example, it is preferable to use a ratio relative to the epoxy resin component or the thermoplastic resin having an epoxy group. 1 equivalent of the epoxy group in the hydroxyl group, or the carboxyl group in the carboxyl group-containing resin component is 0.5 to 2.0 equivalents, and more preferably 0.8 to 1.2 equivalents. It is preferable that a sufficient reaction can be performed via the blending ratio within the above range.

The mixing ratio of the thermosetting resin is preferably in the range of 1 to 30% by weight, and more preferably in the range of 1 to 20% by weight in the ion-trapping composition.

In addition, as other monomers forming the polymer, other monomers described in the second embodiment can be appropriately used.

In addition, in the present embodiment, from the viewpoint that a thermoplastic resin and a thermosetting resin are appropriately crosslinked to obtain good reliability, a thermoplastic resin having an epoxy group or a carboxyl group is preferably used, and an acrylic resin having an epoxy group is more preferably used. Or an acrylic resin having a carboxyl group. Examples of the acrylic resin having an epoxy group include the aforementioned esters and coatings of acrylic acid or methacrylic acid having an alkyl group. Copolymers of epoxy-containing monomers. Examples of the monomer including an epoxy group include the same monomers as described above. As a commercial item of the acrylic resin which has an epoxy group, the trade name made by Nagasechemtex Co., Ltd .: SG-P3 etc. are mentioned. Examples of the acrylic resin having a carboxyl group include copolymers of the above-mentioned esters of acrylic acid or methacrylic acid having an alkyl group and a monomer including a carboxyl group such as (meth) acrylic acid. As a commercial item of the acrylic resin which has a carboxyl group, the trade name: SG-708-6 made by Nagasechemtex Co., Ltd. is mentioned.

The mixing ratio of the thermoplastic resin is not particularly limited as long as the multilayer adhesive sheet functions as a thermosetting type when heated under predetermined conditions. In the ion-trapping composition, it is preferably 30 to 95% by weight. Within the range, it is more preferably within a range of 50 to 60% by weight.

When the ion-trapping layer formed of the ion-trapping composition is previously cross-linked to some extent, a polyfunctional compound that reacts with a functional group at the molecular chain end of the polymer or the like may be added as a crosslinking agent. Thereby, the adhesion characteristics at high temperatures can be improved, and the heat resistance can be improved. As the crosslinking agent, the crosslinking agent described in the first embodiment can be appropriately used.

Moreover, a filler can be mix | blended suitably in the said ion-trapping composition according to the use. The blending of the filler can impart conductivity to the multilayer adhesive sheet including the ion-trapping layer obtained from the ion-trapping composition, increase its thermal conductivity, adjust its elastic modulus, and the like. Examples of the filler include inorganic fillers and organic fillers, and inorganic fillers are preferred from the viewpoints of improving workability, improving thermal conductivity, adjusting melt viscosity, and imparting thixotropic properties. As the filler, the filler described in the first embodiment can be used.

In addition, in the ion-trapping composition, in addition to the above components, other additives may be appropriately blended as necessary. As other additives, those described in the first embodiment can be appropriately used.

The ion trapping composition preferably includes a thermoplastic resin, a thermosetting resin, and a silica filler in addition to the organic low-molecular-weight compound, and is preferably 100 parts by weight with respect to the total of the thermoplastic resin, the thermosetting resin, and the silica filler. 10 to 99 parts by weight of a thermoplastic resin, 1 to 30 parts by weight of a thermosetting resin, and 0 to 60 parts by weight of a silica filler, more preferably 20 to 98 parts by weight of a thermoplastic resin, 2 to 30 parts by weight of a thermosetting resin, two The silica filler is 0 to 60 parts by weight. When it is in the said range, since it can have a high elastic modulus at high temperature, and can obtain favorable reliability, it is preferable.

The method for producing the ion-trapping composition is not particularly limited. For example, an organic low-molecular-weight compound capable of forming a complex with metal ions, and a thermoplastic resin, a thermosetting resin, and other additives may be charged into a container as necessary. , Dissolved in an organic solvent, and stirred until homogeneous, and obtained in the form of an ion-trapping composition solution.

The organic solvent is not particularly limited as long as the components constituting the ion-trapping layer can be uniformly dissolved, kneaded, or dispersed, and conventionally known organic solvents 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. From the viewpoint of fast drying speed and availability, it is preferable to use methyl ethyl ketone, cyclohexanone, or the like.

[Next layer]

The adhesive layer in the multilayer adhesive sheet of this embodiment is composed of an adhesive composition form. The adhesive composition is not particularly limited, and can be used as long as it is an adhesive or the like that can be used in the art. From the viewpoint of improving the adhesion to an adherend such as a substrate, it is preferable that the composition that does not substantially form the metal ions is not substantially contained. Mixed organic low molecular weight compounds. Here, “substantially free” means that the organic low molecular weight compound is less than 0.1 part by weight, more preferably less than 0.05 part by weight, and more preferably less than 0.01 part by weight with respect to 100 parts by weight of the resin component of the adhesive composition. The adhesive layer that does not substantially contain such an organic low-molecular-weight compound does not undergo excessive curing even after heating. Therefore, voids generated between an adherend such as a substrate and the adhesive layer can be diffused well in the forming step. In addition, the organic low-molecular-weight compound has a low molecular weight and is therefore easy to transfer. When a bonding sheet including the organic low-molecular-weight compound is used as a wafer bonding film in a dicing / wafer-bonding film, the organic low-molecular-weight compound is transferred to the dicing. Problems in the belt. However, since the multilayer adhesive sheet of the present embodiment has the adhesive layer, it is possible to suppress the organic low molecular weight compound from being transferred to the dicing tape.

The composition other than the organic low molecular weight compound capable of forming a complex with a metal ion in the adhesive composition may be the same composition as the ion trapping composition described above. Specifically, the adhesive composition may include the aforementioned thermosetting resin, thermoplastic resin, filler, and other additives, and the blending ratio thereof is also the same as that of the ion-trapping composition. The composition of the adhesive composition and the ion-trapping composition may be all the same or different, with or without the addition of an organic low molecular weight compound capable of forming a complex with a metal ion.

The adhesive composition preferably includes a thermoplastic resin, a thermosetting resin, and a silicon dioxide filler. The thermoplastic resin, a thermosetting resin, and a silicon dioxide filler are preferably 100 to 100 parts by weight, and the thermoplastic resin is preferably 10 to 99 weight parts. Parts, 1 to 30 parts by weight of thermosetting resin, 0 to 60 parts by weight of silicon dioxide filler, more preferably 20 to 98 parts by weight of thermoplastic resin, 2 to 30 parts by weight of thermosetting resin, and 0 to 60 part of silicon dioxide filler Parts by weight. When it is in the said range, since it can have a high elastic modulus at high temperature, and can obtain favorable reliability, it is preferable.

[Multilayer Adhesive Film]

The multilayer adhesive sheet of this embodiment may be a double layer composed of the ion trap layer and the adhesive layer, or may further include between the ion trap layer and the adhesive layer as long as the effect of the embodiment is not impaired. Other layers may have the ion trapping layer on both sides of the adhesion layer.

The multilayer adhesive sheet of this embodiment is produced, for example, as follows. First, the ion-trapping composition solution is prepared. Then, the ion-trapping composition solution is applied to a substrate separator to a predetermined thickness to form a coating film, and then the coating film is dried under predetermined conditions. The substrate separator can be surface-coated with polyethylene terephthalate (PET), polyethylene, polypropylene, or a release agent such as a fluorine-containing release agent or a long-chain alkyl acrylate-based release agent. After the plastic film or paper. The coating method is not particularly limited, and examples thereof include roll coating, screen coating, and gravure coating. In addition, as the drying conditions, for example, the drying temperature is within a range of 70 to 160 ° C, and the drying is performed within a range of 1 to 5 minutes. Thereby, the ion-trapping layer of the multilayer adhesive sheet of this embodiment can be obtained.

Then, the adhesive composition solution was prepared, and an adhesive layer was produced by the same method as the ion-trapping layer.

The thus-obtained ion-trapping layer and the adhesive layer can be laminated to obtain a multilayer adhesive sheet according to this embodiment. These layers are adhesive layers, so The bonding can be followed, and if necessary, temperature and pressure can be applied, or a known adhesive can be used for bonding. The conditions of the temperature and pressure can be appropriately set depending on the ion-trapping layer and the adhesion layer to be used.

The film thicknesses of the ion-trapping layer and the adhesive layer may be the same or different, and each is preferably 5 to 100 μm, and more preferably 5 to 20 μm. When the film thickness is more than 5 μm, it can be adhered to the adherend without voids, which is preferable.

The multilayer adhesive sheet of the present embodiment has an ion-capturing layer including an organic low-molecular-weight compound capable of forming a complex with metal ions. Therefore, metal ions mixed in from outside in various steps in the manufacture of a semiconductor device can be captured. It is difficult for the metal ions to reach the circuit formation surface formed on the wafer, which can suppress the decrease in electrical characteristics, and thus can improve product reliability. In addition, the multilayer adhesive sheet of this embodiment has an adhesive layer that does not substantially include the organic low-molecular-weight compound, and therefore has good adhesion to an adherend such as a substrate. Since the voids diffuse during the forming process, adhesion to the adherend can be improved.

In the above-mentioned embodiment, a case where a thermosetting resin or a thermoplastic resin is used as a main component contained in the ion-trapping composition or the adhesive composition has been described. However, in this embodiment, the above-mentioned thermosetting resin may be used instead. And thermoplastic resins include inorganic adhesive components such as ceramics, cements, and solders.

The multilayer adhesive sheet of this embodiment can be suitably used for the manufacture of a semiconductor device. Specific examples include a wafer bonding film for fixing a semiconductor wafer to an adherend such as a lead frame, a protective film for protecting a back surface of a semiconductor wafer of a flip-chip semiconductor device, and sealing of a semiconductor. crystal Sheet of sealing sheet used.

When using the multilayer bonding sheet of this embodiment as a wafer bonding film, it is preferable to stack a semiconductor wafer (semiconductor wafer) on the ion trapping layer 3A (FIG. 4) side, and a dicing film (or adhesive layer) on the bonding layer 3B (FIG. 4) side.物).

The ion trapping layer of the multilayer adhesive sheet was cut to a weight of 2.5 g, heated at 175 ° C for 5 hours, and then immersed in 50 mL of a 10 ppm Cu (II) ion aqueous solution, and left at 120 ° C for 20 hours. The concentration of Cu (II) ions in the solution is preferably less than 9.8 ppm, more preferably 0 to 9.5 ppm, and still more preferably 0 to 9 ppm. By being in the above range, it is possible to more easily capture metal ions mixed in from outside in various processes of manufacturing a semiconductor device. As a result, it is difficult for metal ions mixed in from the outside to reach the circuit formation surface formed on the wafer, it is possible to suppress the decrease in electrical characteristics, and it is possible to improve product reliability.

[Semiconductor device and manufacturing method thereof]

This embodiment mode includes a semiconductor device in which a wafer is laminated on an adherend using the multilayer adhesive sheet, and a step of laminating a wafer onto the adherend using the multilayer adhesive sheet. Hereinafter, an embodiment of a semiconductor device and a method of manufacturing the same when a multilayer bonding sheet according to this embodiment is used as a wafer bonding film will be described with reference to the drawings.

Hereinafter, a method for manufacturing a semiconductor device using a dicing / wafer bonding film 10 in which a multilayer bonding sheet 3 (hereinafter also referred to as a wafer bonding film 3) of the present embodiment is laminated on a conventionally known dicing film will be described (FIG. 1). . The dicing film according to this embodiment has a structure in which an adhesive layer 2 is laminated on a substrate 1. As a method for manufacturing a semiconductor device using such a dicing / wafer bonding film 10, the method in the first embodiment can be appropriately adopted.

<Fifth Embodiment>

As shown in FIG. 1, the dicing / wafer bonding film of this embodiment has a configuration in which an adhesive 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. In addition, as a method for forming the bonding sheet, as shown in FIG. 5, a configuration in which the bonding sheet 3 'is formed only on the semiconductor wafer bonding portion 3a (refer to FIG. 1) may be employed.

[Cut film]

Examples of the dicing film include a dicing film in which an adhesive layer 2 is laminated on a substrate 1.

(Base material)

The substrate 1 serves as a strength matrix for the dicing / wafer bonding films 10 and 11. Examples include: low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra-low density polyethylene, random copolymer polypropylene, block copolymer polypropylene, homopolypropylene, polybutene, Polyolefins such as polymethylpentene, ethylene-vinyl acetate copolymers, ionomer resins, ethylene- (meth) acrylic copolymers, ethylene- (meth) acrylate (random, alternating) copolymers, ethylene -Polyester such as butene copolymer, ethylene-hexene copolymer, polyurethane, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyetheretherketone , Polyimide, polyetherimide, polyimide, fully aromatic polyimide, polyphenylene sulfide, aromatic polyimide (paper), glass, glass cloth, fluororesin, polyvinyl chloride, Polyvinylidene chloride, cellulose resin, polysiloxane resin, metal (foil), paper, etc. When the adhesive layer 2 is an ultraviolet curable type, it is preferable that the base material 1 is transmissive to ultraviolet rays.

Examples of the material of the substrate 1 include a crosslinked body of the aforementioned resin. And other polymers. The plastic film may be used without stretching, or may be used after being subjected to a uniaxial or biaxial stretching treatment as required. By using a resin sheet provided with heat shrinkability through a stretching process or the like, and by thermally shrinking the substrate 1 after dicing, the bonding area between the adhesive layer 2 and the bonding sheet 3 can be reduced, and the semiconductor wafer can be easily recovered .

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

The base material 1 may be appropriately selected and used from the same or different types of materials, and a material obtained by blending several materials may also be used as required. In addition, in order to impart antistatic performance to the substrate 1, a vapor-deposited layer containing a conductive material having a thickness of about 30 Å to about 500 Å, including a metal, an alloy, and their oxides, may be provided on the substrate 1. The substrate 1 may be a single layer or two or more layers.

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

In addition, the base material 1 may include various additives (for example, colorants, fillers, plasticizers, anti-aging agents, antioxidants, surfactants, and flame retardants) as long as the effects of the present embodiment are not impaired. Wait).

(Adhesive layer)

The storage elastic modulus of the adhesive layer 2 at 26 ° C. is 1.0 × 10 ⁴ Pa or more and 1.0 × 10 ⁷ Pa or less. Via the adhesive layer 2 having such a range of storage elastic modulus, a moderately crosslinked structure can be formed in the adhesive layer. This can restrict the transfer of the ion trapping agent from the adhesive sheet to the adhesive layer, etc. As a result, it is possible to suppress a decrease in the ion trapping property of the adhesive sheet.

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 adhesive layer is formed and can control the adhesive of the adhesive sheet 3 in a peelable manner. For example, general pressure-sensitive adhesives such as an acrylic adhesive and a rubber-based adhesive can be used. As the pressure-sensitive adhesive, from the viewpoints of cleanliness and cleanability of an electronic component such as a semiconductor wafer or glass, which avoids contamination, using an ultra-pure water or an organic solvent such as an alcohol, an acrylic polymer is preferably used as a base polymer. Acrylic adhesive.

Examples of the acrylic polymer include an acrylic polymer using an acrylate as a main monomer component. Examples of the acrylate include an alkyl (meth) acrylate (for example, methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, sec-butyl ester, tert-butyl ester, Amyl, isoamyl, hexyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, decyl, isodecyl, undecyl, dodecyl, tridecyl Esters, tetradecyl esters, hexadecyl esters, octadecyl esters, eicosyl esters and other alkyl groups having 1 to 30 carbon atoms, especially straight or branched chain alkyl esters having 4 to 18 carbon atoms, etc. ) And one or two or more cycloalkyl (meth) acrylates (for example, cyclopentyl ester, cyclohexyl ester, etc.) as monomer components, acrylic polymers and the like. In addition, (meth) acrylate means an acrylate and / or a methacrylate, and (meth) in this invention all has the same meaning.

In order to improve cohesion, heat resistance, and the like, the acrylic polymer may include units corresponding to other monomer components that can be copolymerized with the alkyl (meth) acrylate or naphthenate, as necessary. Examples of such a monomer component include a carboxyl group-containing monomer such as acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, rich Maleic 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, ( 12-hydroxylauryl methacrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, etc .; monomers containing sulfonic acid groups, such as styrene sulfonic acid, allyl sulfonic acid, 2- ( (Meth) acrylamido-2-methylpropanesulfonic acid, (meth) acrylamidoaminopropanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acrylamidonaphthalenesulfonic acid, etc .; containing Phosphate-based monomers, such as 2-hydroxyethyl acrylamide phosphate; acrylamide, acrylonitrile, and the like. These copolymerizable monomer components may be used alone or in combination of two or more. The use amount of these copolymerizable monomers is preferably 40% by weight or less of the total monomer components.

In addition, the acrylic polymer may include a polyfunctional monomer or the like as a comonomer component as necessary for cross-linking. Examples of such a polyfunctional monomer include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, and Pentylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylic acid Esters, epoxy (meth) acrylates, polyester (meth) acrylates, urethane (meth) acrylates, and the like. These polyfunctional monomers may be used alone or in combination of two or more. It is preferable that the usage-amount of a polyfunctional monomer is 30 weight% or less of all monomer components from a viewpoint of adhesive characteristics etc.

The acrylic polymer can be obtained by polymerizing a single monomer or a mixture of two or more monomers. Polymerization can be via solution polymerization, emulsion polymerization, Bulk polymerization, suspension polymerization, and the like can be performed in any manner. From the standpoint of preventing contamination of clean adherends, it is preferred that the content of low-molecular-weight substances is small, and from the standpoint that the adhesive layer exhibits a predetermined storage elastic modulus, the weight average molecular weight of the acrylic polymer is preferably about 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 higher from the viewpoint of peeling adhesion. It is more preferably -60 ° C or higher. The glass transition temperature is preferably -40 to 15 ° C. Therefore, it is appropriate that the glass transition temperature of the homopolymer is -70 ° C or higher for the main monomer used to form the acrylic polymer. The measuring method of the glass transition temperature (Tg) of an acrylic polymer is based on the description of an Example.

The iodine value of the acrylic polymer is preferably in the range of 5 to 10, and more preferably in the range of 5.5 to 9. When the iodine value is less than 5, there is a case where the effect of reducing the adhesive force after radiation irradiation is insufficient when the adhesive layer 2 is a radiation-curable type. On the other hand, when the iodine value exceeds 10, the adhesive force of the dicing film to the adhesive sheet is increased, and sometimes it is difficult to pick it up. The numerical 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 in the examples.

The hydroxyl value of the acrylic polymer is preferably in the range of 7 to 30, and more preferably in the range of 10 to 25. When the hydroxyl value is less than 7, the effect of reducing the adhesive force after irradiation with radiation when the adhesive layer 2 is a radiation-curable type may be insufficient. On the other hand, when the said hydroxyl value exceeds 30, the adhesive force of a dicing film to a wafer bonding film will increase, and it may become difficult to pick up. The numerical range of the hydroxyl value is a value measured by an acetylation method based on JIS K 0070-1992. The details of the measurement procedure are based on the description in the examples.

In addition, in order to increase the weight-average molecular weight of an acrylic polymer or the like as a base polymer, an external crosslinking agent may be suitably used in the adhesive. Specific means of the external crosslinking method include a method of adding and reacting a so-called crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound, and a melamine-based crosslinking agent. When an external cross-linking agent is used, its amount is appropriately determined depending on the balance with the base polymer to be cross-linked and the use purpose as an adhesive. Generally, it is preferable to mix about 5 weight part or less with respect to 100 weight part of said base polymers, and it is more preferable to mix | blend 0.1-5 weight part. 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-based crosslinking agent with respect to 100 parts by weight of the acrylic resin. In addition, various other conventionally known thickeners, anti-aging agents, and other additives may be used in the adhesive in addition to the aforementioned components.

The adhesive layer 2 may be formed of a radiation-curable adhesive. At this time, before the radiation of the adhesive layer, the storage elastic modulus at 26 ° C. needs to be 1.0 × 10 ⁴ Pa or more and 1.0 × 10 ⁷ Pa or less. The radiation-curable adhesive can be easily reduced in 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 a portion 2 a corresponding to the semiconductor wafer bonding portion 3 a with radiation, a difference in adhesion with a portion 2 b other than the portion 2 a may be provided.

In addition, by curing the radiation-curable adhesive layer 2 according to the adhesive sheet 3 ', it is possible to easily form the portion 2a in which the adhesive force significantly decreases. Since the adhesive sheet 3 'is adhered to the portion 2a which is cured and the adhesive force is reduced, the interface between the portion 2a and the adhesive sheet 3' has a property of being easily peeled off when picked up. On the other hand, the portion not irradiated with radiation has sufficient adhesive force to form a portion 2b.

As described above, in the adhesive layer 2 of the dicing / wafer bonding film 10 shown in FIG. 1, the part 2 b formed by the uncured radiation-curable adhesive is adhered to the adhesive sheet 3, and the retention during dicing can be ensured. force. In this way, the radiation-curable adhesive can support the adhesive sheet 3 for fixing a semiconductor wafer to an adherend such as a substrate with a good adhesive-peel balance. In the adhesive layer 2 of the dicing / wafer bonding film 11 shown in FIG. 5, the portion 2 b can fix a wafer ring.

As the radiation-curable adhesive, a radiation-curable adhesive having a radiation-curable functional group such as a carbon-carbon double bond and exhibiting adhesiveness can be used without particular limitation. As the radiation-curable adhesive, for example, an addition type radiation curing in which a radiation-curable monomer component or an oligomer component is added to a general pressure-sensitive adhesive such as an acrylic adhesive and a rubber-based adhesive can be exemplified. Type adhesive.

Examples of the radiation-curable monomer component to be blended include urethane oligomer, urethane (meth) acrylate, trimethylolpropane tri (meth) acrylate, and tetrahydroxy Methylmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , 1,4-butanediol di (meth) acrylate and the like. Examples of the radiation-curable oligomer component include various oligomers such as urethanes, polyethers, polyesters, polycarbonates, and polybutadienes. The weight-average molecular weight is about 100 to about A range of 30,000 is appropriate. The amount of the radiation-curable monomer component or oligomer component can be appropriately determined according to the type of the adhesive layer, so as to reduce the amount of adhesive force of the adhesive layer. Generally speaking, relative to the composition 100 parts by weight of the base polymer such as the acrylic polymer of the adhesive is, for example, about 5 parts by weight to about 500 parts by weight, and preferably about 40 parts by weight to about 150 parts by weight.

In addition, as the radiation-curable adhesive, in addition to the additive-type radiation-curable adhesive described above, examples include polymerization using a carbon-carbon double bond in a polymer side chain or a main chain or at the end of the main chain. As a base polymer, the internal radiation-curing adhesive. The internal radiation-curing adhesive does not need to include or does not include a large amount of oligomer components as low molecular weight components, so the oligomer components and the like do not move in the adhesive over time, and can form a stable layer structure adhesion. Agent layers are therefore preferred.

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

The method of introducing a carbon-carbon double bond into the acrylic polymer is not particularly limited, and various methods can be adopted, but it is relatively easy to design a carbon-carbon double bond into a polymer side chain. For example, first, 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 maintained to maintain the radiation curability of the carbon-carbon double bond. In the case of condensation or addition reaction.

Examples of combinations of these functional groups include, for example, a carboxyl group and an epoxy group, a carboxyl group and an aziridinyl group, a hydroxyl group and an isocyanate group, and the like. Among these combinations of functional groups, a combination of a hydroxyl group and an isocyanate group is preferred in terms of ease of reaction tracking. In addition, if the carbon -A combination of an acrylic polymer having a carbon double bond, the functional group may be on either of the acrylic polymer and the compound. In the preferred combination, the acrylic polymer preferably has a hydroxyl group and the compound has an isocyanate. Situation. In this case, examples of the isocyanate compound having a carbon-carbon double bond include methacryl 醯 isocyanate, 2-methacryl 醯 oxyethyl isocyanate, and m-isopropenyl-α, α-dimethylbiphenyl 醯Isocyanate, etc. In addition, as the acrylic polymer, an ether compound in which the above-exemplified hydroxyl-containing monomer or 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether are copolymerized can be used. And other polymers.

The intrinsic radiation-curing adhesive may use the basic polymer (especially an acrylic polymer) having a carbon-carbon double bond alone, and may also be compatible with the radiation curability within a range that does not impair the characteristics. Monomer or oligomer. The radiation-curable oligomer component and the like are usually in a range of 30 parts by weight, and preferably in a range of 0 to 10 parts by weight based on 100 parts by weight of the base polymer.

The radiation-curable adhesive may include a photopolymerization initiator when cured by ultraviolet rays or the like. Examples of the photopolymerization initiator include: α-keto alcohol compounds, such as 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α, α ' -Dimethylacetophenone, 2-methyl-2-hydroxyphenylacetone, 1-hydroxycyclohexylphenyl ketone, etc .; acetophenone compounds, 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 ether, benzoin isopropyl ether, fennel methyl ether, etc .; ketal compounds, such as biphenyl dimethyl ketal, etc .; aromatic sulfone Fluorine compounds, such as 2-naphthalenesulfonyl chloride, etc .; Photoactive oxime compounds, such as 1-phenyl-1,2-propanedione-2- (O-ethoxy Carbonyl) oxime, etc .; benzophenone compounds, such as benzophenone, benzophenone benzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, etc .; thioxanthone compounds, Such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2, 4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc .; camphorquinone; haloketone; fluorenylphosphine oxide; fluorenylphosphonate and the like. The compounding quantity of a photoinitiator is about 0.05 weight part-about 20 weight part with respect to 100 weight part of base polymers, such as an acrylic polymer which comprises an adhesive agent.

When forming the adhesive layer 2 via a radiation-curable adhesive, it is preferable to irradiate a part of the adhesive layer 2 with radiation such that the adhesive force of the portion 2a is less than the adhesive force of the portion 2b. In the dicing / wafer bonding film of FIG. 1, for example, the relationship between the SUS304 plate (# 2000 polishing) as the adherend is the adhesion force of part 2a <the adhesion force of part 2b.

Examples of the method for forming the portion 2a in the adhesive layer 2 include: after forming a radiation-curable adhesive layer 2 on the substrate 1, the portion 2a is partially irradiated with radiation to be cured. method. The local radiation irradiation can be performed through a photomask formed with a pattern corresponding to a portion 3b other than the semiconductor wafer sticking portion 3a. In addition, a method of curing by irradiating ultraviolet rays in a spot shape can be mentioned. The radiation-curable adhesive layer 2 can be formed by transferring the radiation-curable adhesive layer provided on the separator to the substrate 1. The local radiation irradiation may be performed on the radiation-curable adhesive layer 2 provided on the separator.

In addition, when forming the adhesive layer 2 via a radiation-curable adhesive, it is possible to use light-shielding of all or a part of at least one side of the substrate 1 except for a portion corresponding to the semiconductor wafer adhesion portion 3a. Substrate, in After the radiation-curable adhesive layer 2 is formed on the substrate, radiation is irradiated to cure a portion corresponding to the semiconductor wafer pasting portion 3a, thereby forming the portion 2a with reduced adhesion. The light-shielding material can be produced by printing or vapor-depositing a material that can be used as a photomask on a support film. Through the manufacturing method, the dicing / wafer bonding film 10 according to the present embodiment can be efficiently manufactured.

In addition, when curing failure occurs due to oxygen during radiation irradiation, it is preferable to block oxygen (air) from the surface of the radiation-curable adhesive layer 2 by any method. Examples thereof include a method of covering the surface of the adhesive layer 2 with a separator, or a method of radiating radiation such as ultraviolet rays in a nitrogen atmosphere.

The thickness of the adhesive layer 2 is not particularly limited, but is preferably from about 1 μm to about 50 μm from the viewpoint of simultaneously preventing defects on the wafer dicing surface and fixing and holding the adhesive layer. It is preferably 2 μm to 30 μm, and more preferably 5 μm to 25 μm.

The adhesive layer 2 may include various additives (for example, colorants, thickeners, extenders, fillers, tackifiers, plasticizers, and Aging agents, antioxidants, surfactants, cross-linking agents, etc.).

[Next film]

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

The thickness of the adhesive sheet 3 is not particularly limited. Since the transfer of the ion trapping agent from the adhesive sheet 3 to the adhesive layer can be suppressed, the thickness can be easily reduced in order to increase the capacity of the semiconductor device. The thickness of the adhesive sheet is preferably The thickness can be reduced to a range of 3 μm to 150 μm, the thickness can be reduced to a range of 4 μm to 120 μm, and a range of 5 μm to 100 μm is more preferred.

For the adhesive sheet 3, after immersing an adhesive sheet having a weight of 2.5 g in 50 mL of an aqueous solution containing 10 ppm copper ions and leaving it at 120 ° C. for 20 hours, the copper ion concentration in the aqueous solution is preferably 0 to 9.8 ppm, more preferably It is 0 to 9.5 ppm, and more preferably 0 to 9.0 ppm. The adhesive sheet has such a copper ion trapping property, and can trap metal ions such as a semiconductor wafer from the outside during the manufacturing process of the semiconductor device. As a result, it is difficult for metal ions mixed in from the outside to reach the circuit formation surface formed on the wafer, it is possible to suppress the decrease in electrical characteristics, and it is possible to improve product reliability. In this embodiment, as a method for making the copper ion concentration after the copper ion capture is 0 to 9.8 ppm, in addition to the method of including an ion trapping agent in the adhesive sheet as described above, it can also be introduced into 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 implantation of boron or an n-type dopant, and the like.

The tensile storage elastic modulus of the adhesive sheet at 60 ° C. before thermal 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, and still more preferably 0.1 MPa or more and 50 MPa or less. By adjusting the tensile storage elastic modulus at 60 ° C before thermal curing to 0.01 MPa or more, the shape of the film can be maintained, and good workability can be imparted. In addition, by adjusting the tensile storage elastic modulus at 60 ° C. before thermal curing to 1000 MPa or less, good wettability to an adherend can be imparted.

[Manufacturing method of dicing / wafer bonding film]

The dicing / wafer bonding films 10 and 11 according to the present embodiment can be passed, for example, via The dicing film and the adhesive sheet are separately made, and finally they are pasted to make them. Specifically, it can be produced according to 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 calendering method, a casting method in an organic solvent, a blow extrusion method in a closed system, a T-die extrusion method, a coextrusion method, and a dry lamination method. Wait.

Next, an adhesive composition for forming an adhesive layer was prepared. The adhesive composition contains a resin, an additive, and the like described in the item of the adhesive layer. The prepared adhesive composition is applied on the substrate 1 to form a coating film, and then the coating film is dried (heat-crosslinked as necessary) under a predetermined condition to form an adhesive layer 2. The coating method is not particularly limited, and examples thereof include roll coating, screen coating, and gravure coating. The drying conditions are performed, for example, in a range of a drying temperature of 80 to 150 ° C. and a drying time of 0.5 to 5 minutes. Alternatively, after the adhesive composition is applied to the separator to form a coating film, the coating film may be dried under the aforementioned drying conditions to form the adhesive layer 2. After that, the adhesive layer 2 is adhered to the substrate 1 together with the separator. Thus, a dicing film having a substrate 1 and an adhesive layer 2 was produced. The dicing film may include 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 this 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 until homogeneous, thereby being obtained in the form of an adhesive composition solution.

The organic solvent is not limited as long as it is an organic solvent that can uniformly dissolve, knead, or disperse the components constituting the adhesive sheet, and a conventional one can be used. Well-known organic solvents. 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. From the viewpoint of fast drying speed and availability, it is preferable to use methyl ethyl ketone, cyclohexanone, or the like.

The adhesive composition solution prepared as described above is applied to a substrate separator to a predetermined thickness to form a coating film, and then the coating film is dried under predetermined conditions. The substrate separator can be surface-coated with a polyethylene terephthalate (PET), polyethylene, polypropylene, or a release agent such as a fluorine-containing release agent or a long-chain alkyl acrylate-based release agent. Plastic film or paper. The coating method is not particularly limited, and examples thereof include roll coating, screen coating, and gravure coating. The drying conditions are performed, for example, in a range of 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 is peeled from the dicing film, and the adhesive sheet and the dicing film are affixed such that the adhesive sheet and the adhesive layer are adhesive surfaces. Adhesion can be performed, for example, by crimping. In this case, the lamination temperature is not particularly limited, and for example, it is preferably 30 to 50 ° C, and more preferably 35 to 45 ° C. In addition, the linear pressure is not particularly limited, but is preferably 0.1 to 20 kgf / cm, and more preferably 1 to 10 kgf / cm. Then, the substrate separator on the adhesive film is peeled, and the dicing / wafer bonding film of this embodiment can be obtained.

[Semiconductor device and manufacturing method thereof]

As the semiconductor device and the manufacturing method thereof of the present embodiment, the semiconductor device and the manufacturing method described in the first embodiment can be appropriately adopted.

Examples

Hereinafter, preferred embodiments of the present invention will be described specifically and exemplarily. but, The materials, blending amounts, and the like described in this example are not limited to the gist of the present invention unless they are specifically limited. In addition, hereinafter, when there is a part, it means a weight part.

[First Embodiment]

The following examples and the like correspond to the adhesive sheet of the first embodiment.

(Example 1)

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

The adhesive composition solution was applied to a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a release treatment of polysiloxane, and then dried at 130 ° C. for 2 minutes. . Thereby, the adhesive sheet of Example 1 with a thickness of 20 μm was produced.

(Example 2)

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

The adhesive composition solution was applied to a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a release treatment of polysiloxane, and then dried at 130 ° C. for 2 minutes. . Thereby, the adhesive sheet of Example 2 with a thickness of 20 μm was produced.

(Example 3)

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

The adhesive composition solution was applied to a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a release treatment of polysiloxane, and then dried at 130 ° C. for 2 minutes. . Thereby, the adhesive sheet of Example 3 with a thickness of 20 μm was produced.

(Comparative example 1)

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

製造，TT-LX，三唑化合物) 1份

Manufacturing, TT-LX, triazole compound) 1 part

The adhesive composition solution was applied to a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a release treatment of polysiloxane, and then dried at 130 ° C. for 2 minutes. . Thereby, the adhesive sheet of the comparative example 1 with a thickness of 20 micrometers was produced.

(Comparative example 2)

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

The adhesive composition solution was applied to a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a release treatment of polysiloxane, and then dried at 130 ° C. for 2 minutes. . Thereby, the adhesive sheet of the comparative example 2 of thickness 20 micrometers was produced.

(Comparative example 3)

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

The adhesive composition solution was applied to a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a release treatment of polysiloxane, and then dried at 130 ° C. for 2 minutes. . Thereby, the adhesive sheet of Comparative Example 3 with a thickness of 20 μm was produced.

(Comparative Example 4)

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

The adhesive composition solution was applied to a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a release treatment of polysiloxane, and then dried at 130 ° C. for 2 minutes. . Thereby, a bonding sheet of Comparative Example 4 having a thickness of 20 μm was prepared.

(Evaluation of copper ion trapping property)

The adhesive sheets (thickness: 20 μm) of the examples and comparative examples were cut to 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. The pieces were placed at a diameter of 58 mm and a height of 37 mm Into a cylindrical closed Teflon (registered trademark) container, 50 ml of a 10 ppm copper (II) ion aqueous solution was added. Then, it was left to stand at 120 degreeC for 20 hours in the constant temperature dryer (PV-231 made by Espec Corporation). After the film was taken out, the copper ion concentration in the aqueous solution was measured using ICP-AES (SII NanoTechnology Co., Ltd., SPS-1700HVR). When the concentration of the copper ion 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 1.

(Void disappearance)

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

(Wet Reflow Resistance)

The adhesive sheets (thickness: 20 μm) of the examples and comparative examples were each affixed to a semiconductor wafer of 10 mm square at a temperature of 40 ° C., and the semiconductor wafer was mounted on the BGA substrate through each adhesive sheet. The installation conditions are 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 with a dryer, and then sealed with a sealing resin (manufactured by Nitto Denko Corporation, GE-100). The sealing conditions were: heating temperature of 175 ° C for 90 seconds. Then, under the conditions of 85 ° C, 60% RH, and 168 hours, the BGA substrate on which the semiconductor wafer was mounted was mounted to IR reflow soldering which was set to hold at 260 ° C or higher for 10 seconds. In the furnace. Then, the sealed semiconductor device was cut with a glass knife, and its cross section was observed with an ultrasonic microscope, and it was confirmed whether there was peeling at the boundary between each thermosetting wafer bonding film and the BGA substrate. Nine semiconductor wafers were confirmed. When the number of peeled semiconductor wafers was 3 or less, the evaluation was ○, and when it was 4 or more, the evaluation was ×. The results are shown in Table 1 below.

(result)

In Examples, good results were obtained for copper ion trapping property, void disappearance property, and wet reflow resistance. On the other hand, in Comparative Example 1, TT-LX functioned as an alkaline catalyst, promoted the reaction between the carboxyl group of the acrylic resin and the epoxy resin, hardened violently, and the void disappearance property during molding was reduced. In Comparative Example 2, since the acrylic resin does not have a functional group that reacts with the curable resin or the complex-forming organic compound (triazole compound), it is possible to ensure void-disappearance during molding. However, since the acrylic resin is not cross-linked, it cannot withstand the reflow test, and it causes peeling at the adhering interface to generate voids. In addition, in Comparative Example 3, since dodecyl gallate reacted with the epoxy group of the acrylic resin, it hardened violently, and the void disappearance property at the time of molding decreased. In addition, since Comparative Example 4 does not contain a complex-forming organic compound capable of forming a complex with a cation, it cannot capture metal ions.

[Second Embodiment]

The following examples and the like correspond to the adhesive sheet of the second embodiment.

(Example 1)

Ion trapping agent (IXE-100 manufactured by Toa Synthesis Co., Ltd.) 25 parts, 80 parts acrylic resin (SG-80H manufactured by Nagasechemtex Co., Ltd., including epoxy group, weight average molecular weight 350,000), 10 parts epoxy resin (JER828 manufactured by Mitsubishi Chemical Corporation), phenol resin ( 10 parts of MEH7800 manufactured by Meiwa Chemical Co., Ltd. and 125 parts of spherical silica (SO-25R manufactured by Admatechs Co., Ltd.) were dissolved in methyl ethyl ketone to prepare a concentration of 23.6% by weight.

This adhesive composition solution was applied as a release liner to a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a release treatment of polysiloxane, and then Dry at 130 ° C for 2 minutes. Thus, an adhesive sheet having a thickness of 25 μm was produced.

(Example 2)

5 parts of ion trapping agent (BT-120 manufactured by Chengbei Chemical Co., Ltd.), 50 parts of acrylic resin (SG-80H manufactured by Nagasechemtex Co., Ltd., including epoxy group, weight average molecular weight 350,000), epoxy resin (JER828 manufactured by Mitsubishi Chemical Corporation) 25 parts of phenolic resin (MEH7800 manufactured by Meiwa Chemical Co., Ltd.) and 50 parts of spherical silica (SO-25R manufactured by Admatechs Corporation) were dissolved in methyl ethyl ketone to prepare The concentration was 23.6% by weight.

This adhesive composition solution was applied as a release liner to a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a release treatment of polysiloxane, and then Dry at 130 ° C for 2 minutes. Thus, an adhesive sheet having a thickness of 25 μm was produced.

(Example 3)

Ion trapping agent (IXE-100 manufactured by Toa Synthesis Co., Ltd.) 25 parts, 80 parts acrylic resin (SG-708-6 manufactured by Nagasechemtex Co., Ltd., including carboxyl group, weight average molecular weight 800,000), 10 parts epoxy resin (JER828 manufactured by Mitsubishi Chemical Corporation), phenol resin ( 10 parts of MEH7800 manufactured by Meiwa Chemical Co., Ltd. and 80 parts of spherical silica (SO-25R manufactured by Admatechs Co., Ltd.) were dissolved in methyl ethyl ketone to prepare a concentration of 23.6% by weight.

This adhesive composition solution was applied as a release liner to a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a release treatment of polysiloxane, and then Dry at 130 ° C for 2 minutes. Thus, an adhesive sheet having a thickness of 25 μm was produced.

(Example 4)

25 parts of ion trapping agent (IXE-100 manufactured by Toa Synthesis Co., Ltd.), 50 parts of acrylic resin (SG-708-6 manufactured by Nagasechemtex Co., Ltd., including carboxyl group, weight average molecular weight 350,000), epoxy resin (JER828 manufactured by Mitsubishi Chemical Corporation), 30 parts of phenolic resin (MEH7800 manufactured by Meiwa Chemical Co., Ltd.), and 110 parts of spherical silica (SO-25R manufactured by Admatechs Corporation) were dissolved in methyl ethyl ketone to prepare The concentration was 23.6% by weight.

This adhesive composition solution was applied as a release liner to a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a release treatment of polysiloxane, and then Dry at 130 ° C for 2 minutes. Thus, an adhesive sheet having a thickness of 25 μm was produced.

(Comparative example 1)

Ion trapping agent (IXE-100 manufactured by Toa Synthesis Co., Ltd.) 25 parts, 80 parts acrylic resin (UH2000 manufactured by Toa Synthesis Co., Ltd., weight average molecular weight 12,000), 10 parts epoxy resin (HP-7200 manufactured by DIC Corporation), phenolic resin (Mingwa Chemical Co., Ltd. 10 parts of MEH7800) and 100 parts of spherical silica (SO-25R manufactured by Admatechs Co., Ltd.) were dissolved in methyl ethyl ketone to prepare a concentration of 23.6% by weight.

This adhesive composition solution was applied as a release liner to a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a release treatment of polysiloxane, and then Dry at 130 ° C for 2 minutes. Thus, an adhesive sheet having a thickness of 25 μm was produced.

(Comparative example 2)

80 parts of acrylic resin (SG-80H manufactured by Nagasechemtex Co., Ltd., weight average molecular weight 350,000), 10 parts of epoxy resin (JER828 manufactured by Mitsubishi Chemical Corporation), and phenol resin (manufactured by Meiwa Chemical Co., Ltd. 10 parts of MEH7800) and 100 parts of spherical silica (SO-25R manufactured by Admatechs Co., Ltd.) were dissolved in methyl ethyl ketone to prepare a concentration of 23.6% by weight.

This adhesive composition solution was applied as a release liner to a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a release treatment of polysiloxane, and then Dry at 130 ° C for 2 minutes. Thus, an adhesive sheet having a thickness of 25 μm was produced.

(Measurement of tensile storage elastic modulus at 260 ° C after heat curing)

After the adhesive sheets of Examples and Comparative Examples were left in an oven at 175 ° C for 5 hours, they were measured using a viscoelasticity measuring device (RSA-II, manufactured by Rheometric). Tensile storage elastic modulus after curing at 260 ° C. For the measurement, a measurement sample obtained by pasting and cutting a plurality of prepared adhesive sheets into a length of 30 mm, a width of 10 mm, and a thickness of 0.20 mm was used. The measurement of the tensile storage elastic modulus was performed in a temperature range of -40 to 300 ° C, a frequency of 1 Hz, a strain amount of 0.1%, and a heating rate of 10 ° C / min. The measured values at 260 ° C at this time are shown in Table 2.

(Evaluation of copper ion trapping property)

Each adhesive sheet of the Examples and Comparative Examples was cut to a weight of about 2.5 g, and the cut sample was placed in a cylindrical closed Teflon (registered trademark) container with a diameter of 58 mm and a height of 37 mm, and 10 ppm of copper was added. (II) 50 ml of an ionic aqueous solution. Then, it was left to stand at 120 degreeC for 20 hours in the constant temperature dryer (PV-231 made by Espec Corporation). After the film was taken out, the copper ion concentration in the aqueous solution was measured using ICP-AES (SII NanoTechnology Co., Ltd., SPS-1700HVR). When the concentration of the copper ion 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 difference between the initial copper ion concentration (10 ppm) and the copper ion concentration measured after the test is listed in Table 2 as the ion trapping amount (ppm).

(Data retention test)

The test is based on the standard JESD22-A117B specified by JEDEC. Specifically, data was written in a semiconductor package produced by the following procedure, and the data retention of the sample after the accelerated test was placed in a 150 ° C dryer for 1000 hours was confirmed. When there are 5 or less packages, the evaluation is ○, and when there are more than 6 packages, the evaluation is ×. The results are shown in Table 2.

(Semiconductor Packaging Production)

The circuit-formed wafer was ground to a thickness of 50 μm. The wafer and the actual After the respective bonding sheets of Examples and Comparative Examples were bonded at 60 ° C., dicing (dicing apparatus: manufactured by DISCO Corporation, DFD6361) was performed to prepare a 10 mm × 10 mm wafer with the bonding sheet bonded. The produced wafer with a bonding sheet was bonded to a lead frame (Alloy42). Wafer bonding was performed using a wafer bonding machine (SPA-300, manufactured by Shinkawa Co., Ltd.) under a condition of applying a load (0.1 MPa) at a temperature of 120 ° C and heating for 1 second. Then, wire bonding was performed at 175 ° C using an Au wire having a wire diameter of 23 µm, and sealing was performed at 175 ° C for 2 minutes with a sealing resin (manufactured by Nitto Denko Corporation, GE-100). Then, the sealing resin was heat-cured at 175 ° C for 5 hours to produce a semiconductor package.

As can be seen from the results in Table 2, the adhesive storage elastic modulus, copper ion capture property, and data retention property of the adhesive sheet of the example at 260 ° C after thermal curing were all good results. On the other hand, the copper ion capture of the adhesive sheet of Comparative Example 1 Although good, data retention is caused by data retention errors in multiple samples. It is thought that this is because the tensile storage elastic modulus at 260 ° C after heat curing is a low value of 0.4 MPa, so peeling occurs between the bonding sheet and the semiconductor wafer during the accelerated test, and the metal ion trapping effect of the bonding sheet is reduced. . In addition, since the adhesive sheet of Comparative Example 2 did not contain an ion trapping agent, it hardly exhibited copper ion trapping property. As a result, a data retention error occurred in all samples in the data retention test.

[Third Embodiment]

The following examples and the like correspond to the bonding sheet according to the third embodiment.

(Example 1)

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

The adhesive composition solution was applied to a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a release treatment of polysiloxane, and then dried at 130 ° C. for 2 minutes. . Thereby, the adhesive sheet of Example 1 with a thickness of 5 μm was produced.

(Example 2)

The following (a) to (c) were dissolved in methyl ethyl ketone to obtain a concentration of 20 weight % Adhesive solution.

The adhesive composition solution was applied to a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a release treatment of polysiloxane, and then dried at 130 ° C. for 2 minutes. . Thereby, the adhesive sheet of Example 2 with a thickness of 5 μm was produced.

(Example 3)

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

The adhesive composition solution was applied to a mold release site composed of a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a mold release treatment of polysiloxane. After processing the film, it was dried at 130 ° C for 2 minutes. Thereby, the adhesive sheet of Example 3 with a thickness of 15 μm was produced.

(Comparative example 1)

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

The adhesive composition solution was applied to a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a release treatment of polysiloxane, and then dried at 130 ° C. for 2 minutes. . Thereby, the adhesive sheet of Comparative Example 1 with a thickness of 5 μm was produced.

(Comparative example 2)

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

The adhesive composition solution was applied to a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a release treatment of polysiloxane, and then dried at 130 ° C. for 2 minutes. . Thus, an adhesive sheet of Comparative Example 2 having a thickness of 15 μm was produced.

(Comparative example 3)

(A) and (b) below were dissolved in methyl ethyl ketone to obtain a 20% by weight adhesive composition solution.

The adhesive composition solution was applied to a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a release treatment of polysiloxane, and then dried at 130 ° C. for 2 minutes. . Thereby, the adhesive sheet of Comparative Example 3 with a thickness of 5 μm was produced.

(Comparative Example 4)

The following (a) and (c) were dissolved in methyl ethyl ketone to obtain a 20% by weight adhesive composition solution.

(a) Acrylic resin including epoxy group (Nagasechemtex)

The adhesive composition solution was applied to a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a release treatment of polysiloxane, and then dried at 130 ° C. for 2 minutes. . Thereby, a bonding sheet of Comparative Example 4 having a thickness of 5 μm was produced.

(Comparative example 5)

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

The adhesive composition solution was applied to a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a release treatment of polysiloxane, and then dried at 130 ° C. for 2 minutes. . Thereby, a bonding sheet of Comparative Example 5 having a thickness of 5 μm was prepared.

(Comparative Example 6)

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

(a) Acrylic resin including hydroxyl (Nagasechemtex shares

The adhesive composition solution was applied to a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a release treatment of polysiloxane, and then dried at 130 ° C. for 2 minutes. . Thereby, the adhesive sheet of Comparative Example 6 with a thickness of 5 μm was produced.

The components (a) used in the examples and comparative examples are summarized in Table 3. Moreover, the compounding quantity of each component in an Example and a comparative example is summarized in Table 4.

(Measurement of (a) weight average molecular weight of component)

The component (a) used in each of the examples and comparative examples was measured for weight average molecular weight by gel permeation chromatography. The weight-average molecular weight refers to a polystyrene conversion value using gel permeation chromatography (GPC) using a calibration curve based on a standard polystyrene. In gel permeation chromatography, four columns of TSK G2000H HR, G3000H HR, G4000H HR, and GMH-H HR (all manufactured by Tosoh Corporation) were used in series. Tetrahydrofuran was used as the eluent at a flow rate of 1 ml / min. The temperature was 40 ° C., the concentration of the sample was 0.1% by weight in a tetrahydrofuran solution, and the sample injection amount was 500 μl. A differential refractometer was used as a detector.

(Evaluation of copper ion trapping property)

Each adhesive sheet of the Examples and Comparative Examples was cut to a weight of about 2.5 g, and the cut sample was placed in a cylindrical closed Teflon (registered trademark) container with a diameter of 58 mm and a height of 37 mm, and 10 ppm of copper was added. (II) 50 ml of an ionic aqueous solution. Then, it was left to stand at 120 degreeC for 20 hours in the constant temperature dryer (PV-231 made by Espec Corporation). After the film was taken out, the copper ion concentration in the aqueous solution was measured using ICP-AES (SII NanoTechnology Co., Ltd., SPS-1700HVR). When the concentration of the copper ion 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 5.

(Evaluation of wafer damage during wafer bonding)

Each adhesive sheet of the examples and comparative examples was pasted on a mirror wafer having a thickness of 500 μm at 60 ° C., and then diced to produce a 5 mm × 5 mm wafer with the adhesive sheet attached. The produced wafer with the adhesive sheet is at 120 ° C, The wafer was bonded to a 10 mm × 10 mm wafer under the conditions of 0.25 kg and 1 second. Wafer bonding was performed using a wafer bonding machine (SPA-300 manufactured by Shinkawa Co., Ltd.) under a condition of applying a load (0.25 MPa) at a temperature of 120 ° C and heating for 1 second. A case where no damage occurred in all of the 50 wafers bonded to the wafer was evaluated as ○, and a case where damage such as a defect or crack occurred was evaluated as ×. The results are shown in Table 5.

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

The sample after the wafer bonding in the wafer damage evaluation was heated at 175 ° C. for 1 hour to cure the adhesive sheet. A shear tester (Dage 4000, manufactured by Dage, Inc.) was used to measure the shear adhesion between the adhesive wafer and the wafer. The conditions of the shear test were: a measurement speed of 500 μm / sec, a measurement gap of 100 μm, and a plateau temperature of 175 ° C. A case where the shear adhesive force was 0.02 MPa or more was evaluated as ○, and a case where the shear adhesion force was less than 0.02 MPa was evaluated as x. The results are shown in Table 5.

(Wet Reflow Resistance)

Each adhesive sheet of the examples and comparative examples was attached to a 10 mm square semiconductor wafer at a temperature of 40 ° C, and the semiconductor wafer was mounted on the BGA substrate via each adhesive sheet. The installation conditions are a temperature of 120 ° C, a pressure of 0.1 MPa, and a time of 1 second. Then, the BGA substrate on which the semiconductor wafer was mounted was heat-treated at 175 ° C for 30 minutes with a dryer, and then sealed with a sealing resin (manufactured by Nitto Denko Corporation, GE-100). The sealing conditions were: heating temperature of 175 ° C for 90 seconds. Then, under the conditions of 85 ° C., 60% RH, and 168 hours, the BGA substrate on which the semiconductor wafer was mounted was mounted to IR reflow for temperature setting to maintain the temperature at 260 ° C. for 10 seconds In the furnace. Then, the sealed semiconductor device was cut with a glass knife, and ultrasonic waves were used. The cross section was observed under a microscope, and the presence or absence of peeling at the boundary between each thermosetting wafer bonding film and the BGA substrate was confirmed. Nine semiconductor wafers were confirmed. When the number of peeled semiconductor wafers was 3 or less, the evaluation was ○, and when it was 4 or more, the evaluation was ×. The results are shown in Table 5.

It is clear from Table 5 that the copper ion trapping property of the adhesive sheet of the example, the wafer damage property during wafer bonding, the shear adhesion force, and the wet reflow resistance are all good results. On the other hand, since the adhesive sheets of Comparative Examples 1 and 2 included silicon dioxide, defects or cracks occurred during wafer bonding. Since the adhesive sheet of Comparative Example 3 does not contain a complexing agent, it cannot capture a copper ion. The adhesive sheet of Comparative Example 4 does not contain the component (b). Therefore, the adhesive sheet is not cured even if it is subjected to a heat curing treatment. Therefore, the adhesive force at high temperature is reduced, and the semiconductor wafer is peeled from the BGA substrate in the wet reflow resistance test. The component (a) in the adhesive sheet of Comparative Example 5 has a low weight average molecular weight, and therefore has a low modulus of elasticity at high temperatures, and a sufficient high-temperature shear adhesion cannot be obtained. In addition, for the same reason, in the wet reflow resistance test Peeling occurs. The component (a) in the adhesive sheet of Comparative Example 6 has a sufficient weight average molecular weight, and thus a shear adhesive force at a high temperature was obtained. However, the component (a) and the component (b) do not have a functional group capable of being crosslinked with each other. Therefore, the component (a) and the component (b) are not crosslinked by a heat curing treatment. Therefore, the adhesive force at high temperatures is reduced, Peeling occurred in the wet reflow test.

[Fourth embodiment]

The following examples and the like correspond to the multilayer adhesive sheet of the fourth embodiment.

(Example 1)

(Ion trap layer)

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

(a) Acrylic resin having an epoxy group as a functional group

The ion-trapping composition solution was applied as a release liner to a release-treated film composed of a polyethylene terephthalate film (thickness: 50 μm) after being subjected to a release treatment of polysiloxane. . After drying at 130 ° C. for 2 minutes, an ion-trapping layer having a thickness of 5 μm was prepared.

(Adjacent layer)

A bonding layer having a thickness of 10 μm was prepared by the same procedure as above except that (d) was changed to 0 parts by weight.

(Manufacturing of multilayer adhesive film)

Using a laminator, the produced ion-trapping layer and the adhesive layer were adhered under the conditions of a temperature of 40 ° C., a pressure of 0.2 MPa, and a speed of 10 mm / sec, to produce a two-layer adhesive sheet.

(Examples 2 to 10, Comparative Examples 1 to 4)

A multilayer adhesive sheet was obtained in the same manner as in Example 1 except that the composition and film thickness were changed to the values shown in Table 6. In addition, as the organic low molecular weight compound in the table, the following compounds were used.

SG-708-6: an acrylic resin with a carboxyl group as a functional group manufactured by Nagasechemtex Co., Ltd., having a number average molecular weight of 700,000 g / mol and an acid value of 9 mgKOH / g

EPPN-501HY: Tris (hydroxyphenyl) methane type epoxy resin manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 169g / eq

Dodecyl gallate: manufactured by Tokyo Chemical Industry Co., Ltd., trade name: dodecyl gallate

BT-120: 1,2,3-benzotriazole manufactured by Chengbei Chemical Co., Ltd.

Alizarin: manufactured by Tokyo Chemical Industry Co., Ltd.

P5T: manufactured by Toyobo Co., Ltd., 5-phenyl-1H-tetrazole

Methyl gallate: manufactured by Tokyo Chemical Industry Co., Ltd.

2,2’-bipyridine: Tokyo Chemical Industry Co., Ltd.

進行以下的評價。

The following evaluations were performed.

(Evaluation method of metal ion trapping property)

An evaluation sheet (thickness: 20 μm) was produced using the ion-trapping composition used in the examples and comparative examples. This evaluation piece was cut into 2.5 g, heated at 175 ° C for 5 hours, and then placed in a crucible made of Teflon (registered trademark), and 50 mL of a 10 ppm Cu (II) ion aqueous solution was added. Then, it was left to stand at 120 degreeC for 20 hours in the constant temperature dryer (PV-231 made by Espec Corporation). After taking out the sheet for evaluation, the concentration of copper (II) ion in the aqueous solution was measured using ICP-AES (SII NanoTechnology Co., Ltd., SPS-1700HVR). When the concentration of the copper (II) ion in the aqueous solution was less than 9.8 ppm, the evaluation was ○, and when the concentration was 9.8 to 10 ppm, the evaluation was ×. The results are shown in Table 7.

(Does the void disappear after the resin sealing step)

On the ion-trapping layer side of the two-layer adhesive sheet obtained in the examples and comparative examples, a 10 mm square semiconductor wafer was pasted at a temperature of 40 ° C., and a BGA substrate was pasted to the adhesive layer side. The semiconductor wafer is then mounted on a BGA substrate. The installation conditions are a temperature of 120 ° C, a pressure of 0.1 MPa, and a time of 1 second.

Then, the BGA substrate on which the semiconductor wafer was mounted was heat-treated at 175 ° C for 30 minutes with a dryer, and then sealed with a sealing resin (manufactured by Nitto Denko Corporation, GE-100). The sealing conditions were: heating temperature of 175 ° C for 90 seconds.

Next, the sealed semiconductor device was cut with a glass knife, and its cross section was observed with an ultrasonic microscope, and the void area in the adhesion surface of each adhesive sheet and the BGA substrate was measured. When the void area is 20% or less of the adhesion area, it is evaluated as (Circle), when it exceeds 20%, it evaluated as x. The results are shown in Table 7.

It is considered that in Examples 1 to 10, since an ion-trapping layer including an organic low-molecular-weight compound is included, metal ions can be trapped, and packaging defects can be suppressed. In addition, it has an adhesive layer that does not substantially include organic low-molecular-weight compounds. Therefore, even if a thermal history (175 ° C × 1 hour) is assumed to be applied to wafer bonding and wire bonding, excessive curing is not performed, and voids can be formed during the forming process. Medium spreads well.

In Comparative Example 1, since no organic low molecular weight compound was added, metal ions could not be captured, and packaging defects could not be suppressed. In addition, in Comparative Examples 2 to 3, since the organic low molecular weight compound was added to the adhesive layer, the thermal history (175 ° C × 1 hour) of wafer bonding and wire bonding was assumed to be excessively cured, and voids were not good during molding. Ground spread.

[Fifth Embodiment]

The following examples and the like correspond to the dicing / wafer bonding film described in the fifth embodiment.

(Preparation of base material)

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

(Preparation of acrylic polymer A)

In a reaction vessel having a condenser tube, a nitrogen 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 parts of peroxide were charged. Polymerization of benzamidine and 20 parts of acetic acid was performed 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 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. Polymerization treatment was performed at 6 ° C for 6 hours 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 having a condenser tube, a nitrogen introduction tube, a thermometer, and a stirring device, 100 parts of an acrylic polymer having a number average molecular weight of about 300,000 composed of 100 parts of butyl acrylate, 5 parts of acrylonitrile, and 5 parts of acrylic acid 5 parts of polyisocyanate, 15 parts of pentaerythritol triacrylate, and 1 part of α-hydroxycyclohexylphenyl ketone were 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. 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 performed via GPC (gel permeation chromatography). The measurement conditions are as follows. The weight-average molecular weight is calculated in terms of polystyrene.

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

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

Flow: 0.5ml / min

Injection volume: 100 μl

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 measured from 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.

(Determination of hydroxyl value)

The hydroxyl value of the acrylic polymers A to C was evaluated in accordance with JIS K 0070-1992 (acetylation method). That is, about 3 g of each acrylic polymer after drying was added with 10 ml of acetamating reagent, and 30 ml of pyridine and 30 ml of dimethylformamide were added as solvents. This solution was heated in a water bath (95 to 100 ° C) equipped with a condenser for 1.5 hours. Add 3 ml of water and heat for 10 minutes.

Then, it was cooled to room temperature, the condenser was washed with 5 ml of ethanol, and the washing solution was added to the above solution. A stirrer was placed in this solution, and titration was performed using a 0.5 mol / L potassium hydroxide solution while stirring with a magnetic stirrer using a potentiometric titration device. When 1 g of a sample was subjected to ethionization, the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group was taken as the hydroxyl value.

(Determination of iodine value)

The iodine value of the acrylic polymers A to C was evaluated in accordance with JIS K 0070-1992. That is, about 3 g of each acrylic polymer after drying was added with 30 ml of chloroform to dissolve it. Add 25ml of Wijs solution and stir mix. Then, the lid was closed, and it was left in a dark place at 23 ° C for 1 hour. To this solution were added 20 ml of a potassium iodide solution and 100 ml of water, followed by stirring. Titrate the solution with a 0.1 mol / L sodium thiosulfate solution. When the solution turns slightly yellow, add a few drops of starch solution and perform the titration until the blue color disappears. When a halogen is reacted with a 100 g sample, the value of the combined halogen amount converted to the number of g of iodine is the iodine value.

(Preparation of Adhesive Composition Solutions A to C)

24.1 parts of 2-methacrylic acid oxyethyl isocyanate (manufactured by Showa Denko, hereinafter also referred to as "MOI") was added to each polymer of the acrylic polymers A to C, and carried out at 50 ° C for 48 hours in an air stream. Addition reaction treatment for hours to obtain acrylic polymers A '~ C'.

Then, 3 parts of a polyisocyanate compound (trade name "Coronate L", manufactured by Japan Polyurethane Co., Ltd.) and 3 parts of a photopolymerization initiator (trade name "Irgacure 651") were added to 100 parts each of the acrylic polymers A 'to C'. ", Manufactured by Ciba Fine Chemicals Co., Ltd.), and dissolved in toluene to obtain adhesive composition solutions A to C having a concentration of 20% by weight.

(Preparation of cutting film A ~ C)

The obtained adhesive composition solutions A to C were coated on the prepared substrate, and dried to form an adhesive layer having a thickness of 30 μm, thereby obtaining dicing films A to C.

(The production of film A)

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

(a) acrylic rubber (manufactured by Nagasechemtex Co., Ltd.,

This adhesive composition solution was applied as a release liner to a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a release treatment of polysiloxane, and the film was applied at It dried at 2 degreeC for 2 minutes, and produced the adhesive sheet A of 20 micrometers in thickness.

(The production of film B)

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

(e)離子捕捉劑(東亞合成股份有限公司製造，IXE-100)10份

(e) 10 parts of ion trapping agent (manufactured by Toa Synthesis Co., Ltd., IXE-100)

This adhesive composition solution was applied as a release liner to a release-treated film composed of a polyethylene terephthalate film having a thickness of 50 μm after being subjected to a release treatment of polysiloxane, and the film was applied at 130 ° C. After drying at 2 ° C for 2 minutes, an adhesive sheet B having a thickness of 20 µm was produced.

(Examples 1 to 4)

The dicing films A to C and the adhesive sheets A to B were each combined in a combination shown in Table 8 and pasted at room temperature to produce the dicing / wafer bonding films of Examples 1 to 4.

(Measurement of storage elastic modulus of the adhesive layer)

公司製造的黏彈性試驗機ARES，用直徑7.9mm的平行板(剪切試驗用)夾入試驗用樣品，提供1Hz的頻率的剪切應變，以5℃/分鐘的升溫速度測定26℃下的儲能彈性模量(G’：Pa)。結果如表8所示。 Using an adhesive composition solution A to C, an adhesive layer was formed on a release liner (manufactured by Mitsubishi Chemical Polyester Co., Ltd., MRF38, thickness: 38 μm), and this adhesive layer was prepared to have a layer thickness of 3 mm and a diameter of 8 mmΦ, and this was used as Test samples. Then, use Rheometric

The viscoelasticity testing machine ARES manufactured by the company sandwiches test samples with parallel plates (for shear tests) with a diameter of 7.9 mm, provides a shear strain at a frequency of 1 Hz, and measures the temperature at 26 ° C at a temperature rise rate of 5 ° C / min. Storage elastic modulus (G ': Pa). The results are shown in Table 8.

(Evaluation of change rate of copper ion capture amount)

The adhesive sheets A and B were each cut to a weight of about 2.5 g. The cut sample was placed in a cylindrical Teflon (registered trademark) container with a diameter of 58 mm and a height of 37 mm, and 10 ppm of Cu (II) ion was added. 50mL of aqueous solution. Then, it was left to stand at 120 degreeC for 20 hours in the constant temperature dryer (PV-231 made by Espec Corporation). After the film was taken out, the copper (II) ion in the aqueous solution was measured using ICP-AES (SII NanoTechnology Co., Ltd., SPS-1700HVR). Child concentration. From this, the amount of captured copper ions X (initial copper ion concentration 10 ppm-copper ion concentration after test) of the adhesive sheets A and B before sticking to the dicing film was determined.

In addition, after the dicing / wafer bonding films of Examples 1 to 4 were prepared, they were left at room temperature for 30 days. Then, the dicing / wafer bonding film was irradiated with ultraviolet rays (400 mJ / cm ² ), and the adhesive sheets A ′ and B ′ after the adhesive treatment were peeled from the dicing film. These adhesive sheets A ′ and B ′ were used as samples, and the copper ion concentration was measured in the same manner as in the above procedure. In this way, the amount of captured copper ions Y (initial copper ion concentration 10 ppm-copper ion concentration after test) of the adhesive sheets A 'and B' after the sticking treatment with the dicing film was determined.

From the following formula, the change rate (%) of the amount of captured copper ions before and after the film was stuck to the dicing film was calculated.

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

When the change rate of the amount of captured copper ions is 5% or less, it is evaluated as ○, and when it exceeds 5%, it is evaluated as ×. The results are shown in Table 8.

From the results in Table 8, it can be seen that the storage elastic modulus of each of the adhesive layers of the dicing / wafer bonding films of Examples 1 to 4 is 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 trapping agent from the adhesive sheet to the adhesive layer of the dicing film, etc., and it is possible to appropriately exhibit the ion trapping property of the adhesive sheet even after being adhered to the dicing film.

1‧‧‧ substrate

2‧‧‧ Adhesive layer

Parts 2a, 2b, 3b ‧‧‧

3‧‧‧ Adhesive (wafer bonding film)

3’‧‧‧ followed

3a‧‧‧Semiconductor wafer sticking part

3A‧‧‧ ion trap layer

3B‧‧‧ Adjacent Layer

4‧‧‧ semiconductor wafer

5.15‧‧‧semiconductor wafer

6‧‧‧ Adhesive

7‧‧‧ welding wire

8‧‧‧sealing resin

10, 11‧‧‧ dicing / wafer bonding film

13‧‧‧ Wafer Bonding Film

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

FIG. 2 is a schematic cross-sectional view showing an example of mounting a semiconductor wafer via a wafer bonding film of the dicing / wafer bonding film.

FIG. 3 is a schematic cross-sectional view showing an example of three-dimensional mounting of a semiconductor wafer via a wafer bonding film of the dicing / wafer bonding film.

4 is a schematic cross-sectional view of a multilayer adhesive sheet according to an embodiment of the present invention.

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

1‧‧‧ substrate

2‧‧‧ Adhesive layer

Parts 2a, 2b, 3b ‧‧‧

3‧‧‧ Adhesive (wafer bonding film)

3a‧‧‧Semiconductor wafer sticking part

4‧‧‧ semiconductor wafer

10‧‧‧ Dicing / Wafer Bonding Film

Claims (4)

An adhesive sheet for manufacturing a semiconductor device, comprising: a thermoplastic resin having an epoxy group and no carboxyl group; a thermosetting resin; and a complex-forming organic compound having the complex-forming property. The organic compound includes a heterocyclic compound containing a tertiary nitrogen atom as a ring atom, and is capable of forming a complex with a cation, in which 100 parts by weight, including 5 to 95 parts by weight, with respect to the total amount of the bonding sheet used for manufacturing the semiconductor device The thermoplastic resin, 5 to 50 parts by weight of the thermosetting resin, 0 to 60 parts by weight of a filler, and 0.1 to 5 parts by weight of the complex-forming organic compound, and the complex-forming organic compound is triazole Compound, tetrazole compound, or bipyridine compound. The adhesive sheet for manufacturing a semiconductor device according to item 1 of the scope of patent application, wherein the adhesive sheet for manufacturing a semiconductor device weighing 2.5 g is immersed in a 50 ml aqueous solution including 10 ppm of copper ions and left at 120 ° C. for 20 hours. After that, the copper ion concentration in the aqueous solution is 0 to 9.9 ppm. A semiconductor device comprising a bonding sheet for manufacturing a semiconductor device according to item 1 of the scope of patent application. A method for manufacturing a semiconductor device, comprising a step of attaching a semiconductor wafer to an adherend via an adhesive sheet for manufacturing a semiconductor device as described in item 1 of the scope of patent application.