JP2012122008A - Forming method of adhesive layer and adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a forming method of an adhesive layer, by which a thin film adhesive layer is formed in a suitable position and shape while suppressing damage of an adherend, and the adhesive layer for suppressing generation and remaining of a void in an interface or inside is formed, while suppressing displacement of the adherend at the time of adhesion.SOLUTION: The forming method of the adhesive layer includes: an adhesive layer forming step of selectively applying the adhesive composition containing a thermosetting component and an organic solvent on an adhesive surface by using a non-contact type applying device; and a solvent removing step of removing the solvent from the adhesive composition applied on the adhesive surface. The adhesive composition contains 1 to 20 mass% of an inorganic filler in which an average particle diameter is 1 to 200 nm.

Description

  The present invention relates to a method for forming an adhesive layer and an adhesive composition.

  In recent years, in products using semiconductor elements such as digital devices and mobile devices, not only multi-functionalization but also miniaturization and weight reduction are rapidly progressing. As products become smaller and lighter, semiconductor devices such as semiconductor packages are required to be thinned, and in addition, the semiconductor elements themselves contained in the semiconductor devices are required to be thinned. Currently, thinning of a semiconductor element is performed by grinding a silicon wafer before dicing into small pieces, but its thickness is 100 μm or less, for example, about several tens of μm. As a result, the thickness of the adhesive layer that bonds the base material such as the inorganic substrate or the organic substrate and the semiconductor element has a great influence on the thinning of the semiconductor device or the like.

  Formation of the adhesive layer is performed, for example, by applying an adhesive composition to the adhesive surface by a dispensing method or a stamping method (see, for example, Patent Document 1). However, it is not always easy to form an adhesive layer having a thickness of 10 μm or less by a dispensing method or a stamping method, and an adhesive layer having a uniform thickness is formed because the coating amount is likely to vary. It is not easy.

  Further, a screen printing method is known as a method for forming an adhesive layer at an arbitrary position on the adhesive surface. However, in the screen printing method, it is not always easy to form an adhesive layer having a thickness of 10 μm or less, and a screen mesh or a squeegee that is a part of the printing apparatus touches the adhesive surface when forming the adhesive layer. The adherend having the bonding surface may be damaged in the case of a silicon wafer, a fragmented semiconductor element, or the like.

  On the other hand, an adhesive sheet in which the adhesive composition is formed into a film is also known (see, for example, Patent Document 2). By making the adhesive composition into a film, the thickness can be made relatively thin and uniform. However, an adhesive sheet having a thickness of 10 μm or less and a uniform thickness is not always easy to manufacture, and has low handling properties when attached to an adhesive surface, which is not practical. Furthermore, various problems remain such as the production of such an adhesive sheet requires more cost than before.

  In addition, with the increase in functionality of products, a conventional stacked structure in which a plurality of semiconductor elements are stacked, for example, a stacked structure of a plurality of semiconductor elements having different functions and a stacked structure of a memory element for realizing a large capacity of a memory. However, there is a problem that cannot be technically solved by this method of forming an adhesive layer. For example, warping tends to occur due to the thinning of the semiconductor element, and voids are generated at the interface or inside of the adhesive layer when the semiconductor element is bonded or sealed, which may reduce the product yield.

  Furthermore, in a stacked structure in which a plurality of semiconductor elements are stacked, high precision is required for the bonding position of the semiconductor elements in order to optimize wire bonding or flip chip mounting. The accuracy of the bonding position is affected by the accuracy of the adhesive layer forming position, the characteristics of the adhesive layer, and the like.

JP 2008-270282 A JP 2008-288571 A

  The present invention has been made to solve the problems in the conventional method for forming an adhesive layer, and forms a thin adhesive layer in an appropriate position and shape while suppressing damage to the adhesive. An object of the present invention is to provide a method for forming an adhesive layer that can be used. Furthermore, it aims at providing the formation method of the adhesive bond layer which can form the adhesive bond layer which can suppress generation | occurrence | production and residual of the space | gap in an interface or an inside while being able to suppress the position shift of an adhesive substance at the time of adhesion | attachment. .

  In addition, the present invention can form a thin-film adhesive layer at an appropriate position and shape, and can further suppress the positional deviation of the adhesive during bonding, and can also prevent the generation and remaining of voids at the interface or inside. It aims at providing the adhesive composition which can form the adhesive bond layer which can be suppressed.

  As a result of diligent study, the present inventors have used a non-contact type coating apparatus, and also used an adhesive composition containing a thermosetting component, an organic solvent, and a specific inorganic filler. The present invention has been completed by finding that the problems can be solved.

  That is, in the method for forming an adhesive layer of the present invention, an adhesive layer in which an adhesive composition containing a thermosetting component and an organic solvent is selectively applied onto an adhesive surface using a non-contact type coating apparatus. A forming step and a solvent removing step of removing the solvent from the adhesive composition applied on the adhesive surface. The method for forming an adhesive layer of the present invention is characterized in that an adhesive composition containing 1 to 20% by mass of an inorganic filler having an average particle diameter of 1 to 200 nm is used.

  Moreover, the adhesive composition of this invention is used for formation of the adhesive bond layer by a non-contact-type coating device. The adhesive composition of the present invention includes a thermosetting component and an organic solvent, and contains 1 to 20% by mass of an inorganic filler having an average particle diameter of 1 to 200 nm.

  According to the method for forming an adhesive layer of the present invention, while using a non-contact type coating apparatus and using a specific adhesive composition, while suppressing defects in the coating apparatus and damage to the adhesive, A thin adhesive layer can be formed at an appropriate position and shape. Furthermore, it is possible to form an adhesive layer that can suppress the positional deviation of the adhesive during bonding and can suppress the generation or remaining of voids at the interface or inside.

  Moreover, according to the adhesive composition of the present invention, it is possible to form a thin film-like adhesive layer in an appropriate position and shape while suppressing a problem of the coating apparatus by using a specific composition. Furthermore, it is possible to form an adhesive layer that can suppress the positional deviation of the adhesive during bonding and can suppress the generation and remaining of voids at the interface or inside.

Embodiments of the present invention will be described below.
The method for forming an adhesive layer of the present invention comprises an application step of selectively applying an adhesive composition containing a thermosetting component and an organic solvent on an adhesive surface using a non-contact type application device, And a solvent removal step of removing the solvent from the adhesive composition applied on the surface. The method for forming an adhesive layer of the present invention is characterized in that an adhesive composition containing 1 to 20% by mass of an inorganic filler having an average particle diameter of 1 to 200 nm is used.

  According to the method for forming an adhesive layer of the present invention, while using a non-contact type coating apparatus and using a specific adhesive composition, while suppressing defects in the coating apparatus and damage to the adhesive, A thin adhesive layer can be formed at an appropriate position and shape. Furthermore, it is possible to form an adhesive layer that can suppress the displacement of the adhesive during bonding and can suppress the generation and remaining of voids at the interface or inside.

  Accordingly, the present invention exhibits a particularly remarkable effect in the electronic industry field, the semiconductor industry field, and the like where high accuracy is required for the formation position and shape of the adhesive layer. In addition, since it is possible to suppress misalignment of the adhesive during bonding, generation of voids, and the like, the yield and reliability of various products having such an adhesive can be improved. Furthermore, by adjusting the composition and forming method of the adhesive composition, excellent adhesive strength, heat resistance, and tack-free properties can be imparted, and the yield and reliability of various products can be further improved.

  In the application step, the adhesive composition is selectively applied onto the adhesive surface using the non-contact type application device as described above. By using a non-contact type coating apparatus, it is possible to form a thin-film adhesive layer at an appropriate position and shape while suppressing damage to the adhesive. Here, as an adhesive having an adhesive surface, for example, a semiconductor element is preferable, but the adhesive is not necessarily limited thereto.

  Examples of the non-contact type coating apparatus include an ink jet apparatus, a spray apparatus, and a jet dispensing apparatus. Among these, an ink jet apparatus and a spray apparatus that can adhere the adhesive composition in a thin film form are preferable, and an ink jet apparatus that can easily obtain a uniform thickness is preferable. In an inkjet apparatus, a thin film-like adhesive layer having a particularly uniform thickness can be satisfactorily formed by discharging an adhesive composition from the fine discharge nozzle onto an adhesive surface.

  The adhesive composition contains a thermosetting component and an organic solvent as described above, and contains 1 to 20% by mass of an inorganic filler having an average particle diameter of 1 to 200 nm.

  When the average particle diameter of the inorganic filler is less than 1 nm, sufficient thixotropy cannot be imparted to the adhesive composition, and the positional deviation of the adhesive during bonding may not be effectively suppressed. When the positional deviation occurs in the adhesive, for example, since the adhesive layer is exposed more, the water absorption rate increases, and as a result, the moisture resistance reliability decreases. On the other hand, when it exceeds 200 nm, there is a possibility that the fine discharge nozzle in the non-contact type coating apparatus may be clogged and the adhesive layer may not be stably formed, and the positional deviation of the adhesive during bonding is large. There is a risk. The average particle size of the inorganic filler is particularly preferably 3 to 150 nm. The average particle size of the inorganic filler is measured by a laser diffraction / scattering method.

  In addition, when the content of the inorganic filler is less than 1% by mass in the entire adhesive composition, the content of the inorganic filler is too small, so that thixotropy is not sufficiently imparted to the adhesive composition. There is a possibility that the displacement of the adhesive at the time cannot be effectively suppressed. Further, due to the positional deviation of the adhesive, the water absorption rate of the adhesive layer is increased as described above, and as a result, the moisture resistance reliability may be decreased. On the other hand, when it exceeds 20 mass%, the fine discharge nozzle in the non-contact type coating apparatus may be clogged, and the adhesive layer may not be stably formed. Further, when the adhesive layer is formed, there is a possibility that sufficient adhesive force cannot be obtained. Furthermore, voids may be generated at the interface or inside of the adhesive layer during bonding, and the generated voids may remain without disappearing to the end. As a result, there is a possibility that the reflow reliability and the like of various products having an adhesive will not be sufficient. As for content of an inorganic filler, 3-18 mass% is more preferable, and 3-15 mass% is further more preferable.

  Such an adhesive composition preferably has a viscosity at 25 ° C. of 100 mPa · s or less, particularly preferably 5 to 50 mPa · s. By setting it as such a viscosity, especially the discharge property in a non-contact-type coating apparatus can be made favorable, and the thin film-like adhesive bond layer can be stably formed in an appropriate position and shape. The viscosity of the adhesive composition can be usually adjusted by adjusting the content ratios of the thermosetting component, the organic solvent, and the inorganic filler.

  In the solvent removing step, the organic solvent is removed from the adhesive composition applied on the adhesive surface in the applying step to form an adhesive layer. By using a volatile organic solvent as the solvent, the solvent can be easily volatilized and removed by heating. The heating method is not particularly limited as long as the organic solvent can be effectively volatilized and removed from the adhesive composition, and can be performed using, for example, an oven. The heating may be performed after the application of the adhesive composition, or may be performed on the adhesive surface in advance, and the solvent may be volatilized simultaneously with the application of the adhesive composition.

  Here, since the adhesive layer adheres an adhesive such as a semiconductor element and an adherend such as a substrate to which the adhesive is adhered, it needs to be in a state where a sufficient adhesive force can be exhibited at the time of adhesion. There is. Accordingly, the heating in the solvent removal step needs to be performed in a so-called semi-cured state (B-stage state) in which the organic solvent can be volatilized but the curing reaction of the thermosetting component is not completed.

  In addition, by setting it as a semi-hardened state, the characteristic (tack-free property) which does not adhere even if it contacts other members, for example in normal temperature can be provided, and it becomes easy to hold | maintain the shape of an adhesive bond layer. For this reason, in the formation method of the adhesive bond layer of this invention, it is preferable to perform the semi-hardening process which performs the heating for making it a semi-hardened state. Although it depends on the composition of the adhesive composition and the like, it can generally be brought into a semi-cured state by heating at a temperature of 40 to 120 ° C. for 1 to 180 minutes. Here, the semi-curing step may be performed together with the solvent removal step, or may be performed separately after the solvent removal step.

  As described above, the adhesive composition contains a thermosetting component, an organic solvent, and an inorganic filler. The thermosetting component contains, for example, an epoxy resin, an epoxy curing agent, and a curing accelerator. The content of such a thermosetting component is preferably 5 to 50% by mass in the entire adhesive composition, for example, from the viewpoint of dischargeability in a non-contact type coating apparatus, formability of an adhesive layer, and the like. .

  As the epoxy resin, an epoxy resin having two or more epoxy groups in one molecule, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, biphenyl type epoxy resin, glycidyl ether type epoxy resin, An alicyclic epoxy resin, a heterocyclic epoxy resin, or the like can be used.

  As the epoxy curing agent, any compound that is usually used for curing an epoxy resin can be used without particular limitation. Examples of the amine curing system include dicyandiamide and aromatic diamine, and the phenol curing system includes phenol. Examples include novolak resin, cresol novolak resin, bisphenol A type novolak resin, triazine-modified phenol novolak resin and the like. These can be used alone or in combination of two or more, but from the viewpoint of heat resistance, moisture resistance reliability and the like. A phenolic curing agent is preferred.

  The compounding ratio of the epoxy resin and the phenolic curing agent is preferably such that the equivalent ratio of the epoxy equivalent of the epoxy resin and the hydroxyl equivalent of the phenolic curing agent is 0.1 to 1.2, 0.3 to 1.0 More preferably. If it is less than 0.1, the curability is insufficient, and if it exceeds 1.2, the reactivity on the high temperature side as will be described later is lost, and the effect of disappearance or miniaturization of voids at the time of sealing is sufficiently obtained. There is a risk of not being able to.

  As the curing accelerator, those usually used as curing accelerators for epoxy resins can be used, and imidazole compounds such as 2-ethyl-4-methylimidazole and 1-benzyl-2-methylimidazole, boron trifluoride amine. And tertiary amine compounds such as complexes, triphenylphosphine (TPP), and 1,8-diazabicyclo (5,4,0) undecene-7. These curing accelerators can be used alone or in combination.

  The organic solvent is not particularly limited as long as it can dissolve the thermosetting component, but preferably has a boiling point of 120 ° C. or higher so that the discharge nozzle in the non-contact type coating apparatus is not clogged. Specific examples of the solvent include diglyme, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, and gamma-butyrolactone. These may be used alone or in combination of two or more. Can be used as a mixture.

  30-80 mass% is preferable in the whole adhesive composition, for example, and, as for content of an organic solvent, 40-70 mass% is more preferable. By setting it as such content, the viscosity of an adhesive composition can be made into an appropriate range. In addition, content of this organic solvent is not necessarily limited to what was added independently as an organic solvent. For example, some commercially available inorganic fillers are dispersed in an organic solvent, but the content of the organic solvent when such a material is used as it is (the content of the organic solvent in the adhesive composition). The amount) includes an organic solvent in which an inorganic filler is dispersed in addition to an organic solvent added alone. That is, the content of the substantial organic solvent in the adhesive composition only needs to be 30 to 80% by mass.

  The inorganic filler is not particularly limited as long as it is made of an inorganic material and has an average particle diameter of 1 to 200 nm. Examples of such a material include silica fine particles and alumina fine particles. In particular, silica fine particles are preferable because of excellent thermal stability and the like. Examples of the silica fine particles include those obtained by a so-called wet method synthesized by a neutralization reaction between sodium silicate and sulfuric acid, but are not necessarily limited to these. The wet method is further roughly classified into a precipitation method and a gelation method, and either method may be used.

  Here, since the adhesive composition contains an organic solvent, the inorganic filler needs to be appropriately dispersible in the organic solvent. Therefore, the inorganic filler is preferably subjected to surface treatment with a coupling agent such as epoxy silane, amino silane, acryl silane, vinyl silane, phenyl silane, mercapto silane, isocyanate silane, ureido silane and the like.

  Commercially available products can be used as the inorganic filler, for example, “NIPGEL” series manufactured by Tosoh Silica Co., Ltd., “OSCAL” series manufactured by Catalytic Chemical Industry Co., Ltd., and high products manufactured by Fuso Chemical Industry Co., Ltd. An organosol of purity, Ultra Fine Powder manufactured by Denki Kagaku Kogyo Co., Ltd., Organosol manufactured by Nissan Chemical Industries, Ltd., Admanano Co., Ltd. manufactured by Admatechs Co., Ltd. can be used.

  In addition, some of the commercially available inorganic fillers are dispersed in an organic solvent, but the content of the inorganic filler in the case where such a filler is used as it is (inorganic filler in the adhesive composition). Content) does not include the organic solvent in which the inorganic filler is dispersed, and includes only the inorganic filler. That is, the content of the substantial inorganic filler in the adhesive composition only needs to be 1 to 20% by mass.

  The adhesive composition can contain a silane coupling agent, a surfactant and the like in addition to the above-described thermosetting component, organic solvent, and inorganic filler. Examples of the silane coupling agent include silane coupling agents such as epoxy silane and acrylic silane, and these can be used alone or in combination.

  The surfactant is added to improve wettability when the adhesive composition is applied to the adhesive surface, and is a silicone-based surfactant, a fluorine-based surfactant, an acrylic-based surfactant. These may be used alone or in combination of two or more.

  Such an adhesive composition has, for example, two curing temperatures, and the reaction between the epoxy resin and the epoxy curing agent proceeds at the low-temperature curing temperature, and the self-polymerization of the epoxy resin at the high-temperature curing temperature. The reaction proceeds. These reactions can be measured by differential scanning calorimetry (DSC) using a differential scanning calorimeter. For example, a low temperature side peak is measured at 100 to 160 ° C., and a high temperature side peak is measured at 140 to 200 ° C. In the above description, the temperature range of the low temperature side peak partially overlaps the temperature range of the high temperature side peak, but in the actual adhesive composition, the high temperature side peak appears at a higher temperature than the low temperature side peak.

  By having two curing temperatures, for example, as will be described later, the adhesive is a semiconductor element, and this semiconductor element is bonded to an adherend such as a base material, and substantially all of these are sealed with an insulating material. When a semiconductor device is used, the reaction between the epoxy resin and the epoxy curing agent, which is a reaction on the low temperature side, is mainly performed until sealing, and the self-polymerization reaction of the epoxy resin, which is a reaction on the high temperature side, is performed at the time of sealing. Can do. As a result, at the time of sealing, the adhesive layer can be re-adhered using the temperature and pressure, and even if there are voids or delamination at the interface or inside of the adhesive layer, these voids or delamination Can be eliminated or miniaturized.

The method for forming an adhesive layer of the present invention can be suitably applied to the manufacture of a semiconductor device.
Manufacturing of a semiconductor device includes, for example, a pre-process for forming a semiconductor element itself and a post-process for mounting the semiconductor element on a base material to obtain a semiconductor device. In the pre-process, for example, a circuit formation process that forms a circuit pattern on the surface of the silicon wafer by film formation, resist coating, exposure, development, etching, resist removal, etc., inspection process, cleaning process, heat treatment process, impurity introduction process, diffusion Process, planarization process, and the like. Further, the post-process includes an adhesive layer forming process, a dicing process, a die bonding process, a wire bonding process, an assembly process such as a sealing process, an inspection process for performing a function and reliability inspection, and the like. Note that the order of the steps can be changed as necessary.

  The method for forming an adhesive layer of the present invention can be suitably applied particularly to the formation of an adhesive layer in a subsequent adhesive layer forming step. For example, the adhesive layer is formed on the back surface opposite to the element forming surface of a silicon wafer. The present invention can be suitably applied to the formation of an adhesive layer.

  In addition, the formation method of the adhesive bond layer of this invention can be applied suitably also when performing an adhesive bond layer formation process after a dicing process. In this case, the adhesive layer forming method of the present invention can be applied when forming the adhesive layer in the adhesive layer forming step for individual semiconductor elements cut from the silicon wafer in the dicing step. Examples of the adherend to which the semiconductor element is bonded include an organic substrate, an inorganic substrate, and other semiconductor elements.

  When a semiconductor device is manufactured by applying the adhesive layer forming method of the present invention, for example, as described above, the adhesive layer forming method of the present invention is applied to the back surface of the silicon wafer in the adhesive layer forming step. An agent layer is formed. The formation range of the adhesive layer can be, for example, an individual semiconductor element portion excluding a cut portion in the dicing process, but is not necessarily limited to such a formation range. After the adhesive layer forming step, individual semiconductor elements are obtained by cutting the silicon wafer having the adhesive layer formed on the back surface in the dicing step.

  Further, in the die bonding step, the semiconductor element and an object to be bonded, such as an organic substrate, an inorganic substrate, or another semiconductor element, are bonded using an adhesive layer. Adhesion can be performed by heating the adhesive layer to advance the curing reaction. For example, it can be performed by holding an object to be bonded on a heated stage by vacuum or the like, moving a semiconductor element on the object to be bonded by a collet, heating both, and thermocompression bonding.

  The thermocompression bonding temperature is preferably 60 to 200 ° C, for example, and more preferably 70 to 180 ° C. When the temperature is lower than 60 ° C., the wettability of the adhesive layer with respect to the adherend becomes insufficient, and voids are generated at the interface or inside of the adhesive layer. When it exceeds 200 ° C., the viscosity of the adhesive layer is excessively lowered, and there is a possibility that the semiconductor element is displaced and the adhesive layer is protruded. Further, the curing reaction of the adhesive layer proceeds excessively, and there is a possibility that the re-adhesiveness of the adhesive layer already described in the sealing process performed thereafter cannot be sufficiently obtained.

  Furthermore, in the wire bonding step, the electrode formed on the semiconductor element and the electrode formed on the adherend are connected by a bonding wire. The connection by the bonding wire is performed, for example, by pressing a bonding wire inserted into a capillary attached to the tip of the bonding arm against the electrode and bonding each electrode and the bonding wire with heat by ultrasonic vibration.

  In order to prevent the wire flow, the adhesive layer is preferably not semi-cured but semi-cured. By setting the adhesive layer in a semi-cured state, attenuation of ultrasonic vibration during wire bonding can be effectively suppressed, and occurrence of defects such as bonding failure of bonding wires and insufficient bonding strength can be suppressed.

  Further, in the sealing step, sealing is performed so that substantially the entire adherend to which the semiconductor element is bonded is covered with an insulating resin. In the sealing step, for example, an adherend to which a semiconductor element is bonded is placed in a cavity formed by a fixed mold and a movable mold, and a molten insulating resin is injected and filled in the cavity. In addition, the semiconductor device is formed by applying pressure and heating with a movable mold. The temperature at the time of sealing is, for example, about 180 ° C.

  Thus, in the sealing process, since pressure and heating are substantially performed on the adhesive layer, the curing reaction, in particular, the self-polymerization reaction of the epoxy resin, which is a reaction on the high temperature side, proceeds and adhesion The agent layer can be reattached. Thereby, even if there are voids or separation at the interface or inside of the adhesive layer, these voids or separation can be eliminated or miniaturized. As a result, a semiconductor device having good reflow reliability and the like can be obtained.

  As described above, the method for forming an adhesive layer of the present invention can be preferably applied to the manufacture of a semiconductor device. Here, the semi-curing step can be carried out entirely or partially during other steps other than the adhesive layer forming step or between the steps as required. For example, you may carry out in order to adjust the hardness of an adhesive bond layer between a die-bonding process and a wire bonding process. Such a semi-curing process can be performed using a heating furnace or the like, and for example, can be performed using a curing furnace or the like that performs a pre-cure.

  Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1
As shown in Table 1, 100 parts by weight of jER1001 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) as epoxy resin A, BRG-556 of phenol resin (trade name, manufactured by Showa Polymer Co., Ltd.) 10 as a curing agent for epoxy 2 parts by mass of KBM403 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 1.5 parts by mass of U-CAT SA 102 (trade name, manufactured by San Apro Co., Ltd.) as curing accelerators A and B 2E4MZ (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) 0.2 parts by mass, organosilica sol PMA-ST (manufactured by Nissan Chemical Industries, trade name) as inorganic filler A, 370 parts by mass, BYK-302 as surfactant (Made by Big Chemie Japan) 0.2 parts by mass, gamma-butyrolactone GBL (Mitsubishi Chemical Corporation) as organic solvent Ltd., trade name) 416 parts by weight were mixed and dissolved by heating at 60 ° C., to produce an adhesive composition.

This adhesive composition had a viscosity at 25 ° C. of 12 mPa · s and a solid component of 25% by mass. In addition, organosilica sol PMA-ST (trade name, manufactured by Nissan Chemical Industries, Ltd.) of inorganic filler A is obtained by dispersing silica (SiO ₂ ) in propylene glycol monomethyl acetate, and the particle diameter of SiO ₂ is 10 The content of ˜20 nm and SiO ₂ is 30% by mass. Here, the content of the inorganic filler in the adhesive composition is the content of SiO ₂ alone without this propylene glycol monomethyl acetate.

(Example 2)
As shown in Table 1, as epoxy resins A and B, jER1001 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) 80 parts by mass, EOCN103S (trade name, manufactured by Nippon Kayaku Co., Ltd.) 20 parts by mass, and epoxy curing agent BRG-556 (trade name, manufactured by Showa Polymer Co., Ltd.) 10 parts by weight of phenol resin, 2 parts by weight of KBM403 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, U as curing accelerators A and B -CAT SA 102 (manufactured by San Apro Co., Ltd., trade name) 1.5 parts by mass, 2E4MZ (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) 0.2 parts by mass, organo filler sol PMA-ST (Nissan Chemical Industries) as inorganic filler A Co., Ltd., trade name) 370 parts by mass, as a surfactant BYK-302 (manufactured by Big Chemie Japan) 0.2 parts by mass Gamma as an organic solvent - butyrolactone GBL (Mitsubishi Chemical Corporation, trade name) 416 parts by weight were mixed and dissolved by heating at 60 ° C., to produce an adhesive composition. This adhesive composition had a viscosity at 25 ° C. of 11 mPa · s and a solid component of 25% by mass.

(Example 3)
As shown in Table 1, 100 parts by weight of jER1001 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) as epoxy resin A, BRG-556 of phenol resin (trade name, manufactured by Showa Polymer Co., Ltd.) 10 as a curing agent for epoxy 2 parts by mass of KBM403 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 1.5 parts by mass of U-CAT SA 102 (trade name, manufactured by San Apro Co., Ltd.) as curing accelerators A and B 2E4MZ (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) 0.2 parts by mass, 190 parts by mass of organosilica sol PMA-ST (trade name, manufactured by Nissan Chemical Industries, Ltd.) as inorganic filler A, and BYK-302 as a surfactant (Made by Big Chemie Japan) 0.2 parts by mass, gamma-butyrolactone GBL (Mitsubishi Chemical Corporation) as organic solvent Ltd., trade name) 439 parts by weight were mixed and dissolved by heating at 60 ° C., to produce an adhesive composition. This adhesive composition had a viscosity at 25 ° C. of 11 mPa · s and a solid content of 23% by mass.

Example 4
As shown in Table 1, 100 parts by weight of jER1001 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) as epoxy resin A, BRG-556 of phenol resin (trade name, manufactured by Showa Polymer Co., Ltd.) 10 as a curing agent for epoxy 2 parts by mass of KBM403 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 1.5 parts by mass of U-CAT SA 102 (trade name, manufactured by San Apro Co., Ltd.) as curing accelerators A and B 2E4MZ (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) 0.2 parts by mass, inorganic filler A as organosilica sol PMA-ST (manufactured by Nissan Chemical Industries, trade name) 93 parts by mass, and surfactant BYK-302 (Made by Big Chemie Japan) 0.2 parts by mass, gamma-butyrolactone GBL (Mitsubishi Chemical Corporation) as an organic solvent , Trade name) 340 parts by weight were mixed and dissolved by heating at 60 ° C., to produce an adhesive composition. This adhesive composition had a viscosity at 25 ° C. of 13 mPa · s and a solid content of 26% by mass.

(Example 5)
As shown in Table 1, 100 parts by weight of jER1001 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) as epoxy resin A, BRG-556 of phenol resin (trade name, manufactured by Showa Polymer Co., Ltd.) 10 as a curing agent for epoxy 2 parts by mass of KBM403 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 1.5 parts by mass of U-CAT SA 102 (trade name, manufactured by San Apro Co., Ltd.) as curing accelerators A and B 2E4MZ (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) 0.2 part by mass, organosilica sol IPA-ST-ZL (manufactured by Nissan Chemical Industries, trade name) as inorganic filler B, 370 parts by mass, BYK as surfactant -302 (by Big Chemie Japan) 0.2 parts by mass, gamma-butyrolactone GBL (Mitsubishi Chemical) as the organic solvent Wherein, trade name) 416 parts by weight were mixed and dissolved by heating at 60 ° C., to produce an adhesive composition.

This adhesive composition had a viscosity at 25 ° C. of 11 mPa · s and a solid component of 25% by mass. Incidentally, organosilica sol IPA-ST-ZL of the inorganic filler B (manufactured by Nissan Chemical Industries, Ltd., trade name), which silica (SiO ₂₎ is dispersed in isopropanol, the particle diameter of SiO ₂ is 70 The content of 100 nm and SiO ₂ is 30% by mass. The content of the inorganic filler in the adhesive composition is the content of SiO ₂ alone without this isopropanol.

(Example 6)
As shown in Table 1, 100 parts by weight of jER1001 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) as epoxy resin A, BRG-556 of phenol resin (trade name, manufactured by Showa Polymer Co., Ltd.) 10 as a curing agent for epoxy 2 parts by mass of KBM403 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 1.5 parts by mass of U-CAT SA 102 (trade name, manufactured by San Apro Co., Ltd.) as curing accelerators A and B 2E4MZ (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) 0.2 parts by mass, colloidal silica Snowtex XS (manufactured by Nissan Chemical Industries, trade name) 280 parts by mass as inorganic filler C, BYK-302 as surfactant (Made by Big Chemie Japan) 0.2 parts by mass, gamma-butyrolactone GBL (Mitsubishi Chemical Corporation) as an organic solvent , Trade name) 288 parts by weight were mixed and dissolved by heating at 60 ° C., to produce an adhesive composition.

This adhesive composition had a viscosity at 25 ° C. of 11 mPa · s and a solid component of 25% by mass. The colloidal silica Snowtex XS (trade name, manufactured by Nissan Chemical Industries, Ltd.), which is an inorganic filler C, is a silica (SiO ₂ ) sol stabilized with Na, and the particle diameter of SiO ₂ is 4 to 6 nm. The content of ₂ is 30% by mass. The content of the inorganic filler in the adhesive composition is the content of this SiO ₂ alone.

(Comparative Example 1)
As shown in Table 1, 100 parts by weight of jER1001 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) as epoxy resin A, BRG-556 of phenol resin (trade name, manufactured by Showa Polymer Co., Ltd.) 10 as a curing agent for epoxy 2 parts by mass of KBM403 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 1.5 parts by mass of U-CAT SA 102 (trade name, manufactured by San Apro Co., Ltd.) as curing accelerators A and B 2E4MZ (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) 0.2 parts by mass, BYK-302 (manufactured by BYK Japan) as a surfactant, 0.2 parts by mass, gamma-butyrolactone GBL (Mitsubishi Chemical Corporation) as an organic solvent Product, trade name) 342 parts by mass were mixed and dissolved by heating at 60 ° C. to prepare an adhesive composition. This adhesive composition had a viscosity at 25 ° C. of 12 mPa · s and a solid component of 25% by mass.

(Comparative Example 2)
As shown in Table 1, 100 parts by weight of jER1001 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) as epoxy resin A, BRG-556 of phenol resin (trade name, manufactured by Showa Polymer Co., Ltd.) 10 as a curing agent for epoxy 2 parts by mass of KBM403 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 1.5 parts by mass of U-CAT SA 102 (trade name, manufactured by San Apro Co., Ltd.) as curing accelerators A and B 2E4MZ (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) 0.2 parts by mass, Admafin SO-E3 (manufactured by Admatex Co., Ltd., trade name) as inorganic filler D, 110 parts by mass, BYK-302 as surfactant Big Chemie Japan Co., Ltd.) 0.2 parts by mass, gamma-butyrolactone GBL (Mitsubishi Chemical Corporation, Name) 672 parts by weight were mixed and dissolved by heating at 60 ° C., to produce an adhesive composition. This adhesive composition had a viscosity at 25 ° C. of 14 mPa · s and a solid component of 25% by mass. In addition, the above-described admaffin SO-E3 (manufactured by Admatechs Co., Ltd., trade name) is made of SiO ₂ and has an average particle diameter of 1 μm.

(Comparative Example 3)
As shown in Table 1, as epoxy resins A and B, jER1001 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) 80 parts by mass, EOCN103S (trade name, manufactured by Nippon Kayaku Co., Ltd.) 20 parts by mass, and epoxy curing agent BRG-556 (trade name, manufactured by Showa Polymer Co., Ltd.) 10 parts by weight of phenol resin, 2 parts by weight of KBM403 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, U as curing accelerators A and B -CAT SA 102 (manufactured by San Apro Co., Ltd., trade name) 1.5 parts by mass, 2E4MZ (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) 0.2 parts by mass, ADMUFFIN SO-E3 (AD Corp. Made by Matex, trade name: 110 parts by mass, BYK-302 (manufactured by Big Chemie Japan) as a surfactant, 0.2 part by mass, organic Gamma as medium - butyrolactone GBL (Mitsubishi Chemical Corporation, trade name) 672 parts by weight were mixed and dissolved by heating at 60 ° C., to produce an adhesive composition. This adhesive composition had a viscosity at 25 ° C. of 13 mPa · s and a solid component of 25% by mass.

(Comparative Example 4)
As shown in Table 1, 100 parts by weight of jER1001 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) as epoxy resin A, BRG-556 of phenol resin (trade name, manufactured by Showa Polymer Co., Ltd.) 10 as a curing agent for epoxy 2 parts by mass of KBM403 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 1.5 parts by mass of U-CAT SA 102 (trade name, manufactured by San Apro Co., Ltd.) as curing accelerators A and B 2E4MZ (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) 0.2 parts by mass, organosilica sol PMA-ST (manufactured by Nissan Chemical Industries, trade name) as inorganic filler A 5000 parts by mass, BYK-302 as surfactant (Made by Big Chemie Japan) 0.2 parts by mass, gamma-butyrolactone GBL (Mitsubishi Chemical Corporation) as organic solvent Inc., trade name) were mixed 800 parts by weight, dissolved by heating at 60 ° C., to produce an adhesive composition. This adhesive composition had a viscosity at 25 ° C. of 12 mPa · s and a solid content of 27% by mass.

Next, the following evaluation was performed about the adhesive composition of an Example and a comparative example.
First, for the adhesive composition, using a viscoelasticity measuring device Rheometer ARES (trade name, manufactured by Rheometric Scientific, Inc.), the ratio of the melt viscosity between 5 radians per second and 50 radians per second at a measurement temperature of 80 ° C. with variable angular velocity. Was calculated (in the table, thixotropy). As an example, the adhesive composition of Example 1 was 14800 Pa · s at 5 radians per second, 5500 Pa · s at 50 radians per second, and the ratio was 2.7.

  Moreover, while forming an adhesive bond layer using an adhesive composition, the semiconductor device was manufactured and the following evaluation was performed. First, a silicon wafer having a diameter of 200 mm and a thickness of 100 μm is placed on a coating stage at a temperature of 70 ° C., and bonded using an ink jet apparatus (piezo type, nozzle diameter 70 μmφ, nozzle interval 0.4 mm). The agent composition was applied. Then, it hold | maintained for 30 minutes at 90 degreeC, the adhesive composition was dried, and the adhesive bond layer was formed.

  Under the present circumstances, while observing the discharge state from the discharge nozzle of an inkjet apparatus, the film thickness of the obtained adhesive bond layer was measured (in the table | surface, discharge property, film thickness). In addition, the thing in which clogging did not generate | occur | produce in a discharge nozzle was determined that discharge property is favorable ((circle)), and the thing in which clogging occurred in the discharge nozzle was determined to be defective (x). The film thickness of the adhesive layer was measured using Alpha Step 500 (manufactured by KLA-Tencor).

  The silicon wafer on which this adhesive layer was formed was diced into 10 mm squares to obtain semiconductor elements. Then, on the 0.3 mm thick organic package substrate, the semiconductor element was heated to 150 ° C., laminated in two steps at a pressure of 2.0 N, thermocompression bonded, and further cured at 150 ° C. for 1 hour. At this time, the position shift of the semiconductor element was measured (position shift in the table). For the measurement of misalignment, the mounting position accuracy in the X direction and Y direction of the chip is measured with a side micrometer, and if both are less than 25 μm, it is judged as acceptable (◯), and any of them exceeds 25 μm. It was determined to be rejected (x). Further, using an ultrasonic imaging apparatus (Hitachi Engineering & Service Co., Ltd.), the vicinity of the adhesive layer and the presence or absence of peeling were observed (in the table, voids after lamination, etc.).

  The organic package substrate on which the chips are laminated is sealed to a thickness of 0.8 mm with KE-G1250 (trade name, manufactured by Kyocera Chemical Co., Ltd.), which is a sealing material, and cured at 175 ° C. for 8 hours to obtain a semiconductor device. It was. About this semiconductor device, the space | gap near an adhesive bond layer and the presence or absence of peeling were observed using the ultrasonic imaging device (Hitachi Engineering & Service Co., Ltd.).

  In addition, after the moisture absorption reflow test in which the semiconductor device is subjected to a JEDEC level 3 moisture absorption treatment and a 260 ° C. reflow treatment, an ultrasonic imaging device (Hitachi Engineering & Service Co., Ltd.) is used to peel the vicinity of the adhesive layer. Was observed (reflow reliability in the table).

  About the adhesive composition of the comparative example 1 which does not contain an inorganic filler, although the discharge property in an inkjet apparatus is favorable, thixotropy is low and position shift generate | occur | produces in a semiconductor element. In addition, the adhesive compositions of Comparative Examples 2 and 3 that contain an inorganic filler but have a large particle size have low ejection properties in the ink jet device, and misalignment occurs in the semiconductor elements. About the adhesive composition of the comparative example 4 which contains an inorganic filler excessively, the discharge property in an inkjet apparatus is low, and a space | gap and peeling generate | occur | produce in an adhesive bond layer. On the other hand, about the adhesive composition of Examples 1-6, the discharge property in an inkjet apparatus is favorable, and can form a thin film adhesive layer stably. Further, misalignment of the semiconductor element, voids in the adhesive layer, occurrence of peeling, and the like can be suppressed.

Claims (6)

An application step of selectively applying an adhesive composition containing a thermosetting component and an organic solvent on an adhesive surface using a non-contact type coating apparatus, and the adhesive composition applied on the adhesive surface A method of forming an adhesive layer having a solvent removal step of removing the solvent from the object,
The said adhesive composition contains 1-20 mass% of inorganic fillers with an average particle diameter of 1-200 nm, The formation method of the adhesive bond layer characterized by the above-mentioned.   The method for forming an adhesive layer according to claim 1, wherein the thermosetting component includes an epoxy resin, an epoxy curing agent, and a curing accelerator.   The method for forming an adhesive layer according to claim 1, wherein the inorganic filler is silica.   The method for forming an adhesive layer according to any one of claims 1 to 3, further comprising a semi-curing step for bringing the adhesive composition into a semi-cured state by heating at 40 to 120 ° C.   The content of the thermosetting component in the adhesive composition is 5 to 50% by mass, and the viscosity at 25 ° C of the adhesive composition is 100 mPa · s or less. The method for forming an adhesive layer according to any one of claims 1 to 4. An adhesive composition used for forming an adhesive layer by a non-contact type coating apparatus,
An adhesive composition comprising 1 to 20% by mass of an inorganic filler having an average particle diameter of 1 to 200 nm and containing a thermosetting component and an organic solvent.