Adhesive composition for semiconductor package

Abstract

The present invention relates to an adhesive composition for a semiconductor package, having a relatively high storage modulus after curing under predetermined conditions, an adhesive film for a semiconductor, a dicing die bonding film, a semiconductor device, and a method for manufacturing a semiconductor device.

Description

Adhesive composition for semiconductor packaging

[0001] Cross-citation with related applications

[0002] This application claims the benefit of priority to Republic of Korea Patent Application No. 10-2023-0094412, filed July 20, 2023, and Republic of Korea Patent Application No. 10-2024-0095090, filed July 18, 2024, the entire contents of which are incorporated herein by reference.

[0003] The present invention relates to an adhesive composition for a semiconductor package, an adhesive film for a semiconductor, an adhesive film for a semiconductor, a semiconductor device, and a method for manufacturing a semiconductor device.

[0004] The need for higher density and integration in semiconductor packaging is growing. Consequently, semiconductor chips are gradually increasing in size, and stacking packages, which stack semiconductor chips in multiple layers to improve integration, is becoming widely adopted.

[0005] Due to the trend of miniaturization of semiconductor package size and increase in capacity, the demand for die applications that apply thinner semiconductor chips is increasing.

[0006] Due to the thin thickness of the semiconductor chip, cracks may occur in the semiconductor chip or the semiconductor chip may warp or sag (deflection) during the packaging process, which may not only make it difficult to proceed with the continuous process of manufacturing the semiconductor package but may also reduce the reliability of the final product.

[0007] The present invention provides an adhesive composition for a semiconductor package that can prevent cracks or warpage from occurring in a semiconductor chip even during a packaging process using a thin semiconductor chip, and has excellent adhesive strength and embedding properties.

[0008] In addition, the present invention provides an adhesive film for a semiconductor including the adhesive composition for the semiconductor package.

[0009] In addition, the present invention provides a dicing die bonding film including the above-described semiconductor adhesive film.

[0010] In addition, the present invention provides a semiconductor device having high reliability and internal structural stability while including a thin semiconductor chip.

[0011] In addition, the present invention relates to a method for manufacturing a semiconductor device that can prevent cracks or warpage from occurring in a semiconductor chip even during a packaging process using a thin semiconductor chip, and can implement excellent adhesive strength and embedding properties between a substrate and a semiconductor chip or between two or more semiconductor chips.

[0012]

[0013] The present specification provides an adhesive composition for a semiconductor package, which comprises a thermoplastic resin, a thermosetting resin and a curing agent, and has a storage modulus of 30 MPa or more at 130°C measured after curing under conditions of a temperature of 120°C to 300°C and a pressure of 0.5 Kgf / cm2 to 10 Kgf / cm2.

[0014] In this specification, an adhesive film for a semiconductor including the adhesive composition for a semiconductor package is provided.

[0015] In this specification, a dicing die bonding film including the above semiconductor adhesive film is provided.

[0016] In addition, the present specification provides a semiconductor device including a substrate; one or more semiconductor chips formed on the substrate; and an adhesive layer positioned between the substrate and the semiconductor chips formed on the substrate or between two or more semiconductor chips among the semiconductor chips; wherein the adhesive layer includes a cured product of the adhesive composition for a semiconductor package.

[0017] Hereinafter, the adhesive composition for a semiconductor package, the semiconductor device, and the method for manufacturing the semiconductor device according to specific embodiments of the invention will be described in more detail.

[0018]

[0019] Unless explicitly stated otherwise in this specification, terminology is used only to describe specific embodiments and is not intended to limit the invention.

[0020] As used herein, the singular forms also include the plural forms unless the context clearly dictates otherwise.

[0021] As used herein, the term "including" means specifying a particular characteristic, region, integer, step, operation, element and / or component, but does not exclude the presence or addition of other particular characteristics, regions, integers, steps, operations, elements, components and / or groups.

[0022] In this specification, (meth)acrylate includes both acrylate and methacrylate.

[0023]

[0024] According to one embodiment of the invention, an adhesive composition for a semiconductor package can be provided, which comprises a thermoplastic resin, a thermosetting resin, and a curing agent, and has a storage modulus of 30 MPa or more at 130°C measured after curing under conditions of a temperature of 120°C to 300°C and a pressure of 0.5 Kgf / cm2 to 10 Kgf / cm2.

[0025] The present inventors have completed the invention by confirming that when an adhesive composition for a semiconductor package is used, which has a storage modulus of 30 MPa or more at 130°C measured after curing under predetermined conditions, cracks or warpage can be prevented from occurring in a semiconductor chip even during a packaging process using a thin semiconductor chip, and excellent adhesive strength and embedding properties can be achieved.

[0026] The storage modulus at 130°C measured after curing the adhesive composition for the semiconductor package at a temperature of 120°C to 300°C and a pressure of 0.5 Kgf / cm2 to 10 Kgf / cm2 may be 30 MPa or more, 50 MPa or more, or 50 to 500 MPa, or 60 to 400 MPa.

[0027] The step of curing the adhesive composition for the semiconductor package at a temperature of 120°C to 300°C and a pressure condition of 0.5 Kgf / cm2 to 10 Kgf / cm2 may be applied under a pressure condition of 0.5 Kgf / cm2 to 10 Kgf / cm2, or 1 Kgf / cm2 to 8 Kgf / cm2.

[0028] The step of curing the adhesive composition for the semiconductor package at a temperature of 120°C to 300°C and a pressure of 0.5 Kgf / cm2 to 10 Kgf / cm2 may change the curing time in consideration of specific curing conditions, etc., and may be performed for 10 to 200 minutes, including the curing step and the steps before and after it, for example.

[0029] More specifically, under the above conditions of a temperature of 120°C to 300°C and a pressure of 0.5 Kgf / cm2 to 10 Kgf / cm2, curing can be performed by including a step of raising the temperature from 25°C to 125°C for 30 minutes under a pressure condition of 7 Kgf / cm2, a step of maintaining the temperature at 125°C for 30 minutes after the raising, and a step of cooling to 60°C after the maintaining.

[0030] The storage modulus of previously known semiconductor adhesive films measured at 130°C after curing was often in a very low range, for example, less than 10 MPa.

[0031] In contrast, since the adhesive composition for a semiconductor package has a storage modulus at 130° C. measured after the curing within the above-described range, it can be firmly bonded to a semiconductor chip having a thin thickness, for example, a thickness of 100 μm or less or 50 μm or less, while significantly reducing the stress applied to the semiconductor chip or significantly reducing deformation of the semiconductor chip. Accordingly, as described above, by using the adhesive composition for a semiconductor package of the embodiment, it is possible to prevent cracks or warpage from occurring in the semiconductor chip even during a packaging process using a thin semiconductor chip.

[0032] However, the above “curing under conditions of a temperature of 120°C to 300°C and a pressure of 0.5 Kgf / cm2 to 10 Kgf / cm2” is not intended to limit a specific use or process to which the adhesive composition for a semiconductor package of the above embodiment is applied, and is a specific condition set to define the storage modulus at 130°C that the adhesive composition for a semiconductor package of the above embodiment has after curing.

[0033]

[0034] The above-described adhesive composition for a semiconductor package can be used for connecting a substrate and a semiconductor chip having a thickness of 100 um or less or 50 um or less, or for connecting two or more semiconductor chips having a thickness of 100 um or less or 50 um or less.

[0035] The above semiconductor chip may have a thickness of 100 um or less, 50 um or less, 40 um or less, 30 um or less, or 1 um or more, 2 um or more, 5 um or more, or 10 um or more.

[0036] The storage modulus at 130°C can be determined by measuring the storage modulus (G') according to temperature while increasing the temperature from -30°C to 280°C at a rate of 10°C per minute with a frequency of 1 Hz and a strain of 0.0% using a DMA (Dynamic mechanical analysis) device. The storage modulus at 130°C of the cured adhesive composition for a semiconductor package can be confirmed.

[0037]

[0038] Meanwhile, the adhesive composition for the semiconductor package may have a storage modulus of 30 MPa or more at 130°C measured after curing under conditions of a temperature of 120°C to 300°C and a pressure of 0.5 Kgf / cm2 to 10 Kgf / cm2, without containing an excessive amount of an inorganic filler or substantially without containing the inorganic filler.

[0039] When using an adhesive composition or adhesive film containing an excessive amount of inorganic filler in a packaging process using a thin semiconductor chip, it may increase the stress applied to the semiconductor chip or cause deformation of the semiconductor chip, and may also increase the film viscosity, which may be detrimental to the embedding properties.

[0040] In contrast, the adhesive composition for the semiconductor package uses substantially less inorganic filler or does not contain any inorganic filler, so that cracks or warpage can be prevented from occurring in the semiconductor chip even during the packaging process using a thin semiconductor chip.

[0041] More specifically, the adhesive composition for the semiconductor package may contain 5 wt% or less, 4.9 wt% or less, 4.8 wt% or less, 4.6 wt% or less, 1 wt% or less, 0.1 wt% or less, or 0.01 wt% or less of the inorganic filler, and may also contain substantially no inorganic filler.

[0042] The adhesive composition for the semiconductor package may not contain an inorganic filler, or the adhesive composition for the semiconductor package may further contain an inorganic filler in an amount of 4.9 wt% or less.

[0043] The specific type of the above-mentioned inorganic filler is not particularly limited, and the above-mentioned inorganic filler may be an inorganic fine particle having a particle size of 1000 μm or less.

[0044]

[0045] Meanwhile, the melt viscosity of the adhesive composition for semiconductor packages measured at 110°C by applying a shear rate of 5 rad / s may be 3,000 Pa·s to 50,000 Pa·s, or 4,000 Pa·s to 30,000 Pa·s, or 4,500 Pa·s to 25,000 Pa·s, or 4,000 Pa·s to 20,000 Pa·s.

[0046] The above melt viscosity may be a value measured before the above-described curing of the adhesive composition for the semiconductor package.

[0047] The melt viscosity of the adhesive composition for the semiconductor package can be measured by a known method, and for example, the adhesive composition for the semiconductor package can be manufactured in the form of an adhesive film and then measured.

[0048] More specifically, a sample of an adhesive film obtained from the adhesive composition for the semiconductor package is laminated to a thickness of 300 ㎛ to 800 ㎛, laminated using a roll laminator at 60 ℃, and then formed into a circle with a diameter of 8 mm, and then the melt viscosity can be measured using a method such as TA ARES-G2 equipment. At this time, the melt viscosity can also be a viscosity value measured at 110 ℃ by applying a heating rate of 20 ℃ / min at a shear rate of 5 Rad / s.

[0049] The above melt viscosity refers to an absolute value indicating the degree of stickiness that a material in a fluid state resists against the direction of movement.

[0050] The adhesive composition for the semiconductor package can undergo a die attach process at a temperature of about 110°C during the semiconductor package process, and since the melt viscosity of the adhesive composition for the semiconductor package measured at 110°C is 3,000 Pa·s to 50,000 Pa·s, or 4,000 Pa·s to 30,000 Pa·s, the space formed between a substrate and a semiconductor chip or between two or more semiconductor chips can be efficiently filled, thereby preventing the occurrence of voids or poor connection conditions.

[0051]

[0052] As described above, the adhesive composition for the semiconductor package may include a thermoplastic resin.

[0053] Examples of the above thermoplastic resin include (meth)acrylate resins, polyimides, polyether imides, polyester imides, polyamides, polyether sulfones, polyether ketones, polyvinyl chloride, polybutadiene resins, acrylonitrile-butadiene copolymers, acrylonitrile-butadiene-styrene resins, styrene-butadiene copolymers, and phenoxy resins.

[0054] The thermoplastic resin may have a glass transition temperature of -50°C to 70°C. By using a thermoplastic resin having the above-described glass transition temperature, the final semiconductor adhesive film can secure high adhesive strength and can be easily manufactured in the form of a thin film, etc.

[0055] Meanwhile, the (meth)acrylate resin including a repeating unit substituted with the glycidyl group or epoxy group has the characteristic of high reactor density and can have a glass transition temperature of -20°C to 30°C.

[0056] Here, if the epoxy group content in the (meth)acrylate resin is less than 1 wt%, compatibility and adhesiveness with the epoxy resin are insufficient, and if it exceeds 30 wt%, the viscosity increase rate due to curing is too fast, so that the embedding or adhesion of the bonding target may not be sufficiently achieved.

[0057] The (meth)acrylate resin including the repeating unit substituted with the above glycidyl group or epoxy group may have a weight average molecular weight of 50,000 g / mol to 1,200,000 g / mol.

[0058] As a non-limiting example, the weight-average molecular weight can be measured using an Agilent PL-GPC 220 instrument equipped with a 300 mm long PolarGel MIXED-L column (Polymer Laboratories). The measurement temperature is 65 °C, dimethylformamide is used as a solvent, and the flow rate is measured at a rate of 1 mL / min. The sample is prepared at a concentration of 10 mg / 10 mL and then supplied in an amount of 100 μL. The Mw and Mn values ​​are derived with reference to a calibration curve formed using polystyrene standards. The molecular weights (g / mol) of the polystyrene standards are 8 types: 580 / 3,940 / 8,450 / 31,400 / 70,950 / 316,500 / 956,000 / 4,230,000.

[0059] The above (meth)acrylate resin is an epoxy group-containing acrylic copolymer, and may contain 1 to 30 wt%, or 2 to 20 wt%, or 2.5 to 15 wt% of glycidyl acrylate or glycidyl methacrylate based on the total weight.

[0060] If the epoxy group content in the above (meth)acrylate resin is less than 1 wt%, the compatibility and adhesiveness with the epoxy resin are insufficient, and if it exceeds 30 wt%, the viscosity increase rate due to curing is too fast, so that the embedding or adhesion of the bonding target may not be sufficiently achieved.

[0061] The content of the thermoplastic resin can be determined by considering the flowability of the composition and the physical properties of the final adhesive film when manufacturing the adhesive film.

[0062]

[0063] Meanwhile, the thermoplastic resin may include two or more types of (meth)acrylate resins having different glass transition temperatures.

[0064] More specifically, the thermoplastic resin may include a (meth)acrylate resin having a repeating unit substituted with a glycidyl group or an epoxy group and having a glass transition temperature of -20°C to 5°C; and a (meth)acrylate resin having a repeating unit substituted with a glycidyl group or an epoxy group and having a glass transition temperature of 7°C to 30°C.

[0065] (Meth)acrylate resins having different glass transition temperatures may each have a weight average molecular weight of 50,000 to 1,500,000.

[0066] Since the thermoplastic resin includes a repeating unit substituted with a glycidyl group or an epoxy group and includes a (meth)acrylate resin having a glass transition temperature of -20°C to 5°C, the adhesive composition for a semiconductor package can realize higher workability, making it easier to process into a form such as a film.

[0067] In addition, since the thermoplastic resin includes a (meth)acrylate resin having a repeating unit substituted with a glycidyl group or an epoxy group and having a glass transition temperature of 7°C to 30°C, the adhesive composition for a semiconductor package can have improved wettability characteristics for a wafer along with a higher storage modulus (130°C).

[0068]

[0069] As described above, the adhesive composition for the semiconductor package may include a thermosetting resin.

[0070] More specifically, the thermosetting resin may include a silsesquioxane compound substituted with a glycidyl group or an epoxy group.

[0071] Accordingly, when the adhesive composition for semiconductor packaging including the silsesquioxane compound substituted with the glycidyl group or epoxy group is used, cracks or warping of the semiconductor chip can be prevented even during the packaging process using a thin semiconductor chip, and excellent adhesive strength and embedding properties can be achieved.

[0072] The silsesquioxane compound substituted with the above glycidyl group or epoxy group may include an organic-inorganic hybrid epoxy resin having a repeating unit represented by the following chemical formula 1.

[0073] [Chemical Formula 1]

[0074]

[0075] In the above chemical formula 1, R is a monovalent functional group each independently having one or more epoxy groups, and n is 1 to 30.

[0076] R of the above chemical formula 1 1 Each of which may be independently any one functional group selected from the group consisting of the following structural formulas:

[0077] , , , , , , and .

[0078] In the above structural formula The symbols indicate where the functional group is connected to other groups.

[0079]

[0080] The above organic-inorganic hybrid epoxy resin may have an average epoxy equivalent of 50 g / eq. to 300 g / eq. The average epoxy equivalent is a value calculated based on the weight ratio and epoxy equivalent of each epoxy resin included in the organic-inorganic hybrid epoxy resin.

[0081] Preferably, the organic-inorganic hybrid epoxy resin may have an average epoxy equivalent weight of 50 g / eq. to 300 g / eq., or 100 g / eq. to 300 g / eq., or 100 g / eq. to 250 g / eq., or 150 g / eq. to 250 g / eq., or 150 g / eq. to 200 g / eq., or 160 g / eq. to 180 g / eq.

[0082] In order to realize the effect of adding the organic-inorganic hybrid epoxy resin, the organic-inorganic hybrid epoxy resin preferably has an average epoxy equivalent of 50 g / eq. or more. However, an epoxy equivalent that is too high may deteriorate the properties of the adhesive composition for semiconductor packages. Therefore, the organic-inorganic hybrid epoxy resin preferably has an average epoxy equivalent of 300 g / eq. or less.

[0083] The above organic-inorganic hybrid epoxy resin preferably has a viscosity of 0.1 Pa·s to 10000 Pa·s, or 0.5 Pa·s to 5000 Pa·s, measured at 25°C.

[0084] If the viscosity of the organic-inorganic hybrid epoxy resin is too high, the properties of the adhesive composition for semiconductor packages and the properties of the adhesive film may deteriorate. Therefore, it is preferable that the organic-inorganic hybrid epoxy resin have a viscosity of 10,000 Pa·s or less.

[0085]

[0086] The above thermosetting resin may further include an epoxy resin together with a silsesquioxane compound substituted with a glycidyl group or an epoxy group.

[0087] Specific examples of such epoxy resins include bisphenol-based epoxy resins, biphenyl-based epoxy resins, naphthalene-based epoxy resins, fluorene-based epoxy resins, phenol novolac-based epoxy resins, cresol novolac-based epoxy resins, xyloxal-based epoxy resins, trishydroxylphenylmethane-based epoxy resins, tetraphenylmethane-based epoxy resins, dicyclopentadiene-based epoxy resins, dicyclopentadiene-modified phenol-based epoxy resins, or mixtures or copolymers of two or more thereof.

[0088] More specifically, when the thermosetting resin further comprises an epoxy resin together with a silsesquioxane compound substituted with a glycidyl group or an epoxy group, the epoxy resin may be a biphenyl-based epoxy resin having a softening point of 50°C to 100°C, a cresol novolac-based epoxy resin having a softening point of 50°C to 100°C, or a bisphenol A epoxy resin having a softening point of 50°C to 100°C.

[0089] When the thermosetting resin further includes an epoxy resin together with a silsesquioxane compound substituted with a glycidyl group or an epoxy group, the thermosetting resin may include 10 to 500 parts by weight of the epoxy resin relative to 100 parts by weight of the silsesquioxane compound substituted with a glycidyl group or an epoxy group.

[0090]

[0091] Meanwhile, the adhesive composition for the semiconductor package may include at least one compound selected from the group consisting of an amine-based curing agent, a phenol-based curing agent, and an acid anhydride-based curing agent as the curing agent.

[0092] As the above hardener, a novolak-based phenol resin can be preferably applied.

[0093] The above novolak phenol resin has a chemical structure in which a ring is positioned between reactive functional groups. Due to these structural characteristics, the novolak phenol resin can further reduce the hygroscopicity of the adhesive composition and enhance stability during a high-temperature IR reflow process, thereby preventing peeling of the adhesive film or reflow cracking.

[0094] Specific examples of the above novolac-based phenol resin include at least one selected from the group consisting of novolac phenol resin, xyloc novolac phenol resin, cresol novolac phenol resin, biphenyl novolac phenol resin, bisphenol A novolac phenol resin, and bisphenol F novolac phenol resin.

[0095] The above novolak-based phenol resin can preferably be applied having a softening point of 60°C or higher, or 60°C to 150°C, or 105°C to 150°C, or 70°C to 120°C.

[0096] A novolak phenolic resin having a softening point of 60°C or higher ensures that the adhesive composition has sufficient heat resistance, strength, and adhesiveness after curing. However, if the softening point of the novolak phenolic resin is too high, the fluidity of the adhesive composition may be reduced, which may lead to the creation of voids within the adhesive during an actual semiconductor manufacturing process, significantly reducing the reliability or quality of the final product.

[0097] The above novolak-based phenol resin preferably has a hydroxyl equivalent of 80 g / eq to 300 g / eq and a softening point of 60°C to 150°C.

[0098]

[0099] The adhesive composition for the semiconductor package can appropriately adjust the content of each of the thermoplastic resin, the thermosetting resin, and the curing agent in consideration of specific physical properties, etc., and for example, the adhesive composition for the semiconductor package can include 5 to 500 parts by weight of the thermoplastic resin and 1 to 150 parts by weight of the curing agent relative to 100 parts by weight of the thermosetting resin.

[0100] The adhesive composition for the semiconductor package may further include at least one compound selected from the group consisting of a phosphorus compound, a boron compound, a phosphorus-boron compound, and an imidazole compound as the curing catalyst.

[0101] The above curing catalyst serves to promote the action of the curing agent or the curing of the semiconductor adhesive resin composition, and any curing catalyst known to be used in the manufacture of semiconductor adhesive films and the like can be used without significant limitation.

[0102] The content of the curing catalyst can be adjusted in consideration of the content of the curing agent and the properties of the final adhesive film to be manufactured. For example, the curing catalyst can be used in an amount of 0.1 to 20 parts by weight, or 0.5 to 15 parts by weight, or 1.0 to 10 parts by weight, or 1.5 to 5 parts by weight, or 1.5 to 3 parts by weight, based on 100 parts by weight of the thermosetting resin.

[0103]

[0104] The adhesive composition for the semiconductor package may further include an organic solvent.

[0105] The content of the organic solvent may be determined by considering the properties of the adhesive composition and the adhesive film including the same, and the productivity of the manufacturing process thereof.

[0106] For example, the organic solvent may be included in an amount of 10 to 90 parts by weight based on 100 parts by weight of the total of the thermosetting resin, thermoplastic resin, curing agent, and other additives.

[0107] The organic solvent may be at least one compound selected from the group consisting of esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides.

[0108] The above ester solvents are ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, gamma-butyrolactone, epsilon-caprolactone, delta-valerolactone, alkyl oxyacetic acid (e.g., methyl oxyacetic acid, ethyl oxyacetic acid, methyl methoxyacetic acid, ethyl methoxyacetic acid, butyl methoxyacetic acid, methyl ethoxyacetic acid, ethyl ethoxyacetic acid, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionate Methyl, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc.

[0109] The above ether solvent may be diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc.

[0110] The above ketone solvent may be methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc.

[0111] The above aromatic hydrocarbon solvent may be toluene, xylene, anisole, limonene, etc.

[0112] The above sulfoxide solvent may be dimethyl sulfoxide, etc.

[0113]

[0114] The above adhesive composition for a semiconductor package may further include a coupling agent.

[0115] The type of the above coupling agent is not particularly limited, but preferably, 2-(3,4 epoxycyclohexyl)-ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyl-diethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2(aminoethyl)3-aminopropylmethyldimethoxysilane, N-2(aminoethyl)3-aminopropyl-trimethoxysilane, N-2(aminoethyl)3-aminopropyltriethoxysilane, 3-aminopropyl-trimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxylyl-N-(1,3 dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, mercapto-containing 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. can be preferably applied. there is.

[0116]

[0117] The above phenols may be compounds having at least two phenolic hydroxyl groups.

[0118] For example, the phenols may be catechol, resorcinol, hydroquinone, biphenol, dihydroxynaphthalene, hydroxyhydroquinone, pyrogallol, methylidenebiphenol (bisphenol F), isopropylidenebiphenol (bisphenol A), ethylidenebiphenol (bisphenol AD), 1,1,1-tris(4-hydroxyphenyl)ethane, trihydroxybenzophenone, trihydroxyacetophenone, polyp-vinylphenol, etc.

[0119] As a compound having at least two phenolic hydroxyl groups, a polycondensation product with at least one compound selected from compounds having at least one phenolic hydroxyl group in the molecule; an aromatic compound having two halomethyl groups, alkoxymethyl groups or hydroxylmethyl groups in the molecule; and at least one compound selected from divinylbenzene and aldehydes can be applied.

[0120] Examples of compounds having at least one phenolic hydroxyl group in the molecule include phenol, alkylphenol, naphthol, cresol, catechol, resorcinol, hydroquinone, biphenol, dihydroxynaphthalene, hydroxyhydroquinone, pyrogallol, methylidenebiphenol (bisphenol F), isopropylidenebiphenol (bisphenol A), ethylidenebiphenol (bisphenol AD), 1,1,1-tris(4-hydroxyphenyl)ethane, trihydroxybenzophenone, trihydroxyacetophenone, and poly-p-vinylphenol. In addition, examples of aromatic compounds having two halomethyl groups, alkoxymethyl groups, or hydroxylmethyl groups in the molecule include 1,2-bis(chloromethyl)benzene, 1,3-bis(chloromethyl)benzene, 1,4-bis(chloromethyl)benzene, 1,2-bis(methoxymethyl)benzene, 1,3-bis(methoxymethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,2-bis(hydroxymethyl)benzene, 1,3-bis(hydroxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, bis(chloromethyl)biphenyl, and bis(methoxymethyl)biphenyl.

[0121] Examples of the above aldehydes include formaldehyde (formalin as its aqueous solution), paraformaldehyde, trioxane, and hexamethylenetetramine.

[0122] Examples of the above polycondensates include phenol novolac resin, which is a polycondensate of phenol and formaldehyde, cresol novolac resin, which is a polycondensate of cresol and formaldehyde, naphthol novolac resin, which is a polycondensate of naphthols and formaldehyde, phenol aralkyl resin, which is a polycondensate of phenol and 1,4-bis(methoxymethyl)benzene, polycondensate of bisphenol A and formaldehyde, polycondensate of phenol and divinylbenzene, and polycondensate of cresol, naphthol, and formaldehyde. In addition, these polycondensates may be rubber-modified or may have an aminotriazine skeleton or dicyclopentadiene skeleton introduced into the molecular backbone.

[0123] In addition, as liquefied compounds obtained by allylating the above-mentioned phenolic hydroxyl group, examples thereof include allylated phenol novolac resin, diallylbisphenol A, diallylbisphenol F, and diallylbiphenol.

[0124]

[0125] The above alcohol may be a compound having at least two alcoholic hydroxyl groups in the molecule.

[0126] For example, the alcohols include 1,3-dioxane-5,5-dimethanol, 1,5-pentanediol, 2,5-flangemethanol, diethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, 1,2,3-hexanetriol, 1,2,4-butanetriol, 1,2,6-hexanetriol, 3-methylpentane-1,3,5-triol, glycerin, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, ribitol, sorbitol, 2,4-diethyl-1,5-pentanediol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 1,3-butylene glycol, 2-ethyl-1,3-hexanediol, N-butyldiethanolamine, N-ethyldiethanolamine, diethanolamine, It can be triethanolamine, N,N-bis(2-hydroxyethyl)isopropanolamine, bis(2-hydroxymethyl)iminotris(hydroxymethyl)methane, N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine, 1,1',1'',1'''-(ethylenedinitrilo)tetrakis(2-propanol), etc.

[0127]

[0128] Meanwhile, according to another embodiment of the invention, an adhesive film for a semiconductor including the adhesive composition for a semiconductor package of the above embodiment can be provided.

[0129] The above adhesive composition for a semiconductor package may be in the form of an adhesive film.

[0130] The above adhesive film may include an adhesive layer in which the adhesive composition for the semiconductor package is dried or cured.

[0131] The above semiconductor adhesive films may each have a thickness of 1 μm to 300 μm. The above thickness may refer to the thickness of a single layer or one layer of the semiconductor adhesive film. In addition, the semiconductor adhesive films may each have a thickness of 1 μm or more, 3 μm or more, 5 μm or more, or 10 μm or more. In addition, the semiconductor adhesive films may each have a thickness of 300 μm or less, or 100 μm or less, or 90 μm or less, or 70 μm or less. When the thickness of the semiconductor adhesive film increases or decreases by a specific value, the physical properties measured in the semiconductor adhesive film may also change by a specific value.

[0132] In addition, the semiconductor adhesive film may be in the form of a multilayer film in which a single film having a thickness of 1 ㎛ to 300 ㎛ forms a plurality of layers.

[0133] The above adhesive film can be used as a die attach film (DAF) for bonding a lead frame or substrate to a die or for bonding dies to dies. Accordingly, the adhesive film can be processed into a form such as a die bonding film or a dicing die bonding film.

[0134] The above adhesive film may have a configuration in which a support substrate and an adhesive layer are sequentially laminated.

[0135] The above adhesive film may have a configuration in which a support substrate, an adhesive layer, and a protective film are sequentially laminated.

[0136] The above adhesive film may have a configuration in which a support substrate, an adhesive layer, an adhesive layer, and a protective film are sequentially laminated.

[0137] As the above-mentioned supporting material, a resin film having excellent heat resistance or chemical resistance; a crosslinked film obtained by crosslinking the resin constituting the resin film; or a film obtained by applying a silicone resin or the like to the surface of the resin film and then performing a peeling treatment, etc. may be used.

[0138] As the resin constituting the above resin film, polyolefins such as polyester, polyethylene, polypropylene, polybutene, and polybutadiene, vinyl chloride, ethylene-methacrylic acid copolymer, ethylene vinyl acetate copolymer, polyester, polyimide, polyethylene terephthalate, polyamide, and polyurethane can be applied.

[0139] The thickness of the above-mentioned support substrate is not particularly limited, but may be 3 to 400 ㎛, or 5 to 200 ㎛, or 10 to 150 ㎛.

[0140] The above adhesive layer may include the above-described adhesive composition for a semiconductor package. The details of the above-described adhesive composition for a semiconductor package are as described above.

[0141] The type of the above protective film is not particularly limited, and a plastic film known in this field can be applied. For example, the above protective film may be a plastic film containing a resin such as low-density polyethylene, linear polyethylene, medium-density polyethylene, high-density polyethylene, ultra-low-density polyethylene, random copolymer of polypropylene, block copolymer of polypropylene, homopolypropylene, polymethylpentene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-ionomer copolymer, ethylene-vinyl alcohol copolymer, polybutene, or copolymer of styrene.

[0142]

[0143] According to another embodiment of the invention, a dicing die-bonding film may be provided, comprising: a base film; an adhesive layer formed on the base film; and an adhesive layer formed on the adhesive layer and including the adhesive film for semiconductors of the other embodiment.

[0144] Specific details regarding the above semiconductor adhesive film are as described above in the other embodiments.

[0145] The type of base film included in the dicing die-bonding film is not particularly limited, and for example, a plastic film or metal foil known in this field can be used. For example, the base film may be a low-density polyethylene, a linear polyethylene, a medium-density polyethylene, a high-density polyethylene, an ultra-low-density polyethylene, a random copolymer of polypropylene, a block copolymer of polypropylene, a homopolypropylene, a polymethylpentene, an ethylene-vinyl acetate copolymer, an ethylene-methacrylic acid copolymer, an ethylene-methyl methacrylate copolymer, an ethylene-ionomer copolymer, an ethylene-vinyl alcohol copolymer, a polybutene, a copolymer of styrene, or a mixture of two or more thereof. The meaning of the base film including a mixture of two or more polymers as described above includes a film having a structure in which two or more layers of films each including the above-mentioned polymers are laminated, or a single-layer film including two or more of the above-mentioned polymers.

[0146] The thickness of the above-mentioned base film is not particularly limited, and is usually formed to a thickness of 10 ㎛ to 200 ㎛, preferably 50 ㎛ to 180 ㎛. If the thickness is less than 10 ㎛, there is a concern that the control of the cut depth in the dicing process may become unstable, and if it exceeds 200 ㎛, there is a concern that a large amount of burrs may be generated in the dicing process, or the elongation may decrease, so that the expanding process may not be performed accurately.

[0147] The above-mentioned substrate film may be subjected to conventional physical or chemical treatments such as matting treatment, corona discharge treatment, primer treatment, or cross-linking treatment as needed.

[0148] Meanwhile, the adhesive layer may include an ultraviolet-curable adhesive or a heat-curable adhesive. When using an ultraviolet-curable adhesive, ultraviolet rays are irradiated from the substrate film side to increase the cohesive force and glass transition temperature of the adhesive, thereby reducing the adhesive force. In the case of a heat-curable adhesive, temperature is applied to reduce the adhesive force.

[0149] In addition, the above UV-curable adhesive may include a (meth)acrylate resin, a UV-curable compound, a photoinitiator, and a crosslinking agent.

[0150] The (meth)acrylate resin described above may have a weight average molecular weight of 100,000 g / mol to 1.5 million g / mol, preferably 200,000 g / mol to 1 million g / mol. If the weight average molecular weight is less than 100,000 g / mol, the coating property or cohesiveness may be reduced, and there is a risk that residue may remain on the adherend upon peeling, or the adhesive may be destroyed. In addition, if the weight average molecular weight exceeds 1.5 million g / mol, there is a risk that the base resin may interfere with the reaction of the ultraviolet-curable compound, and the peeling force may not be reduced efficiently.

[0151] Such (meth)acrylate-based resins may be, for example, copolymers of (meth)acrylic acid ester-based monomers and crosslinkable functional group-containing monomers. At this time, examples of the (meth)acrylic acid ester-based monomers include alkyl (meth)acrylates, and more specifically, monomers having an alkyl group having 1 to 12 carbon atoms, such as pentyl (meth)acrylate, n-butyl (meth)acrylate, ethyl (meth)acrylate, methyl (meth)acrylate, hexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, or decyl (meth)acrylate, or a mixture of two or more thereof. As the number of carbon atoms in the alkyl monomer increases, the glass transition temperature of the final copolymer decreases. Therefore, an appropriate monomer should be selected based on the desired glass transition temperature.

[0152] In addition, examples of the crosslinkable functional group-containing monomer include one or a mixture of two or more types of a hydroxyl group-containing monomer, a carboxyl group-containing monomer, or a nitrogen-containing monomer. At this time, examples of the hydroxyl group-containing compound include 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate, examples of the carboxyl group-containing compound include (meth)acrylic acid, and examples of the nitrogen-containing monomer include (meth)acrylonitrile, N-vinyl pyrrolidone, or N-vinyl caprolactam, but are not limited thereto.

[0153] The above (meth)acrylate resin may additionally include low molecular weight compounds containing carbon-carbon double bonds such as vinyl acetate, styrene or acrylonitrile from the viewpoint of improving other functionalities such as compatibility.

[0154] In addition, the type of the above-mentioned UV-curable compound is not particularly limited, and for example, a multifunctional compound (e.g., multifunctional urethane acrylate, multifunctional acrylate monomer or oligomer, etc.) having a weight average molecular weight of 100 g / mol to 300,000 g / mol, or 500 g / mol to 100,000 g / mol can be used. A person skilled in the art can easily select an appropriate compound according to the intended use.

[0155] The content of the above-mentioned UV-curable compound may be 5 to 400 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the above-mentioned base resin. If the content of the UV-curable compound is less than 5 parts by weight, there is a concern that the adhesive strength after curing may not decrease sufficiently, resulting in poor pick-up properties. On the other hand, if the content exceeds 400 parts by weight, there is a concern that the adhesive may have insufficient cohesion before UV irradiation, or that peeling from a release film or the like may not occur easily.

[0156] The type of the photoinitiator is not particularly limited, and a general initiator known in this field can be used, and the content may be 0.05 to 20 parts by weight based on 100 parts by weight of the UV-curable compound. If the content of the photoinitiator is less than 0.05 parts by weight, there is a concern that the curing reaction by UV irradiation is insufficient, which may result in a decrease in pick-up property, and if it exceeds 20 parts by weight, there is a concern that the crosslinking reaction may occur in short units during the curing process, or unreacted UV-curable compound may be generated, which may cause residue on the surface of the adherend, or the peeling force may be excessively low after curing, which may result in a decrease in pick-up property.

[0157] In addition, the type of crosslinking agent included in the adhesive to provide adhesive strength and cohesive strength is not particularly limited, and conventional compounds such as isocyanate compounds, aziridine compounds, epoxy compounds, or metal chelate compounds can be used. The crosslinking agent may be included in an amount of 2 to 40 parts by weight, preferably 2 to 20 parts by weight, based on 100 parts by weight of the base resin. If the content is less than 2 parts by weight, there is a concern that the cohesive strength of the adhesive may be insufficient, and if it exceeds 20 parts by weight, there is a concern that the adhesive strength before ultraviolet irradiation may be insufficient, resulting in chip flying, etc.

[0158] The above adhesive layer may further include a tackifier such as a rosin resin, a terpene resin, a phenol resin, a styrene resin, an aliphatic petroleum resin, an aromatic petroleum resin, or an aliphatic aromatic copolymerized petroleum resin.

[0159] The thickness of the adhesive layer is not particularly limited, but may range from 1 μm to 500 μm, for example.

[0160] Meanwhile, as described above, the adhesive layer is formed on the adhesive layer and may include the semiconductor adhesive film of the embodiment described above. The content regarding the semiconductor adhesive film includes all of the matters described above in the other embodiment.

[0161] The method for manufacturing the above-described dicing die-bonding film is not particularly limited, and for example, a method of sequentially forming an adhesive portion, an adhesive portion, and a release film on a base film, or a method of separately manufacturing a dicing film (base film + adhesive portion) and a die-bonding film or a release film on which an adhesive portion is formed, and then laminating them, etc. may be used.

[0162]

[0163] Meanwhile, according to another embodiment of the invention, a method for dicing a semiconductor wafer may be provided, including a pretreatment step of completely dividing or partially dividing a semiconductor wafer including a dicing die-bonding film of the other embodiment and a wafer laminated on at least one surface of the dicing die-bonding film; and a step of irradiating ultraviolet rays to a base film of the pretreated semiconductor wafer and picking up individual chips separated by the dividing of the semiconductor wafer.

[0164] The content regarding the above dicing die bonding film includes all the content described above in the other embodiments.

[0165] Except for the details of the above dicing method, devices, methods, etc. commonly used in the known semiconductor wafer dicing method can be used without any particular restrictions.

[0166] The above semiconductor wafer dicing method may further include a step of expanding the semiconductor wafer after the above preprocessing step. In this case, a step of irradiating the substrate film of the expanded semiconductor wafer with ultraviolet rays and picking up individual chips separated by the division of the semiconductor wafer is performed thereafter.

[0167] By using a dicing die-bonding film including the above dicing film, a burr phenomenon that may occur during the dicing process of a semiconductor wafer can be minimized, thereby preventing contamination of semiconductor chips and improving the reliability and lifespan of semiconductor chips.

[0168]

[0169] Meanwhile, according to another embodiment of the invention, a semiconductor device may be provided, including: a substrate; one or more semiconductor chips formed on the substrate; and an adhesive layer positioned between the substrate and the semiconductor chips formed on the substrate or between two or more of the semiconductor chips.

[0170] At this time, the adhesive layer may include a cured product of the adhesive composition for a semiconductor package of the above embodiment.

[0171] The above semiconductor chip may have a thickness of 100 um or less, 50 um or less, 40 um or less, 30 um or less, or 1 um or more, 2 um or more, 5 um or more, or 10 um or more.

[0172] In the process of obtaining a cured product of the adhesive composition for the semiconductor package, the curing conditions are not particularly limited, and for example, the curing may be performed under conditions of a temperature of 120°C to 300°C and a pressure of 0.5 Kgf / cm2 to 10 Kgf / cm2. However, as described above, the curing conditions do not limit the specific use or use form of the adhesive composition for the semiconductor package.

[0173] The storage modulus of the adhesive layer at 130°C measured after the curing may be 30 MPa or more, or 50 to 500 MPa, or 60 to 400 MPa.

[0174] More specific details regarding the adhesive layer include those described above regarding the adhesive composition for a semiconductor package of the above embodiment.

[0175] The semiconductor device of the above embodiment can have high reliability and internal structural stability while including a thin semiconductor chip.

[0176] The adhesive composition for the semiconductor package may have a melt viscosity measured at 110°C of 3,000 Pa·s to 50,000 Pa·s, or 4,000 Pa·s to 30,000 Pa·s, or 4,500 Pa·s to 25,000 Pa·s, or 4,000 Pa·s to 20,000 Pa·s when a shear rate of 5 rad / s is applied.

[0177] The adhesive composition for a semiconductor package of the above embodiment has the melt viscosity described above at 110°C, so that it can efficiently fill a space formed between a substrate and a semiconductor chip or between two or more semiconductor chips, thereby preventing the occurrence of voids or poor connection.

[0178] Since the storage modulus of the adhesive layer at 130°C is 30 MPa, it is possible to firmly bond a semiconductor chip having a thin thickness while greatly reducing the stress applied to the semiconductor chip or greatly reducing the deformation of the semiconductor chip, and accordingly, cracks or warping of the semiconductor chip can be prevented even during the packaging process using a semiconductor chip having a thin thickness.

[0179]

[0180] Meanwhile, according to another embodiment of the invention, a method for manufacturing a semiconductor device can be provided, including a step of forming an adhesive layer positioned between a substrate and a semiconductor chip formed on the substrate or between two or more semiconductor chips, and curing the adhesive layer under conditions of a temperature of 120° C. to 300° C. and a pressure of 0.5 Kgf / cm2 to 10 Kgf / cm2.

[0181] At this time, the adhesive layer may include a cured product of the adhesive composition for a semiconductor package of the above embodiment.

[0182] However, as described above, the curing conditions do not limit the specific use or use form of the adhesive composition for semiconductor packages.

[0183] The above semiconductor chip may have a thickness of 100 um or less, 50 um or less, 40 um or less, 30 um or less, or 1 um or more, 2 um or more, 5 um or more, or 10 um or more.

[0184] More specific details regarding the adhesive layer include those described above regarding the adhesive composition for a semiconductor package of the above embodiment.

[0185] In the method for manufacturing the above semiconductor device, a conventional semiconductor packaging method can be used, excluding the above-described contents.

[0186]

[0187] According to the present invention, an adhesive composition for a semiconductor package can be provided which can prevent cracks or warpage from occurring in a semiconductor chip even during a packaging process using a thin semiconductor chip, and has excellent adhesive strength and embedding properties, an adhesive film for a semiconductor including the adhesive composition for a semiconductor package, and a dicing die-bonding film including the adhesive film for a semiconductor can be provided.

[0188] In addition, according to the present invention, a semiconductor device having high reliability and internal structural stability while including a thin semiconductor chip, and a method for manufacturing a semiconductor device that can prevent cracks or warpage from occurring in the semiconductor chip even during a packaging process using a thin semiconductor chip, and can implement excellent adhesive strength and embedding properties between a substrate and a semiconductor chip or between two or more semiconductor chips can be provided.

[0189]

[0190] Figure 1 schematically illustrates a semiconductor device having an overhang structure used in die-deflection evaluation among test examples.

[0191]

[0192] Hereinafter, preferred embodiments are presented to aid understanding of the invention. However, the following examples are intended only to illustrate the invention and are not intended to limit the invention to these embodiments.

[0193]

[0194] [Manufacturing Example: Manufacturing of Thermoplastic Acrylate Resin]

[0195] Manufacturing Example 1

[0196] (Manufacture of thermoplastic acrylate resin)

[0197] 40 g of butyl acrylate, 30 g of ethyl acrylate, 30 g of acrylonitrile, 5 g of methyl methacrylate, and 5 g of glycidyl methacrylate were mixed in 100 g of toluene and reacted at 80°C for about 12 hours to synthesize an acrylate resin (weight average molecular weight 1,000,000 g / mol, glass transition temperature 15°C) in which glycidyl groups were introduced as branched chains.

[0198]

[0199] Manufacturing Example 2

[0200] (Manufacture of thermoplastic acrylate resin)

[0201] 70 g of butyl acrylate, 25 g of acrylonitrile, 5 g of methyl methacrylate, and 10 g of glycidyl methacrylate were mixed with 100 g of toluene and reacted at 80°C for about 12 hours to synthesize an acrylate resin (weight average molecular weight 600,000 g / mol, glass transition temperature -5°C) in which glycidyl groups were introduced as branched chains.

[0202]

[0203] [Example: Preparation of adhesive composition for semiconductor package]

[0204] Examples 1 to 6

[0205] (1) Preparation of adhesive composition for semiconductor package

[0206] An adhesive composition for semiconductor packages (solid content 20 wt%) was obtained by mixing the components and contents shown in Table 1 below into methyl ethyl ketone.

[0207]

[0208] (2) Manufacturing of adhesive film

[0209] The adhesive composition was applied onto a polyethylene terephthalate film (thickness 38 ㎛) that had been subjected to release treatment using a comma coater, and then dried at 110°C for 3 minutes to obtain an adhesive film having an adhesive layer of about 20 ㎛ in thickness.

[0210]

[0211] (3) Measurement of melt viscosity of adhesive film

[0212] The adhesive film obtained above was laminated using a roll laminator at 60°C and laminated to a thickness of 640 μm, and then molded into a circle with a diameter of 8 mm. Then, the melt viscosity of the adhesive film was measured using TA ARES-G2 equipment. At this time, the melt viscosity was determined as the viscosity value measured at 110°C by applying a heating rate of 20°C / min at a shear rate of 5 Rad / s.

[0213]

[0214] (4) Measurement of storage modulus of adhesive film at 130 ℃

[0215] The adhesive film obtained above was laminated using a roll laminator at 60°C and laminated to a thickness of 640 μm to manufacture a sample.

[0216] The above-manufactured sample was placed in a pressurized oven (CMT, Pressurized Cure Oven PCO), and under a pressure condition of 7 Kgf / ㎠, the temperature was increased from 25℃ to 125℃ for 30 minutes, and after the temperature increase, it was maintained at a temperature of 125℃ for 30 minutes, and after the maintenance, it was cooled to 60℃ to perform curing.

[0217] Then, the sample that underwent the above-mentioned curing process was processed into a square with a length of 17.5 mm and a width of 5.3 mm and processed into a measurement sample, and using a DMA (Dynamic mechanical analysis, TA DMA Q800) device, the temperature was increased from -30℃ to 280℃ at a rate of 10℃ per minute with a frequency of 1Hz and a strain of 0.0%, and the storage modulus (G') according to the temperature was measured, thereby measuring the storage modulus (G') of the adhesive film at 130℃.

[0218]

[0219] (5) Manufacturing of dicing die bonding film

[0220] The adhesive film manufactured in the above (2) was transferred to a dicing film (an adhesive layer having a thickness of 10 μm and a polyolefin film having a thickness of 100 μm) to manufacture a dicing die bonding film.

[0221]

[0222] (6) Manufacturing of semiconductor devices

[0223] After peeling off the polyethylene terephthalate film that has undergone a release process from the dicing die-bonding film manufactured above, a semiconductor wafer prepared on top of the adhesive layer is pressed and bonded, a laser is focused inside the wafer to selectively form a modified portion, and then the adhesive film attached to the semiconductor chip is individualized through physical tension at a low temperature of -10°C.

[0224] The above-mentioned individualized chips were die bonded to a substrate or chip substrate using a die bonder (Shinkawa, SPA-400). The bonding conditions were as follows: 110°C, 0.5 second, and approximately 1.5 kgf / cm2. Then, curing was performed for 30 minutes in a pressurized oven (CMT, Pressurized Cure Oven PCO) at 125°C and 7 kgf / cm2.

[0225]

[0226] Weight (g) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Thermoplastic resin Manufacturing Example 1 30 30 40 50 50 50 Manufacturing Example 2 30 30 10 30 50 50 Thermosetting resin EOCN-10 4S 40 30 20 30 30 30 EP 0 4 0 9 10 20 10 10 10 NC-30 0 0 5 5 5 5 Curing agent GPH-6 5 40 40 45 40 40 40 KA-116 0 10 10 5 10 10 Inorganic filler YA-050C 10 Additive 2 MZ-A 4 4 4 4 Melting viscosity of adhesive film at 110°C 6, 10 0 5, 6 0 4, 7 0 0 9, 8 0 16, 20 0 19, 400 Storage at 130°C after curing of adhesive film Elastic modulus (MPa) 3023423711495256

[0227]

[0228] [Comparative example]

[0229] Except for applying the components and contents shown in Table 2 below, adhesive compositions for semiconductor packages were prepared in the same manner as in Example 1. Then, using the adhesive composition, an adhesive film was manufactured in the same manner as in Example 1, and a dicing die bonding film and a semiconductor device were manufactured using the same.

[0230]

[0231] Weight (g) Comparative Example 1 Comparative Example 2 Thermoplastic resin Manufacturing Example 118030 Thermosetting resin EOCN-104S2020 EP0409--EPPN-201 LNC-30001010 Curing agent GPH-653030 KA-11605 Inorganic filler YA-050 C2590 Additive C11Z-CNS2 MZ-A0.32 Melting viscosity of adhesive film at 110℃ 57,000 2,300 Storage modulus of adhesive film at 130℃ thereafter 35

[0232] The ingredients listed in Tables 1 and 2 above are as follows.

[0233] *EPPN-201L: Solid epoxy resin (Japanese gunpowder, epoxy equivalent 190 g / eq.)

[0234] *NC-2000L: Solid epoxy resin (Japanese gunpowder, epoxy equivalent 237 g / eq.)

[0235] *EOCN-104S: Solid epoxy resin (Japanese gunpowder, epoxy equivalent 218 g / eq.)

[0236] *NC-3000: Solid epoxy resin (Japanese gunpowder, epoxy equivalent 275 g / eq.)

[0237] *KDS-8170: Liquid epoxy resin (Kukdo Chemical, epoxy equivalent 157g / eq.)

[0238] *CEL2021P: Liquid epoxy resin (DAICEL, epoxy equivalent 130g / eq.)

[0239] *RE-310S: Liquid epoxy resin (Japanese gunpowder, epoxy equivalent 180 g / eq.)

[0240] *EP0408: Organic-inorganic hybrid epoxy resin having a repeating unit of the above chemical formula 1 (epoxy equivalent 177 g / eq., epoxycyclohexyl POSS, (C8H 13 O) n (SiO 1.5 ) n , viscosity 500 Pa.s, hybrid plastics)

[0241] *EP0409: Organic-inorganic hybrid epoxy resin having a repeating unit of the above chemical formula 1 (epoxy equivalent 167 g / eq., glycidyl POSS, (C6H 11 O2) n (SiO 1.5 ) n , viscosity 48 Pa.s, hybrid plastics)

[0242] *GPH-65: Phenol resin (Japanese gunpowder, hydroxyl equivalent 198 g / eq, softening point: 65 ℃)

[0243] *KA-1160: Phenol resin (DIC, hydroxyl equivalent: 117 g / eq, softening point 86 ℃)

[0244] *KH-6021: Phenolic resin (DIC, hydroxyl equivalent: 121 g / eq, softening point 133 ℃)

[0245] *KPH-F3075: Phenol resin (Kolon Chemical, hydroxyl equivalent: 175 g / eq., softening point 75 ℃)

[0246] *YA-050C: Filler (Admatec, spherical silica, average particle size approximately 50 nm)

[0247] *2MZ-A: Imidazole curing accelerator (SHIKOKU)

[0248]

[0249]

[0250] [Example Exam]

[0251] The following tests were conducted on the adhesive compositions, adhesive films, and semiconductor devices according to the examples and comparative examples, and the results are shown in Tables 3 and 4 below.

[0252]

[0253] (1) Die lifting evaluation

[0254] A semiconductor wafer (diameter 12 inches, thickness 500 ㎛) was subjected to back polishing to manufacture a semiconductor wafer with a thickness of 100 ㎛.

[0255] In each of the above examples and comparative examples, a polyethylene terephthalate film that had been subjected to a release treatment was peeled from the dicing die-bonding film, and then a semiconductor wafer prepared on top of the adhesive layer was pressed and bonded, a laser was focused inside the wafer to selectively form a modified portion, and then dicing was performed using a stealth dicing method in which the wafer and the adhesive layer were individualized along the line of the selectively modified portion through physical tension at a low temperature of -10°C. The lifting of the adhesive layer was confirmed for the semiconductor wafer and the dicing die-bonding film after cutting.

[0256] If lifting occurred in the adhesive layer, it was evaluated as defective, and if no lifting occurred, it was evaluated as good.

[0257]

[0258] (2) Void evaluation

[0259] For each semiconductor device obtained in the examples and comparative examples, a semiconductor device was evaluated as good if the area occupied by voids inside the semiconductor device was 1% or less through Scanning Acoustic Tomography (SAT), and a semiconductor device was evaluated as bad if the area occupied by voids inside the semiconductor device was more than 1%.

[0260]

[0261] (3) Chip Crack Evaluation

[0262] For each semiconductor device obtained in the examples and comparative examples, after undergoing epoxy molding and temperature cycling tests, the presence or absence of cracks in the chip in the cross section was observed using an optical microscope (SEM). If no cracks occurred, it was evaluated as good, and if cracks occurred, it was evaluated as bad.

[0263]

[0264] (4) Die-deflection evaluation

[0265] Using the 20 μm thick adhesive films obtained in each of the examples and comparative examples, they were bonded to a 60 μm semiconductor wafer and individualized into individual chips. As shown in Fig. 1, a semiconductor device having an overhang structure of 750 μm was manufactured by die bonding the semiconductor chip with the base chip.

[0266] After curing, the length of the overhang was measured and evaluated. If the height was within 2 ㎛, it was evaluated as good, and if it exceeded 2 ㎛, it was evaluated as bad.

[0267]

[0268] (5) Reliability evaluation (thermal cycle test)

[0269] For each of the semiconductor devices obtained in the examples and comparative examples, 10 of each were prepared and treated under the conditions of a thermal cycle tester of -65°C to 150°C, with support at the lowest and highest temperatures for 45 minutes each, and the occurrence of peeling was evaluated.

[0270] After 500 cycles, if none of the 10 samples showed any delamination, it was evaluated as good through Scanning Acoustic Tomography (SAT), and if even one sample showed delamination, it was evaluated as bad.

[0271]

[0272]

[0273] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Melt viscosity (Pa.s) of adhesive film 6, 100 5, 600 4, 700 9, 800 16, 200 19, 400 Die lifting occurrence Good Good Good Good Good Good Voids Good Good Good Good Good Chip crack occurrence Good Good Good Good Good Good Die Deflection (um) 1.4 1.4 1.4 1.4 1.5 1.6 Reliability Good Good Good Good Good Good

[0274] Comparative Example 1 Comparative Example 2 Melting viscosity of adhesive film (Pa.s) 57,000 2,300 Die lifting occurrence Bad Good Voids Bad Good Chip crack occurrence Bad Bad Die Deflection (um) 2.1 2.0 Reliability Bad Bad

[0275] Referring to Table 3 above, it was confirmed that the adhesive compositions of the above examples or the adhesive films prepared therefrom have a storage modulus of 30 MPa or more at 130°C measured after curing under conditions of a temperature of 120°C to 300°C and a pressure of 0.5 Kgf / cm2 to 10 Kgf / cm2, and a melt viscosity of 4,000 Pa·s or more.

[0276] It was confirmed that even in the packaging process using thin semiconductor chips of these examples, cracks or warpage can be prevented from occurring in the semiconductor chips, and excellent adhesive strength and embedding properties can be achieved, and in particular, die lifting and chip cracking do not occur, and the die deflection of the experimental example is only 1.6 um or less.

[0277] In contrast, referring to Table 4 above, it was confirmed that the adhesive compositions according to Comparative Examples 1 and 2 caused void defects and poor connection conditions and failed all thermal cycle tests, and also that not only did die lifting and chip cracking occur, but the die deflection of the experimental example also reached 2.0 um or more.

Claims

1. Contains thermoplastic resin, thermosetting resin and curing agent, A storage modulus at 130°C measured after curing under conditions of a temperature of 120°C to 300°C and a pressure of 0.5 Kgf / cm2 to 10 Kgf / cm2 is 30 MPa or more. Adhesive composition for semiconductor packaging.

2. In paragraph 1, Curing is carried out under the above conditions of temperature of 120 ℃ to 300 ℃ and pressure of 0.5 Kgf / ㎠ to 10 Kgf / ㎠. Under pressure conditions of 7 Kgf / ㎠, A method comprising: a step of heating from 25°C to 125°C for 30 minutes, a step of maintaining the temperature at 125°C for 30 minutes after the heating, and a step of cooling to 60°C after the maintaining. Adhesive composition for semiconductor packaging.

3. In paragraph 1, The adhesive composition for the semiconductor package does not contain an inorganic filler, or An adhesive composition for a semiconductor package, wherein the adhesive composition for a semiconductor package further comprises an inorganic filler in an amount of 4.9 wt% or less.

4. In paragraph 1, The above adhesive composition for semiconductor packages is used for connecting a substrate and a semiconductor chip having a thickness of 100 μm or less, or for connecting two or more semiconductor chips having a thickness of 100 μm or less. Adhesive composition for semiconductor packaging.

5. In paragraph 1, An adhesive composition for a semiconductor package, wherein the adhesive composition for a semiconductor package has a storage modulus of 50 to 500 MPa at 130°C, measured after curing under conditions of a temperature of 120°C to 300°C and a pressure of 0.5 to 10 Kgf / cm2.

6. In paragraph 1, An adhesive composition for a semiconductor package, wherein the adhesive composition for a semiconductor package has a melt viscosity of 3,000 Pa·s to 50,000 Pa·s measured at 110°C by applying a shear rate of 5 rad / s.

7. In paragraph 1, An adhesive composition for a semiconductor package, wherein the thermoplastic resin comprises a (meth)acrylate resin containing a repeating unit substituted with a glycidyl group or an epoxy group.

8. In paragraph 1, The thermoplastic resin is a (meth)acrylate resin containing a repeating unit substituted with a glycidyl group or an epoxy group and having a glass transition temperature of -20°C to 5°C; and A (meth)acrylate resin comprising a repeating unit substituted with a glycidyl group or an epoxy group and having a glass transition temperature of 7°C to 30°C; Adhesive composition for semiconductor packaging.

9. In paragraph 1, An adhesive composition for a semiconductor package, wherein the thermosetting resin comprises a silsesquioxane compound substituted with a glycidyl group or an epoxy group.

10. In paragraph 1, An adhesive composition for a semiconductor package, wherein the thermosetting resin further comprises at least one epoxy resin selected from the group consisting of bisphenol-based epoxy resin, biphenyl-based epoxy resin, naphthalene-based epoxy resin, fluorene-based epoxy resin, phenol novolac-based epoxy resin, cresol novolac-based epoxy resin, xylocycloalkyl epoxy resin, trishydroxylphenylmethane-based epoxy resin, tetraphenylmethane-based epoxy resin, dicyclopentadiene-based epoxy resin, and dicyclopentadiene-modified phenol-based epoxy resin.

11. In paragraph 1, An adhesive composition for a semiconductor package, wherein the curing agent comprises at least one selected from the group consisting of an amine-based curing agent, a phenol-based curing agent, and an acid anhydride-based curing agent.

12. In paragraph 1, An adhesive composition for a semiconductor package, comprising 5 to 500 parts by weight of the thermoplastic resin and 1 to 150 parts by weight of the curing agent relative to 100 parts by weight of the thermosetting resin.

13. An adhesive film for a semiconductor, including an adhesive composition for a semiconductor package of paragraph 1.

14. Film for the base; An adhesive layer formed on the above substrate film; and A dicing die bonding film comprising an adhesive layer formed on the adhesive layer and including the semiconductor adhesive film of claim 13.

15. Substrate; One or more semiconductor chips formed on the substrate; and An adhesive layer positioned between the substrate and a semiconductor chip formed on the substrate or between two or more semiconductor chips among the semiconductor chips; A semiconductor device, wherein the adhesive layer comprises a cured product of the adhesive composition for a semiconductor package according to claim 1.

16. In paragraph 15, A semiconductor device, wherein each of the semiconductor chips has a thickness of 100 μm or less.

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