Non-conductive adhesive film for semiconductor package, method for producing semiconductor package, and adhesive resin composition

Abstract

The invention relates to a non-conductive adhesive film for underfilling of a semiconductor package, a method for manufacturing the semiconductor package, and an adhesive resin composition. The non-conductive adhesive film for underfilling of the semiconductor package includes a base material and an adhesive layer. The adhesive layer is formed from an adhesive resin composition. The adhesive resin composition includes (a) two or more different epoxy resins including a liquid epoxy resin and an epoxy group-containing phenoxy resin represented by chemical formula 1, (b) an acid anhydride-based curing agent, and (c) an adhesive resin composition containing: (a) two or more different epoxy resins including a liquid epoxy resin and an epoxy group-containing phenoxy resin represented by chemical formula 1; one or more curing accelerators selected from the group consisting of compounds represented by the following Chemical Formula 2 and compounds represented by the following Chemical Formula 3, and (d) nanosilica having an average particle diameter in the range of 10 to 100 nm. # imgabs0 #

Description

[0001] This application is a divisional application of a Chinese patent application filed on August 23, 2019, with application number 201980085552.8 and invention name “Non-conductive adhesive film for semiconductor package and method for manufacturing semiconductor package using the same”. Technical Field

[0002] The present invention relates to a non-conductive adhesive film for a semiconductor package and a method for manufacturing a semiconductor package using the same, and more particularly to a non-conductive adhesive film for a semiconductor package capable of minimizing warpage deformation of the semiconductor package and a method for manufacturing a semiconductor package using the same. Background Art

[0003] In recent years, with the development of the semiconductor industry, the requirements for the processing speed, design and high functionality of devices have been increasing. In particular, in the case of mobile devices such as mobile phones and tablet PCs, miniaturization, thinning and lightness are also required in addition to high performance. Due to such demands, research is currently being conducted on the three-dimensional stacking method of device components. In particular, the three-dimensional packaging technology using through silicon vias (TSV) (hereinafter referred to as "TSV 3D packaging technology") can greatly shorten the wiring distance, so it has great advantages in terms of high speed, low power consumption and miniaturization of components. In addition, very fine metal wiring and multiple metal and dielectric layers can be formed, and previous semiconductor process equipment can be used directly. Therefore, the application of TSV 3D packaging technology is expected to expand significantly in the future.

[0004] TSV 3D packaging technology is divided into the following processes: TSV drilling and filling process to form silicon through-hole electrodes on the wafer; temporary bonding and debonding process to bond the ultra-thin wafer to the carrier wafer using temporary pre-fixed adhesive materials (temporary bonding and debonding adhesives); back-grinding process for thinning the wafer; and process of three-dimensionally stacking and bonding the manufactured ultra-thin semiconductor chips.

[0005] Among them, non-conductive adhesive films are currently used to bond semiconductor chips when 3D stacking is performed. However, due to the difference in thermal expansion coefficients between the non-conductive adhesive film and the semiconductor chip, the semiconductor package will warp over time due to temperature changes, resulting in poor connection and reduced reliability. Summary of the invention

[0006] Technical issues

[0007] An object of the present invention is to provide a non-conductive adhesive film for a semiconductor package that can minimize warpage deformation of the semiconductor package.

[0008] Furthermore, another object of the present invention is to provide a method for manufacturing a semiconductor package which can simplify the process and improve the production efficiency while improving the reliability of the semiconductor package by using the non-conductive adhesive film.

[0009] Solution to the problem

[0010] The present invention provides a non-conductive adhesive film for a semiconductor package, comprising a substrate and an adhesive layer disposed on one side of the substrate and having a storage modulus of 2 to 4 GPa at 25°C.

[0011] As an example, the adhesive layer has a weight loss rate of 1% or less at 250° C. in thermogravimetric analysis (TGA).

[0012] As another example, the adhesive layer has an onset temperature of 160 to 200°C.

[0013] In addition, the present invention provides a method for manufacturing a semiconductor package, which includes: (S100) the step of alternately stacking the adhesive layers of the above-mentioned non-conductive adhesive film and the semiconductor elements of the TSV structure having connecting terminals on at least one side on a substrate to form a multi-layer stack; (S200) the step of hot pressing the above-mentioned stack to connect the connecting terminals of each semiconductor element in the above-mentioned stack to each other; and (S300) the step of curing the adhesive layer in the stack after the hot pressing.

[0014] Effects of the Invention

[0015] The present invention can minimize warpage and sliding properties when packaging a semiconductor element, thereby improving the reliability of the semiconductor package. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is a cross-sectional view schematically showing a non-conductive adhesive film for a semiconductor package according to an embodiment of the present invention.

[0017] Figure 2 This is a cross-sectional view schematically showing a non-conductive adhesive film for a semiconductor package according to another embodiment of the present invention.

[0018] Figures 3 to 6 It is a cross-sectional view schematically showing a manufacturing process of a semiconductor package according to an embodiment of the present invention.

[0019] <Brief Description of Drawing Symbols>

[0020] 10A, 10B: non-conductive adhesive film 11: base material

[0021] 12: Adhesive layer 20: Substrate

[0022] 30: Semiconductor element 31: Semiconductor substrate

[0023] 32: Through electrode 33: Connection terminal

[0024] 34: Solder layer 100-1, 100-2, 100-n: Unit body

[0025] 200, 300, 400: laminated body DETAILED DESCRIPTION

[0026] Hereinafter, the present invention will be described.

[0027] <Non-conductive adhesive film for semiconductor package>

[0028] Figure 1 is a cross-sectional view schematically showing a non-conductive adhesive film for a semiconductor package according to a first embodiment of the present invention. Figure 2 It is a cross-sectional view schematically showing a non-conductive adhesive film for a semiconductor package according to a second embodiment of the present invention.

[0029] The non-conductive adhesive film 10A of the present invention is an adhesive film used in semiconductor packaging. Figure 1 As shown, it includes a substrate 11 and an adhesive layer 12 disposed on one side of the substrate. Optionally, it may further include another substrate (hereinafter referred to as "second substrate") 13 disposed on the other side of the adhesive layer (see Figure 2 ).

[0030] Below, refer to Figure 1 A non-conductive adhesive film 10A for a semiconductor package according to a first embodiment of the present invention will be described.

[0031] 1) Base material

[0032] In the non-conductive adhesive film of the present invention, the substrate 11 is a portion that supports the adhesive layer and protects the surface of the adhesive layer, and is peeled off and removed when the non-conductive adhesive film is used.

[0033] As the substrate 11 , any plastic film generally known in the art and capable of being peeled off can be used without limitation, and release paper can also be used.

[0034] As non-limiting examples of usable plastic films, there are polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyetherimide film, polyimide film, fluororesin film, polyamide film, acrylic resin film, norbornene resin film, cycloolefin resin film, etc. Such plastic films can be transparent or translucent, or can be colored or uncolored. As an example, substrate 11 can be polyethylene terephthalate (PET). As another example, substrate 11 can be polyimide (PI).

[0035] Such a plastic film may be provided with a release layer. The release layer has a function of allowing the adhesive layer to be easily separated without being damaged and maintaining its shape when the substrate and the adhesive layer are separated. Here, the release layer may be a generally used film-shaped release material.

[0036] The components of the release agent used in the release layer are not particularly limited, and common release agent components known in the art can be used. As non-limiting examples thereof, epoxy-based release agents, release agents composed of fluororesins, silicone-based release agents, alkyd resin-based release agents, water-soluble polymers, etc. can be cited. In addition, as required, powdered fillers such as silicon, silicon dioxide, etc. can be included as components of the release layer. At this time, the powder filler in the form of particles can be mixed with 2 types of powder fillers, and at this time, their average particle size can be appropriately selected considering the surface roughness formed.

[0037] The thickness of such a release layer can be appropriately adjusted within a general range known in the art.

[0038] In the present invention, the thickness of the substrate 11 is not particularly limited and can be adjusted within a common range known in the art, for example, about 25 to 150 μm, specifically about 30 to 100 μm, and more specifically about 30 to 50 μm.

[0039] The demolding force of such a substrate is not particularly limited, and may be, for example, about 1 to 500 gf / inch, and specifically about 10 to 100 gf / inch.

[0040] The method for forming the release layer is not particularly limited, and a known method such as heat pressing, heat roll lamination, extrusion lamination, coating of a coating liquid, and drying can be employed.

[0041] 2) Adhesive layer

[0042] In the non-conductive adhesive film of the present invention, the adhesive layer 12 is arranged on one side of the substrate 11, which can connect the substrate and the semiconductor element or multiple semiconductor elements to each other during semiconductor packaging, and as an underfill, it can redistribute the stress and deformation generated by the difference in thermal expansion coefficient between the substrate and the semiconductor element.

[0043] The adhesive layer 12 of the present invention has a storage modulus of 2 to 4 GPa at 25° C. Therefore, the non-conductive adhesive film of the present invention can not only minimize the warpage of the semiconductor package when the semiconductor package is three-dimensionally stacked by the semiconductor element, but also minimize the handling problem caused by the slip of the semiconductor element, thereby improving the reliability of the semiconductor package.

[0044] As an example, the adhesive layer of the present invention may be formed of an adhesive resin composition comprising (a) two or more different epoxy resins, (b) a curing agent, (c) a curing accelerator, and (d) nanosilica.

[0045] In the adhesive resin composition, two or more different epoxy resins may be used without particular limitation as long as they are generally known epoxy resins in the art. Here, epoxy resin means a polymer containing an epoxy group.

[0046] As an example, two or more different epoxy resins may include liquid epoxy resin and epoxy-containing phenoxy resin. In this case, the adhesive layer of the present invention can reduce the generation of voids between bumps, improve the bump filling property and ensure the bump bonding reliability, and can improve the adhesion to the wafer or substrate to prevent delamination, thereby improving heat resistance.

[0047] Here, the mixing ratio of the liquid epoxy resin to the epoxy-containing phenoxy resin is not particularly limited, but when the mixing ratio of the liquid epoxy resin to the epoxy-containing phenoxy resin is 1:0.5 to 3 by weight, specifically 1:0.5 to 1.5 by weight, the adhesive layer can have a low storage modulus.

[0048] Among the two or more different epoxy resins of the present invention, the liquid epoxy resin is a thermosetting resin that is a liquid at 25±5° C. Such a first epoxy resin imparts adhesiveness and curability to the adhesive resin composition and imparts curing uniformity to the cured adhesive layer.

[0049] As non-limiting examples of liquid epoxy resins that can be used in the present invention, there are liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, liquid naphthalene type epoxy resin, liquid aminophenol type epoxy resin, liquid hydrogenated bisphenol type epoxy resin, liquid alicyclic epoxy resin, liquid alcohol ether type epoxy resin, liquid cycloaliphatic type epoxy resin, liquid fluorene type epoxy resin, liquid siloxane type epoxy resin, etc. Among them, liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, and liquid naphthalene type epoxy resin are suitable from the aspects of adhesion, curability, durability, and heat resistance. They can be used alone or in combination of two or more.

[0050] Specifically, as products of liquid epoxy resins, there are bisphenol F type epoxy resin (product name: YDF8170) manufactured by Nippon Steel Chemical, bisphenol A type epoxy resin (product name: EXA-850CRP) manufactured by DIC, bisphenol F type epoxy resin (product name: YDF870GS) manufactured by Nippon Steel Chemical, naphthalene type epoxy resin (product name: HP4032D) manufactured by DIC, aminophenol type epoxy resin (grade: JER630, JER630LSD) manufactured by Mitsubishi Chemical, siloxane-based epoxy resin (product name: TSL9906) manufactured by Momentive High-Tech, 1,4-cyclohexanedimethanol diglycidyl ether (product name: ZX1658GS) manufactured by Nippon Steel Chemical Co., Ltd., but are not limited to these.

[0051] Among the two or more epoxy resins of the present invention, the epoxy-containing phenoxy resin is a thermoplastic polymer containing an epoxy group at at least one end. The epoxy group in the molecule has a very small equivalent weight compared to the molecular weight, so although it participates in curing, it can provide fluidity at high temperatures. Due to such an epoxy-containing phenoxy resin, the adhesive layer of the present invention can be formed in a film shape in a semi-cured (B-stage) state at room temperature (about 25±5°C).

[0052] The epoxy-containing phenoxy resin that can be used in the present invention is not particularly limited as long as it is a polymer containing a phenoxy group in the polymer chain and an epoxy group at at least one terminal.

[0053] For example, the phenoxy resin may be a compound represented by the following Chemical Formula 1, but is not limited thereto.

[0054] [Chemical formula 1]

[0055]

[0056] (In the above chemical formula 1,

[0057] a and b are integers from 1 to 4 respectively,

[0058] Multiple R1 and multiple R2 are the same or different from each other, and are independently selected from hydrogen, halogen, C1~C10 Alkyl, C3~C 20 Cycloalkyl, C5~C 20 The group consisting of aryl and nitro, specifically, each independently selected from hydrogen, halogen, C1-C5 alkyl, C3-C 10 Cycloalkyl, C5~C 10 A group consisting of an aryl group and a nitro group;

[0059] R3 to R8 are the same as or different from each other and are independently hydrogen or hydroxyl, wherein at least one of R3 to R8 is hydroxyl;

[0060] X1 is a single bond or C1~C 10 The alkylene group is specifically a single bond or a C1 to C5 alkylene group,

[0061] Y1 and Y2 are the same or different from each other and are independently hydrogen, hydroxyl or epoxy, wherein at least one of Y1 and Y2 is epoxy,

[0062] n is an integer from 30 to 400).

[0063] The two or more epoxy resins of the present invention may further include an epoxy resin known in the art, preferably a multifunctional epoxy resin, in addition to the liquid epoxy resin and the epoxy group-containing phenoxy resin.

[0064] As an example, two or more epoxy resins may include liquid epoxy resin, epoxy-containing phenoxy resin and multifunctional epoxy resin. In this case, the mixing ratio between liquid epoxy resin, epoxy-containing phenoxy resin and multifunctional epoxy resin is not particularly limited, for example, the mixing ratio of liquid epoxy resin, epoxy-containing phenoxy resin and multifunctional epoxy resin can be 1: 0.5 ~ 3: 0.5 ~ 3 weight ratio, specifically 1: 0.5 ~ 1.5: 0.5 ~ 1.5 weight ratio. In this case, the adhesive layer of the present invention has excellent adhesion, low storage modulus, and can minimize the generation of smoke (fume).

[0065] The multifunctional epoxy resin that can be used in the present invention is an epoxy resin containing two or more epoxy groups. Such a multifunctional epoxy resin imparts electrical insulation, heat resistance, chemical stability, strength (toughness) and moldability to the adhesive layer.

[0066] The multifunctional epoxy resin that can be used in the present invention is not particularly limited as long as it contains two or more, specifically 2 to 5 epoxy groups per molecule (monomer).

[0067] Non-limiting examples of the multifunctional epoxy resin include epoxy resins obtained by epoxidizing a condensate of phenol or alkylphenols and hydroxybenzaldehyde, phenol novolac epoxy resins, cresol novolac epoxy resins, phenol aralkyl epoxy resins, biphenyl epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, linear aliphatic epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, XYLOK epoxy resins, multifunctional epoxy resins, phenol novolac epoxy resins, bisphenol A / bisphenol F / bisphenol AD ​​novolac epoxy resins, bisphenol A / bisphenol F / bisphenol AD ​​glycidyl ether epoxy resins, bishydroxybiphenyl epoxy resins, dicyclopentadiene epoxy resins, naphthalene epoxy resins, etc. Among them, a multifunctional epoxy resin that is non-liquid at 25±5°C is preferred. Here, the term "non-liquid at 25±5°C" refers to epoxy resins that are semi-solid or solid at 25±5°C, and also includes epoxy resins that are close to solid.

[0068] The adhesive resin composition contains a curing agent. The curing agent is a component that cures two or more epoxy resins.

[0069] As the curing agent that can be used in the present invention, any substance that is known as a component that generally cures epoxy resins in the art can be used without limitation. For example, there are acid anhydride curing agents such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexenedicarboxylic anhydride, phthalic anhydride, maleic anhydride, and pyromellitic anhydride; aromatic amine curing agents such as m-phenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone; aliphatic amine curing agents such as diethylenetriamine and triethylenetetramine; phenol aralkyl type phenolic resins, phenol Phenolic curing agents such as novolac phenolic resin, XYLOK phenolic resin, cresol novolac phenolic resin, naphthol phenolic resin, terpene phenolic resin, multifunctional phenolic resin, dicyclopentadiene phenolic resin, naphthalene phenolic resin, novolac phenolic resin synthesized from bisphenol A and resol phenolic resin, etc.; latent curing agents such as dicyandiamide, etc., which can be used alone or in combination of two or more.

[0070] The adhesive resin composition contains a curing accelerator. However, in the present invention, in order to adjust the curing speed and ensure the high temperature stability of the adhesive layer, at least one selected from the group consisting of the compound represented by the following Chemical Formula 2 and the compound represented by the following Chemical Formula 3 is contained as a curing accelerator.

[0071] [Chemical formula 2]

[0072]

[0073] [Chemical formula 3]

[0074]

[0075] In the above chemical formulas 2 and 3,

[0076] n1 is 1 or 2,

[0077] n2 is an integer from 0 to 2,

[0078] X1 to X6 are the same as or different from each other and are each independently N or C(R1), wherein at least one of X1 to X6 is N,

[0079] Y1 to Y6 are the same as or different from each other and are each independently N(R2) or C(R3)(R4), wherein at least one of Y1 to Y6 is N(R2),

[0080] In this case, a plurality of C(R1)s may be identical or different from each other, a plurality of N(R2)s may be identical or different from each other, a plurality of C(R3)(R4)s may be identical or different from each other,

[0081] R1, R2, R3 and R4 are each independently selected from hydrogen, deuterium (D), halogen, cyano, nitro, C1-C 20 Alkyl, C2~C 20 The alkenyl and C2~C 20 A group composed of alkynyl groups.

[0082] Specifically, in the above Chemical Formula 2, 1 to 2 of X1 to X6 may be N, and the rest may be C(R1).

[0083] In addition, in the above chemical formula 3, 1 to 2 of Y1 to Y6 may be N(R2), and the rest may be C(R3)(R4).

[0084] In addition, in the above chemical formulas 2 and 3, R1, R2, R3 and R4 can be independently selected from hydrogen, deuterium (D), halogen, cyano, nitro, C1-C 12 Alkyl, C2~C 12 The alkenyl and C2~C 12 A group composed of alkynyl groups.

[0085] Examples of the curing accelerator represented by the above Chemical Formula 2 include a compound represented by the following Chemical Formula 2a, a compound represented by the following Chemical Formula 2b, and the like, but are not limited thereto.

[0086] [Chemical formula 2a]

[0087]

[0088] [Chemical formula 2b]

[0089]

[0090] Examples of the compound represented by the above Chemical Formula 3 include, but are not limited to, the compound represented by the following Chemical Formula 3a.

[0091] [Chemical formula 3a]

[0092]

[0093] As an example, the curing accelerator may include one or more selected from the group consisting of the compound of Chemical Formula 2a, the compound of Chemical Formula 2b, and the compound of Chemical Formula 3a.

[0094] In the adhesive resin composition of the present invention, the content of the curing accelerator is preferably adjusted by considering the content of two or more epoxy resins or the type and content of the curing agent. As an example, in the adhesive resin composition of the present invention, the content of the two or more epoxy resins can be in the range of about 40 to 80 weight % based on the total amount of the resin composition, the content of the curing agent can be in the range of about 5 to 20 weight % based on the total amount of the resin composition, and the content of the curing accelerator can be in the range of about 0.01 to 1 weight % based on the total amount of the resin composition. In this case, the adhesive layer of the present invention not only has a low storage modulus at room temperature, but is also easy to operate, has excellent bonding strength, can minimize foaming voids, and does not cause poor connectivity.

[0095] The above-mentioned adhesive resin composition comprises nano silicon dioxide. Nano silicon dioxide can adjust viscosity and workability, and can reduce the coefficient of thermal expansion (CTE) while improving adhesion. Thus, when the non-conductive adhesive film of the present invention is used for semiconductor packaging, the warping characteristics and scratch resistance can be improved.

[0096] The shape of such nano-silica is not particularly limited, and can be, for example, square, spherical, etc.

[0097] In addition, the average particle size of nano-silica is not particularly limited, and can be, for example, in the range of 10 to 100 nm. If the average particle size of nano-silica is in the above range, the mechanical properties of the cured product can be further improved.

[0098] In the adhesive resin composition of the present invention, the content of nano silicon dioxide is not particularly limited, for example, the total amount of the adhesive resin composition can be adjusted to 100% by weight, specifically, based on the total amount of the above-mentioned adhesive resin composition, it can be about 10 to 50% by weight. If the content of nano silicon dioxide is the above-mentioned range, an adhesive layer with a low coefficient of thermal expansion (CTE) is formed, so that the difference in the coefficient of thermal expansion between the substrate and the semiconductor element is small and warpage or cracking can be minimized.

[0099] The adhesive resin composition of the present invention may further selectively contain additives generally known in the art in addition to the above-mentioned components according to the purpose of use and the use environment of the above-mentioned composition, for example, solvents such as acetone, methyl ethyl ketone, toluene, ethyl acetate, tackifiers, coupling agents, antistatic agents, adhesion enhancers, wettability enhancers, leveling enhancers, etc., but are not limited thereto.

[0100] The content of such additives is not particularly limited and can be used within a common range known in the art, for example, about 0.01 to 10% by weight based on the total amount of the resin composition.

[0101] The above-mentioned bonding resin composition can be manufactured by methods generally known in the art. For example, two or more epoxy resins (for example, selected from more than one of the group consisting of liquid epoxy resin, phenoxy resin and multifunctional epoxy resin) different from each other, curing agent, curing accelerator, nano silicon dioxide and selective additives can be mixed and stirred at room temperature to the temperature after the appropriate heating using mixing equipment such as ball mill, pearl mill, 3 roll mill (3roll mill), basket mill (basket mill), grinding machine (dyno mill), planetary mill (planetary) and manufacture bonding resin composition.

[0102] The thickness of the adhesive layer of the present invention is not particularly limited, and may be, for example, about 1 to 100 μm, specifically about 5 to 50 μm. However, when the adhesive layer has a thickness within the above range, the film forming properties and thickness uniformity of the film can be improved.

[0103] The adhesive layer of the present invention may have an onset temperature of about 160 to 200° C. As described above, the adhesive layer of the present invention has a high onset temperature and can therefore exhibit stable curing characteristics at high temperatures.

[0104] In addition, the weight loss rate of the adhesive layer of the present invention at 250° C. in thermogravimetric analysis (TGA) can be 1% or less. In this way, the adhesive layer of the present invention has excellent high temperature stability. Therefore, the generation of fume from the non-conductive adhesive film of the present invention can be minimized, and thus, the non-conductive adhesive film of the present invention can encapsulate semiconductor elements in an environmentally friendly and economical manner.

[0105] The non-conductive adhesive film of the present invention can be manufactured by a method generally known in the art. For example, the adhesive resin composition obtained by the above method can be diluted with an organic solvent capable of dilution as needed to an appropriate concentration for easy film production, and then coated on a substrate and dried to manufacture the non-conductive adhesive film.

[0106] The method of coating and drying is not particularly limited as long as a coating film can be formed by bar coating, gravure coating, notch roll coating, reverse roll coating, roll knife coating, die coating, die lip coating or the like.

[0107] The non-conductive adhesive film of the present invention has a low storage modulus and a low coefficient of thermal expansion (CTE), so the reliability of the warping deformation of the semiconductor package is excellent, and the high temperature stability is excellent, so it can be packaged at high temperature and has excellent processability. In addition, the non-conductive adhesive film of the present invention can improve the bump filling performance and ensure the bump bonding reliability, and can also improve the adhesion to the wafer or substrate to prevent delamination, thereby improving the heat resistance.

[0108] The following, Figure 2 A non-conductive adhesive film 10B according to a second embodiment of the present invention will be described.

[0109] like Figure 2 As shown, the non-conductive adhesive film 10B of the present invention may include a substrate (hereinafter referred to as the "first substrate") 11; an adhesive layer 12 arranged on one side of the above-mentioned substrate; and another substrate (hereinafter referred to as the "second substrate") 13 arranged on the other side of the above-mentioned adhesive layer 12.

[0110] The configuration of the non-conductive adhesive film 10B of the second embodiment other than the second substrate, that is, the first substrate 11 and the adhesive layer 12 are the same as those described in the first embodiment, and thus are omitted.

[0111] In the present invention, the second substrate 13 is a portion disposed on the other side of the adhesive layer 13 to support the adhesive layer and protect the surface thereof, and is removable and is removed by being peeled off when a non-conductive adhesive film is used.

[0112] Such a second substrate 13 may be the same as or different from the first substrate, and a specific description thereof is the same as that described for the first substrate, and thus is omitted.

[0113] <Method for Manufacturing Semiconductor Package>

[0114] On the other hand, the present invention can provide a method for manufacturing various semiconductor packages using the non-conductive adhesive films 10A and 10B. In particular, the non-conductive adhesive film has a low storage modulus at room temperature, so the warpage problem of the semiconductor package can be minimized and the reliability can be improved. Therefore, the present invention can improve the integration of semiconductor packages by three-dimensionally stacking semiconductor elements using the non-conductive adhesive film.

[0115] For example, the method for manufacturing a semiconductor package includes: (S100) the step of alternately stacking the adhesive layer of the non-conductive adhesive film and the semiconductor element of the TSV structure with a connection terminal configured on at least one side on a substrate to form a multi-layer stack; (S200) the step of thermocompression bonding the stack to bond the connection terminals of the semiconductor elements in the stack to each other; and (S300) the step of curing the adhesive layer in the stack after the thermocompression bonding. However, the manufacturing method of the present invention can be implemented by changing or selectively mixing the steps of each process as needed.

[0116] Below, refer to Figures 3 to 6 The manufacturing method of the semiconductor package of the present invention is divided into different process steps for explanation, as follows.

[0117] (S100) Step of forming a laminate

[0118] The adhesive layers of the non-conductive adhesive film and the semiconductor elements are alternately laminated in this order on a substrate to form a multi-layer laminate.

[0119] For example, in step (S100), if Figure 3 As shown in (a), a first unit body 100-1 prepared by placing an adhesive layer 12 of non-conductive adhesive films 10A and 10B on one surface of a semiconductor element 30 is stacked on one surface of a substrate 20 to form a first stacked body 200. At this time, the adhesive layer 12 is stacked in contact with the substrate 20. Then, as shown in FIG. Figure 3 As shown in (b), the second unit body 100-2 is stacked on the semiconductor element 30 of the first unit body 200 so that the adhesive layer 12 is in contact with the semiconductor element 30 of the first unit body 100-1 to form the second unit body 300. Figure 4As shown, the third unit cell 100-3 to the nth unit cell 100-n are sequentially stacked on the second stack 300 to form a multilayer stack 400 (where n is greater than 3, specifically a natural number from 3 to 10). At this time, the semiconductor elements in each unit cell can be the same or different from each other.

[0120] As another example, although not shown in the figure, step (S100) can be repeatedly implemented in a manner of configuring the adhesive layer of the above-mentioned non-conductive adhesive film on one side of the substrate and then configuring the semiconductor element on the other side of the above-mentioned adhesive layer to form a multi-layer stacked body in which the adhesive layer of the above-mentioned non-conductive adhesive film and the semiconductor element are alternately stacked in sequence.

[0121] The substrate 20 that can be used in the present invention is a substrate having a circuit pattern 21 formed on one side, for example, a printed circuit board (PCB), various lead frames, or a substrate having electronic components such as resistors or capacitors mounted on the surface of the substrate.

[0122] The semiconductor element 30 that can be used in the present invention can be a memory chip or logic chip such as DRAM, SRAM, MEMS chip, or high bandwidth memory (HBM) DRAM chip. Such a semiconductor element 30 has a TSV (Through Silicon Via) structure, for example, including a semiconductor substrate 31, a plurality of through electrodes (Through Silicon Vias, TSV) 32 formed inside the semiconductor substrate, a connection terminal 33 disposed at least one of the plurality of through electrodes, and a solder layer (for example, a solder ball) 34 disposed at the connection terminal (see Figure 3 ).

[0123] Examples of the semiconductor substrate 31 include a silicon substrate, a SiC substrate, and a GaS substrate.

[0124] The through-electrode 32 is an electrode that directly connects the upper and lower parts of the substrate by filling a conductive material such as copper (Cu), silver (Ag), nickel (Ni) or a carbon component in a hole that penetrates the semiconductor substrate in the vertical direction. There are multiple through-electrodes 32, and a part of them is exposed to the outside. At least a part of the exposed multiple through-electrodes 32 is provided with a connection terminal 33.

[0125] The connection terminal 33 may be a bump, a conductive spacer, a pin grid array (PGA), a lead grid array, or a combination thereof. As an example, the connection terminal may be a bump disposed on a through electrode. A solder layer 34 is disposed on such a connection terminal 33, and when the laminate is thermally pressed, the semiconductor element is electrically connected due to the solder bonding.

[0126] In this step, the semiconductor element may be laminated on the adhesive layer under pressure of about 20 to 100 N. Furthermore, if necessary, the semiconductor element may be laminated under pressure at a temperature lower than the starting temperature of the adhesive layer, for example, at a temperature of 50 to 100° C. At this time, the adhesive layer adheres the substrate to the semiconductor element and the plurality of semiconductor elements to each other in a semi-cured state (B stage).

[0127] (S200) Thermal compression bonding step of laminated body

[0128] The multi-layered laminate 400 obtained in the above step (S100) is subjected to thermocompression bonding. Thus, the connection terminals of the semiconductor elements in the laminate 500 after thermocompression bonding are bonded to each other.

[0129] This step is performed at a temperature of about 200 to 300° C. and a pressure of about 50 to 200 N. For example, Figure 5 As shown, the upper and lower parts of the laminate are thermally compressed by a device capable of thermal compression. At this time, the connection terminals in the laminate are soldered due to the melting of the solder layer, so that they can be electrically connected.

[0130] (S300) Adhesive Layer Curing Step

[0131] In the step (S200) described above, the adhesive layer 12 in the laminated body 500 after thermal compression bonding is cured.

[0132] The adhesive layer has an initial temperature of about 160 to 200°C, so this step is performed at a temperature higher than the initial temperature, such as about 160 to 200°C, preferably about 170 to 200°C.

[0133] The curing time of the adhesive layer is adjusted according to the curing temperature, for example, it can be about 1 to 3 hours.

[0134] Hereinafter, the present invention will be specifically described by way of examples. However, the following examples and experimental examples merely illustrate one embodiment of the present invention, and the scope of the present invention is not limited to the following examples and experimental examples.

[0135] [Examples 1 to 3 and Comparative Example 1: Production of Non-Conductive Adhesive Films]

[0136] 1-1. Production of Adhesive Resin Composition

[0137] The adhesive resin compositions of Examples 1 to 3 and Comparative Example 1 were prepared by mixing the components according to the composition described in Table 1 below. The content of each component described in Table 1 is expressed in % by weight based on the total amount of the resin composition.

[0138] 1-2. Production of non-conductive adhesive film

[0139] Each adhesive resin composition prepared in Example 1-1 was die-coated on one surface of a PET release film (thickness: 50 μm), followed by drying to form an adhesive layer (thickness: 20 μm), thereby preparing a non-conductive adhesive film.

[0140] [Table 1]

[0141]

[0142] [Experimental Example 1: Physical Property Evaluation]

[0143] The physical properties of the non-conductive adhesive films produced in Examples 1 to 3 and Comparative Example 1 were measured as follows, and the results are shown in Table 2 below.

[0144] 1) Onset Temperature

[0145] The onset temperature of the non-conductive adhesive film was measured using a differential scanning calorimetry (DSC).

[0146] 2) Volatile contents

[0147] The non-conductive adhesive film was heated from 30° C. to 800° C. at 10° C. per minute using a thermogravimetric analyzer, and the weight loss rate was measured.

[0148] 3) Storage modulus

[0149] The storage modulus of the non-conductive adhesive film was measured while the temperature was increased from 80° C. to 270° C. at a rate of 10° C. per minute using a dynamic mechanical analysis (DMA).

[0150] [Table 2]

[0151]

[0152]

Claims

1. A non-conductive adhesive film for bottom filling of a semiconductor package, comprising: substrate; and an adhesive layer disposed on one side of the substrate and having a storage modulus of 2.8 to 4 GPa at 25° C., The adhesive layer is formed of an adhesive resin composition, the adhesive resin composition comprising (a) two or more different epoxy resins including a liquid epoxy resin and an epoxy-containing phenoxy resin represented by the following chemical formula 1, (b) an acid anhydride curing agent, (c) one or more curing accelerators selected from the group consisting of a compound represented by the following chemical formula 2 and a compound represented by the following chemical formula 3, and (d) nano-silica, and The mixing ratio of the liquid epoxy resin to the epoxy-containing phenoxy resin is 1:0.5-3 by weight. The adhesive resin composition comprises, based on the total amount of the resin composition, 40 to 80 weight percent of epoxy resin; 5 to 20 weight percent of anhydride curing agent; 0.01 to 1 weight percent of a curing accelerator; and 10 to 50 weight percent of nano-silicon dioxide. The average particle size of the nano-silicon dioxide is in the range of 10 to 100 nm. Chemical formula 1 In the chemical formula 1, a and b are integers from 1 to 4 respectively, Multiple R1 and multiple R2 are the same or different from each other, and are independently selected from hydrogen, halogen, C1~C 10 Alkyl, C3~C 20 Cycloalkyl, C5~C 20 A group consisting of an aryl group and a nitro group, R3 to R8 are the same or different from each other and are independently hydrogen or hydroxyl, wherein, At least one of R3 to R8 is a hydroxyl group, X1 is a single bond or C1~C 10 The alkylene group, Y1 and Y2 are the same or different from each other and are independently hydrogen, hydroxyl or epoxy, wherein at least one of Y1 and Y2 is epoxy, n is an integer from 30 to 400, Chemical formula 2 Chemical formula 3 In the chemical formulas 2 and 3, n1 is 1 or 2, n2 is an integer from 0 to 2, X1 to X6 are the same as or different from each other and are independently N or C(R1), wherein 2 of X1 to X6 are N, Y1 to Y6 are the same as or different from each other and are each independently N(R2) or C(R3)(R4), wherein at least one of Y1 to Y6 is N(R2), In this case, a plurality of C(R1)s may be identical or different from each other, a plurality of N(R2)s may be identical or different from each other, a plurality of C(R3)(R4)s may be identical or different from each other, R1, R2, R3 and R4 are each independently selected from hydrogen, deuterium (D), halogen, cyano, nitro, C1-C 20 Alkyl, C2~C 20 The alkenyl and C2~C 20 A group composed of alkynyl groups. 2 . The non-conductive adhesive film for underfill of a semiconductor package according to claim 1 , wherein the adhesive layer has a weight reduction rate of 1% or less at 250° C. in thermogravimetric analysis (TGA). 3 . The non-conductive adhesive film for underfill of a semiconductor package according to claim 1 , wherein the adhesive layer has an onset temperature of 160 to 200° C.

4. A method for manufacturing a semiconductor package, comprising: (S100) step, forming a multi-layered laminate by alternately laminating an adhesive layer of a non-conductive adhesive film for bottom filling of a semiconductor package according to any one of claims 1 to 3 and a semiconductor element of a TSV structure having a connection terminal on at least one side thereof on a substrate; (S200) step of thermocompression bonding the stacked body to bond the connection terminals of the semiconductor elements in the stacked body to each other; and (S300) is a step of curing the adhesive layer in the laminate after the thermal compression bonding. 5 . The method for manufacturing a semiconductor package according to claim 4 , wherein in the step ( S100 ), the semiconductor element is laminated on the adhesive layer under pressure of 20 to 100 N. 6 . The method for manufacturing a semiconductor package according to claim 5 , wherein the semiconductor elements are laminated under pressure at a temperature of 50 to 100° C. 7 . The method for manufacturing a semiconductor package according to claim 4 , wherein the step ( S200 ) is performed at a temperature of 200 to 300° C. and a pressure of 50 to 200N. 8 . The method for manufacturing a semiconductor package according to claim 4 , wherein in the step ( S300 ), the adhesive layer is cured at a temperature of 150 to 200° C.

9. An adhesive resin composition for bottom filling of a semiconductor package, comprising: (a) two or more different epoxy resins containing a liquid epoxy resin and an epoxy group-containing phenoxy resin represented by the following Chemical Formula 1; (b) anhydride curing agent; (c) one or more curing accelerators selected from the group consisting of a compound represented by the following Chemical Formula 2 and a compound represented by the following Chemical Formula 3; and (d) nano-silicon dioxide, Furthermore, the mixing ratio of the liquid epoxy resin to the epoxy-containing phenoxy resin is 1:0.5-3 by weight. The adhesive resin composition comprises, based on the total amount of the resin composition, 40 to 80 weight percent of epoxy resin; 5 to 20 weight percent of anhydride curing agent; 0.01 to 1 weight percent of a curing accelerator; and 10 to 50 weight percent of nano-silicon dioxide. The average particle size of the nano-silicon dioxide is in the range of 10 to 100 nm. Chemical formula 1 In the chemical formula 1, a and b are integers from 1 to 4 respectively, Multiple R1 and multiple R2 are the same or different from each other, and are independently selected from hydrogen, halogen, C1~C 10 Alkyl, C3~C 20 Cycloalkyl, C5~C 20 A group consisting of an aryl group and a nitro group, R3 to R8 are the same or different from each other and are independently hydrogen or hydroxyl, wherein, At least one of R3 to R8 is a hydroxyl group, X1 is a single bond or C1~C 10 The alkylene group, Y1 and Y2 are the same or different from each other and are independently hydrogen, hydroxyl or epoxy, wherein at least one of Y1 and Y2 is epoxy, n is an integer from 30 to 400, Chemical formula 2 Chemical formula 3 In the chemical formulas 2 and 3, n1 is 1 or 2, n2 is an integer from 0 to 2, X1 to X6 are the same as or different from each other and are independently N or C(R1), wherein 2 of X1 to X6 are N, Y1 to Y6 are the same as or different from each other and are each independently N(R2) or C(R3)(R4), wherein at least one of Y1 to Y6 is N(R2), In this case, a plurality of C(R1)s may be identical or different from each other, a plurality of N(R2)s may be identical or different from each other, a plurality of C(R3)(R4)s may be identical or different from each other, R1, R2, R3 and R4 are each independently selected from hydrogen, deuterium (D), halogen, cyano, nitro, C1-C 20 Alkyl, C2~C 20 The alkenyl and C2~C 20 A group composed of alkynyl groups.

Images