CN114479733A - Chip-level underfill adhesive and preparation method thereof - Google Patents
Chip-level underfill adhesive and preparation method thereof Download PDFInfo
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- CN114479733A CN114479733A CN202210013127.1A CN202210013127A CN114479733A CN 114479733 A CN114479733 A CN 114479733A CN 202210013127 A CN202210013127 A CN 202210013127A CN 114479733 A CN114479733 A CN 114479733A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
Abstract
The invention discloses a chip-level underfill adhesive and a preparation method thereof, wherein the chip-level underfill adhesive comprises the following components in parts by mass: 10-30 parts of epoxy resin; 5-25 parts of a curing agent; 45-75 parts of toughening filler; wherein, the toughening filler is a composite particle which takes spherical inorganic particles as a core, is subjected to surface modification by a silane coupling agent and is grafted with the toughening agent; preferably, the silane coupling agent is selected from one or more compounds having the formula (1). The invention takes spherical inorganic particles as a carrier to realize the uniform dispersion of the filler and the toughening agent in an epoxy resin matrix, takes the inorganic particles as a stress-bearing framework to induce and transfer stress, disperses the stress through the toughening agent grafted on the surface, obviously improves the fracture toughness without losing the strength, and simultaneously inhibits the toughening agent from separating out phase in the underfill. After the filling adhesive provided by the invention is filled in a chip, no crack is generated in 1000-45-125 ℃ cold and hot cycles, and the reliability is higher.
Description
Technical Field
The invention relates to the technical field of electronic adhesives, in particular to a chip-level underfill adhesive and a preparation method thereof.
Background
The chip-level underfill is an epoxy resin polymer composite material filled with inorganic filler, and is generally used for relieving the stress concentration of a solder ball caused by the mismatch of the thermal expansion coefficients of a chip and a substrate in flip chip packaging and improving the packaging reliability. In order to better exert the function of the underfill for protecting the solder ball and the package structure, the Coefficient of Thermal Expansion (CTE) of the underfill material is required to be as close as possible to the CTE (26ppm/K) of the interconnect structure, considering the higher CTE (60-70ppm/K) of the epoxy resin matrix, a large amount of spherical silica filler (greater than or equal to 60 wt%) is usually required to be added into the matrix resin to reduce the CTE and further match the CTE of the solder ball, and the introduction of a large amount of inorganic filler can cause the underfill material to have too strong rigidity, so that the underfill material is easy to generate local stress concentration when being subjected to external stress, and the material fracture failure can not effectively protect the package structure, so the strengthening and toughening of the underfill material are of great significance for exerting the function.
With the increase of I/O density of the interconnection of the flip chip, the size of the chip is larger, the distance between the chip and the substrate is smaller, and meanwhile, the passivation layer (Low-k) material of the chip is made of traditional inorganic SiO2SiN materials are gradually replaced by organic low dielectric PI, BPO and porous SiO2And the like, and the mechanical properties of the materials are generally poor. When the chip is in an aging or service environment, the stress on the solder balls at the edge of the chip is large, and the underfill material is required to have good toughness while dispersing the stress of the solder balls through CTE matching, otherwise, the cracking of the Low-k layer material is easily caused, and the failure of the packaging structure is further caused, so that how to improve the toughness of the underfill adhesive has important significance on the reliability of large-size chip flip-chip packaging.
In the prior art, the toughening of underfill has generally been achieved by adding a toughening agent to the underfill formulation to improve toughness. The common toughening agents mainly comprise the following types:
toughening an elastomer: including random copolymers, core-shell type tougheners, and block copolymers, such as polybutadiene, polybutadiene acrylonitrile copolymers, polysiloxanes, acryl block copolymers, and the like. The traditional carboxyl-terminated liquid nitrile rubber (CTBN) toughening agent has a large phase separation size after being cured, and can exert the toughening effect only by needing high addition amount. From the toughening mechanism point of view, the method is based on the 'sea-island structure' toughening, the toughening agent is aggregated into spherical particles and becomes a disperse phase in a continuous phase formed by an epoxy resin crosslinking network, and the main function of the method is to induce the epoxy resin matrix to yield and plastically deform, so that the fracture toughness is greatly improved. However, the compatibility of rubber elastomers with epoxy resins is poor, and the size of the phase-separated structure formed after curing is large, resulting in limited or even counterproductive toughening effect. In addition, the introduction of the toughening agent generally causes the reduction of fluidity, and therefore, how to realize the "micro-dispersion" of the toughening agent in the resin matrix is crucial to the improvement of the final toughening effect. The core-shell structure type toughening agent is usually powder, and high shear is required for toughening in liquid epoxy resin to realize uniform dispersion. Block copolymer toughening relies on self-assembly behavior for phase separation, but has special requirements for molecular structure.
Toughening thermoplastic resin: the thermoplastic polymer has the characteristics of good toughness, high modulus, higher heat resistance and the like, and not only can improve the toughness of the epoxy resin, but also does not reduce the rigidity and the heat resistance of the epoxy resin. However, the viscosity increases after the addition, and certain requirements are imposed on the operation process.
Flexible chain segment toughening: the toughening agent utilizes the flexible chain segment to graft and modify resin, so that the toughness of a cured product is improved. However, the method generally involves a high-molecular polymerization reaction, and the process control has certain technical difficulties.
Interpenetrating network toughening: the toughening agent plays a role in forced containment by utilizing the synergistic effect generated between two phases in an IPN system. However, after the epoxy resin is cured, the particle diameter of the toughening agent is generally less than a few micrometers, and the dispersed existence of the toughening agent is the key for toughening the epoxy resin. The curing process, curing agent content, initiator concentration and cross-linking agent dosage of the two systems have great influence on the formation of the interpenetrating networks, and all factors need to be strictly controlled.
Disclosure of Invention
Aiming at the technical problems of large phase separation size and low toughening efficiency of the traditional toughening agent after a resin matrix is cured, the invention provides a carrier uniform dispersion technology, a small-size phase separation technology and a micro dispersion technology, which are used for solving the problems of uneven dispersion/overlarge phase separation size of the toughening agent in the traditional toughening method for the underfill, effectively improving the toughness on the premise of not losing the strength and keeping the performances of viscosity, fluidity, modulus and the like. The invention realizes the uniform dispersion of toughening agent molecules in an epoxy resin matrix by taking spherical inorganic filler as a carrier, chemically grafts the toughening agent molecules to the spherical inorganic particles, takes the inorganic particles as the carrier, introduces the toughening agent molecules into underfill, improves the resin compatibility with the underfill, simultaneously takes the spherical inorganic filler as a stress-bearing framework, induces and transmits stress, and uniformly disperses the stress in the resin matrix through the toughening agent grafted on the surface, thereby realizing the high-efficiency dissipation of fracture energy, simultaneously inhibiting the local stress concentration, obviously improving the fracture toughness on the premise of not losing strength, simultaneously inhibiting the precipitation and phase separation of the toughening agent in the underfill and inhibiting the reduction of the traditional toughening fluidity.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a chip-level underfill adhesive, which comprises the following components in percentage by mass:
(A) 10-30 parts of epoxy resin;
(B) 5-25 parts of a curing agent;
(C) 45-75 parts of toughening filler;
the toughening filler is composite particles which take spherical inorganic particles as cores, are subjected to surface modification by a silane coupling agent and are grafted with a toughening agent;
preferably, the silane coupling agent is selected from one or more compounds represented by formula (1);
in the formula (1), m is an integer of 1-3; n is an integer of 0 to 3; r2、R3Each independently selected from methyl or ethyl, and at R2OR OR3When a plurality of the compounds exist, they may be the same as or different from each other; r1Is selected from
Wherein, (X)jSelected from alkyl with 1-6 hydrogen atoms and/or carbon atoms.
In the technical scheme of the invention, in order to improve the dispersibility of the toughening agent in the underfill, inorganic particles are used as a connecting carrier of the toughening agent and an underfill matrix, the inorganic particles are subjected to surface modification by a silane coupling agent with amino groups or phthalic anhydride groups, then the toughening agent is grafted to the surface of the inorganic particles, and the inorganic particles are mixed with the underfill matrix to improve the dispersibility of the toughening agent in the underfill matrix.
In certain embodiments, the epoxy resin is present in an amount of 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 25 parts, 30 parts, or any number therebetween;
in certain embodiments, the mass portion of the curing agent is 5 parts, 7 parts, 10 parts, 12 parts, 15 parts, 20 parts, 25 parts, or any number of mass portions therebetween;
in certain embodiments, the mass portion of the toughening filler is 45 parts, 47 parts, 50 parts, 53 parts, 55 parts, 57 parts, 60 parts, 65 parts, 70 parts, 75 parts, or any number of mass portions therebetween.
As a preferred embodiment, the spherical inorganic particles are selected from spherical SiO2Spherical Al2O3Any one or more of spherical BN, spherical SiN and spherical SiC;
preferably, the spherical inorganic particles have a particle size of 0.1 to 50 μm.
As a preferred embodiment, the silane coupling agent represented by formula (1) is selected from one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (. beta. -aminoethyl) -gamma. -aminopropylmethyl-dimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and 3- (triethoxysilyl) propylsuccinic anhydride.
As a preferred embodiment, the toughening agent is selected from one or more of silicone oil and an a-B-a type acrylic block copolymer containing a reactive group;
preferably, the molecular weight of the A-B-A type acrylic block copolymer containing the active group is 30000-300000;
preferably, in the A-B-A type acrylic block copolymer, the mass proportion of the block B is 30-80%, such as 30%, 40%, 50%, 60%, 70%, 80% or any value of the mass proportion between the blocks;
preferably, the block a is selected from polymethyl methacrylate or polyethyl methacrylate;
preferably, the block B is polybutylmethacrylate;
preferably, the reactive group is an amino group or a carboxyl group; the reactive groups are bonded to block a and/or block B.
Preferably, the silicone oil is epoxy modified silicone oil or amino modified silicone oil;
in some specific embodiments, the epoxy-modified silicone oil has an epoxy equivalent weight of 200 to 600 g/mol; the amine equivalent of the amino modified silicone oil is 2000-10000 g/mol; wherein the epoxy equivalent of the epoxy-modified silicone oil refers to the mass of the epoxy-modified silicone oil containing 1mol of epoxy groups; the amine equivalent of the amino-modified silicone oil refers to the mass of the amino-modified silicone oil containing 1mol of amine groups.
In the technical scheme of the invention, the A-B-A type acrylic block copolymer containing carboxyl or amino active groups can realize grafting through the reaction of the active groups of the A-B-A type acrylic block copolymer with amino and phthalic anhydride groups on a silane coupling agent on the surface of a filler; the epoxy modified silicone oil is grafted by the ring-opening reaction of the epoxy group and the amino group of the silane coupling agent on the surface of the filler, and the epoxy modified silicone oil serving as a toughening agent can solve the problem that the epoxy modified silicone oil is easy to disperse unevenly and separate out of phase when being added independently; the amino modified silicone oil is grafted by amidation reaction of amino and silane coupling agent anhydride group, and can be used as a toughening agent to avoid the problem that the amino modified silicone oil is easy to separate out phase due to uneven dispersion in a formula system when the amino modified silicone oil is added alone.
As a preferred embodiment, the preparation method of the toughening filler comprises the following steps:
step 1, reacting spherical inorganic particles with a silane coupling agent in a solvent I to modify the surfaces of the spherical inorganic particles;
and 2, reacting the surface-modified spherical inorganic particles with a toughening agent in a solvent II to obtain the filler.
As a preferred embodiment, in step 1, the molar ratio of the silane coupling agent to the spherical inorganic particles is 1: 300 to 1800;
preferably, the solvent I is a mixed solution of ethanol and water; the volume ratio of the ethanol to the water is 1-9: 1;
preferably, the mass concentration of the silane coupling agent in the solvent I is 0.05-0.4%; the mass concentration of the surface-modified spherical inorganic particles in the solvent I is 15-60%;
preferably, in step 1, the reaction is a heating reaction; the heating temperature is 50-100 ℃; e.g., 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ or any value therebetween;
preferably, step 1 further comprises post-processing, which comprises centrifugation, washing and drying. In step 1, unreacted silane coupling agent needs to be washed away by post-treatment.
In certain embodiments, the specific operations of step 1 are: dispersing spherical inorganic particles in ethanol and water at a volume ratio of 1-9: 1, adding a silane coupling agent into the mixed solvent, and stirring and refluxing at 50-100 ℃ for reaction for 12-24 hours; cooling, centrifuging, washing and drying.
As a preferred embodiment, in step 2, the mass ratio of the surface-modified spherical inorganic particles to the toughening agent is 20 to 100: 1;
preferably, the solvent II is selected from any one or mixture of acetone and butanone;
preferably, in step 2, the reaction is a heating reaction; the heating temperature of the heating reaction is 50 ℃ to 100 ℃, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ or any value between the two;
preferably, step 2 further comprises post-treatment comprising centrifugation, washing and drying;
preferably, the mass concentration of the spherical inorganic particles in the solvent II is 5-40%; the mass concentration of the toughening agent in the solvent II is 0.1-0.7%.
In certain embodiments, the specific operations of step 2 are: dispersing the surface-modified spherical inorganic particles in a solvent II, adding a toughening agent, and reacting at 50-100 ℃ for 1-5 h; cooling, centrifuging, washing and drying.
In the technical scheme of the invention, polymers such as A-B-A type acrylic block copolymer or silicone oil and the like are used as toughening agents, surface grafting with inorganic particles is realized through a silane coupling agent, and the coating thickness of a toughening agent layer on the surface of the inorganic particles can be controlled by controlling the using amount, reaction time and heating temperature of the polymers.
The second aspect of the present invention provides a method for preparing the chip-scale underfill adhesive, comprising the following steps:
step S1, mixing the epoxy resin and the toughening filler according to the proportion to obtain uniform slurry;
and step S2, adding a curing agent, and mixing to obtain the high-chip-level underfill adhesive.
As a preferred embodiment, in step S1, the mixing is a stepwise mixing; the step-by-step mixing comprises primary mixing and secondary mixing; the primary mixing is 500-1000 rpm/min for 30 s-2 min; the secondary mixing is carried out at 2000-2500 rpm/min for 1-2 min.
In a preferable embodiment, in the step S2, the mixture is mixed at 2000-2500 rpm/min for 1-5 min.
Preferably, the step S2 further includes a defoaming operation after the mixing, wherein the defoaming is vacuum defoaming, and the vacuum degree is preferably from-0.05 MPa to-0.09 MPa.
The technical scheme has the following advantages or beneficial effects:
1. according to the invention, spherical inorganic particles are used as carriers to realize uniform dispersion of filler and toughening agent molecules in an epoxy resin matrix, the inorganic particles are used as a stress-bearing framework to induce and transfer stress, and then the stress is uniformly dispersed in the matrix through the surface-grafted toughening agent, so that the fracture energy is efficiently dissipated, the local stress concentration is inhibited, and the fracture toughness is remarkably improved on the premise of not losing strength; after the flip chip is filled, no crack is generated in the cold and hot circulation at 1000-45-125 ℃, and the reliability is high;
2. according to the invention, by controlling the content of the toughening agent grafted on the surface of the inorganic particle, the effects of small phase separation size and high toughening efficiency of the toughening agent after the resin matrix is cured can be realized, and the synergistic toughening of the inorganic particle filler and the toughening agent can be realized;
3. the invention can realize the improvement of the toughness of the epoxy resin composition under the condition of only using a small amount of the toughening agent, and simultaneously reduce other properties of the toughening agent such as TgPoint, flow properties, etc.
Drawings
FIG. 1 is a schematic diagram of the structure of underfill in examples 1-4 of the present invention and underfill in comparative examples 1-4 in a chip package;
FIG. 2 is a flow chart of the preparation of underfill in examples 1-4 of the present invention;
FIG. 3 is a schematic view of the flow property test method in examples 1 to 4 of the present invention and comparative examples 1 to 4;
FIG. 4 is a graph of the results of comparing the performance of the underfill in examples 1-4 of the present invention with the underfill in comparative examples 1-4 in promoting the dispersion of the toughening agent and suppressing the precipitation of the toughening agent.
Fig. 5 is a graph comparing the performance of flip chips filled with underfill according to example 4 of the present invention with that of comparative example 4 in terms of crack suppression.
Detailed Description
The following examples are only a part of the present invention, and not all of them. Thus, the detailed description of the embodiments of the present invention provided below is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the invention without inventive step, are within the scope of protection of the invention.
Carboxyl group-containing acrylic block copolymer of type A-B-A:
in the invention, the A-B-A type acrylic acid block copolymer containing carboxyl, wherein the block A is polymethyl methacrylate or polyethyl methacrylate, and the block B is polybutyl methacrylate; the molecular weight is 30000-300000; the mass proportion of the block B is preferably 30-80%; examples of the block copolymer include: the trade names of Colorado corporation, LA2250 (molecular weight 80000, block B30% by mass, A is poly (methyl methacrylate)), LA2230 (molecular weight 80000, block B50% by mass, A is poly (methyl methacrylate)), and LA3320 (molecular weight 80000, block B70% by mass, A is poly (methyl methacrylate)).
Amino group-containing acrylic block copolymer of type A-B-A:
in the invention, an amino-containing A-B-A type acrylic block copolymer, wherein a block A is polymethyl methacrylate or polyethyl methacrylate, and a block B is polybutyl methacrylate; the molecular weight is 30000-300000; the mass ratio of the block B is 30-80%; examples thereof include: the company Akema, under the designation M52N (molecular weight 90000, block B30% by mass, A for poly (methyl methacrylate)), M65N (molecular weight 250000, block B50% by mass, A for poly (methyl methacrylate)), M22N (molecular weight 300000, block B70% by mass, A for poly (methyl methacrylate)), and the like.
Silicone oil:
in the present invention, the silicone oil is preferably an epoxy-modified silicone oil or an amino-modified silicone oil; wherein the epoxy group or the amino group can be bonded to the double-ended, single-ended or side-chain Si atom of the silicone oil;
preferably, the structural general formula of the double-end epoxy group modified silicone oil or the double-end amino group modified silicone oil is shown as formula (2):
in the formula (2), X is epoxy group or amino group; r1Each independently selected from any one of hydrogen atom, alkyl group with 1-5 carbon atoms, substituted alkyl group with 1-5 carbon atoms, phenyl group or substituted phenyl group, and R1May be the same or different from each other; r2A single bond or a 2-valent aliphatic or aromatic hydrocarbon group having 1 to 10 carbon atoms; n represents a number of repeating units of 5 to 100.
Preferably, the structural general formula of the single-end epoxy group modified silicone oil or the single-end amino group modified silicone oil is shown as formula (3):
in the formula (3), X is epoxy group or amino group; r1Each independently selected from any one of hydrogen atom, alkyl group with 1-5 carbon atoms, substituted alkyl group with 1-5 carbon atoms, phenyl group or substituted phenyl group, and R1May be the same or different from each other; r2A single bond or a 2-valent aliphatic or aromatic hydrocarbon group having 1 to 10 carbon atoms; n represents a number of repeating units of 5 to 100.
Preferably, the structural general formula of the side chain epoxy group modified silicone oil or the side chain amino group modified silicone oil is shown as formula (3):
in the formula (4), X is epoxy group or amino group; r1Each independently selected from any one of hydrogen atom, alkyl group with 1-5 carbon atoms, substituted alkyl group with 1-5 carbon atoms, phenyl group or substituted phenyl group, and R1May be the same as each otherMay be different; n represents the number of repeating units of 1 to 5; m represents the number of repeating units of 1 to 100.
In some specific examples, epoxy-modified silicone oils may be listed under the trade designation X22-343, X22-163, KF105, having an epoxy equivalent of 525g/mol, 200g/mol, 490g/mol, respectively; examples of the amino-modified silicone oil include the following chemical trade names: KF 861, KF 865 and KF 868, which have amine equivalent weights of 2000g/mol, 5000g/mol and 8800g/mol, respectively.
In the following examples and comparative examples:
spherical silica was purchased from Admatech corporation and prepared by a melt process, a flame-explosion process or a liquid phase process, wherein the filler prepared by the melt process had an average particle diameter of 15 μm (FEB 25A); the average particle diameter of the filler prepared by the combustion explosion method is 2 μm (SE6050) and 0.5 μm (SE 2200); the average particle diameter of the filler prepared by the liquid phase method was 100nm (YC100C-SP 3).
The epoxy resins used include:
bisphenol A epoxy resin available from Vast of America under the trademark EPIKOTE 828.
Naphthalene epoxy resin, available from DIC corporation under the designation HP 7200.
Silane coupling agent used:
3-aminopropyltrimethoxysilane (CH)3O)3SiC3H6NH2Number KBM903, purchased from believer chemical;
3-aminopropyltriethoxysilane (C)2H5O)3SiC3H6NH2Number KBE903, from believing chemicals;
3- (triethoxysilyl) propyl succinic anhydride, trade name SIT8192.6, available from Gelest; the structural formula is shown as the following formula:
the toughening agents used included:
the carboxyl group-containing acrylic block copolymer of type A-B-A was obtained from Coly corporation: the block A is polymethyl methacrylate, and the block B is polybutyl methacrylate; trade marks LA2250 (molecular weight 80000, block B mass 30%), LA2230 (molecular weight 80000, block B mass 50%);
the epoxy equivalent of the modified silicone oil having an epoxy functional group is 200 to 600g/mol, and examples thereof include X22-343 and X22-163 commercially available from shin-Etsu chemical Co., Ltd., and the epoxy equivalent thereof is 525g/mol and 200g/mol, respectively.
The curing agents used included:
diethyltoluenediamine DETDA Ethacure 100 available from Albemarle Japan;
methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, available from Puyang Puhucheng electronics materials, Inc.
Example 1:
the preparation of the chip-level underfill in this example is shown in fig. 2, and the specific steps are as follows:
the method comprises the following steps: dispersing 120g of spherical silica (component D2, with the average particle size of 15 mu m) prepared by a melting method into 500mL of mixed solvent of ethanol and water (ethanol: water volume ratio is 90: 10), adding 1g of 3-aminopropyltrimethoxysilane, stirring and refluxing at 80 ℃ for 12h, cooling, centrifuging and washing, removing the silane coupling agent which is not grafted on the surface, and drying at 100 ℃ for 4h to obtain surface-modified amino-functionalized silica powder; dispersing 60g of the obtained amino-functionalized silicon dioxide powder in 500mL of butanone solvent, adding 1g of carboxyl-terminated acrylic rubber copolymer LA2250 (toughening agent C1), reacting at 80 ℃ for 5h, and then centrifugally drying to obtain toughening filler D1;
step two: weighing 30g of bisphenol A type epoxy resin (component A1), and mixing at a high speed of 1000rpm/min for 2 min;
step three: weighing 61g of the toughening filler (component D1) obtained in the step (1), adding the toughening filler into the epoxy resin, firstly mixing for 2min at 1000rpm/min by a high-speed mixer, and then mixing for 2min at 2500rpm/min to obtain uniform slurry;
step four: and (3) adding 9g of aromatic amine curing agent diethyl toluene diamine DETDA (component B1) into the slurry obtained in the step three, mixing for 2min at a high speed of 2500rpm/min, and performing vacuum defoaming with the vacuum degree controlled at-0.08 MPa to obtain the bottom filling adhesive.
In this example, the filling amount of the toughening filler is about 60 wt%, and the filling amount is the ratio of the mass of the toughening filler to the total mass of the toughening filler, the epoxy resin (i.e., bisphenol a type epoxy resin) and the curing agent.
Example 2:
the preparation of the chip-level underfill in this example is shown in fig. 2, and the specific steps are as follows:
the method comprises the following steps: dispersing 240g of spherical silicon dioxide (component D4, with the average particle size of 2 mu m) prepared by a combustion explosion method into 500mL of mixed solvent of ethanol and water (ethanol: water volume ratio 80: 20), adding 0.5g of 3-aminopropyltriethoxysilane into the mixture, stirring and refluxing for reaction for 24h at 60 ℃, cooling, centrifuging and washing to remove the silane coupling agent which is not grafted on the surface, and drying for 6h at 120 ℃ to obtain surface-modified amino-functionalized silicon dioxide powder; dispersing 60g of the obtained amino functionalized silicon dioxide powder in 1000mL of butanone solvent, adding 1g of carboxyl terminated acrylic rubber copolymer LA2230 (toughening agent C2), reacting for 2h at 60 ℃, centrifuging, washing and drying to obtain a toughening filler D3;
step two: 27.38g of bisphenol F type epoxy resin (component A2) is weighed and mixed for 1min at a high speed of 1500 rpm/min;
step three: weighing 61g of the toughening filler (component D3) obtained in the step 1, adding the toughening filler into the epoxy resin, firstly mixing for 1min at 1500rpm/min of a high-speed mixer, and then mixing for 1min at 2000rpm/min to obtain uniform slurry;
step four: and (3) adding 11.62g (component B1) of aromatic amine curing agent DETDA into the slurry obtained in the step three, mixing for 1min at a high speed of 2000rpm/min, and defoaming in vacuum with the vacuum degree controlled at-0.09 MPa to obtain the bottom filling adhesive.
In this example, the loading of the toughening filler was about 60 wt%.
Example 3:
the preparation of the chip-level underfill in this example is shown in fig. 2, and the specific steps are as follows:
the method comprises the following steps: dispersing 360g of spherical silica (component D6, with the average particle size of 0.5 mu m) prepared by an explosion method in 500mL of a mixed solvent of ethanol and water (ethanol: water volume ratio 60: 40), adding 2g of 3- (triethoxysilyl) propyl succinic anhydride, stirring and refluxing at 70 ℃ for reaction for 12h, cooling, centrifuging and washing, removing the silane coupling agent which is not grafted on the surface, and drying at 140 ℃ for 2 h; dispersing 120g of the obtained surface-modified silicon dioxide powder in 500mL of acetone solvent, adding 2g of epoxy modified silicone oil X22-343 (toughening agent C3), reacting for 2h at 60 ℃, centrifuging, washing and drying to obtain a toughening filler D5;
step two: weighing 18.28g (component A3) of naphthalene ring epoxy resin, and mixing at a high speed of 1500rpm/min for 1 min;
step three: weighing 61g of the toughening filler (component D5) obtained in the step 1, adding the toughening filler into the epoxy resin, firstly mixing for 1min at 1500rpm/min of a high-speed mixer, and then mixing for 1min at 2000rpm/min to obtain uniform slurry;
step four: and (3) adding 20.72g (component B2) of anhydride curing agent methyl tetrahydrophthalic anhydride into the slurry obtained in the step three, mixing for 2min at a high speed of 2000rpm/min, and defoaming in vacuum with the vacuum degree controlled at-0.05 MPa to obtain the bottom filling adhesive.
In this example, the loading of the toughening filler was about 60 wt%.
Example 4:
the preparation of the chip-level underfill in this embodiment is shown in fig. 2, and the specific steps are as follows:
the method comprises the following steps: dispersing 480g of spherical silicon dioxide (component D8, with the average particle size of 100nm) prepared by a liquid phase method in 500mL of mixed solvent of ethanol and water (ethanol: water volume ratio is 50: 50), adding 2g of 3- (triethoxysilyl) propyl succinic anhydride, stirring and refluxing at 70 ℃ for 12h, cooling, centrifuging and washing, removing the silane coupling agent which is not grafted on the surface, and drying at 140 ℃ for 2h to obtain surface modified silicon dioxide powder; dispersing 240g of the obtained silicon dioxide powder in 1000mL of acetone solvent, adding 4g of epoxy-terminated modified silicone oil X22-163 (toughening agent C4), reacting for 2h at 60 ℃, centrifuging, washing and drying to obtain a toughening filler D7;
step two: weighing 18.28g of bisphenol A epoxy resin (component A1), and mixing at 2000rpm/min for 1 min;
step three: weighing 61g of the toughening filler (component D7) obtained in the step (1), adding the toughening filler into the epoxy resin composition, firstly mixing for 3min at 1000rpm/min of a high-speed mixer, and then mixing for 3min at 2000rpm/min to obtain uniform slurry;
step four: and (3) adding 20.72g (component B3) of anhydride curing agent methyl hexahydrophthalic anhydride into the slurry obtained in the step three, mixing for 5min at a high speed of 2000rpm/min, and performing vacuum defoamation, wherein the vacuum degree is controlled to be-0.05 MPa, thus obtaining the bottom filling adhesive.
In this example, the loading of the toughening filler was about 60 wt%.
Comparative example 1:
the method comprises the following steps: weighing 30g of bisphenol A type epoxy resin (component A1), 1g of toughening agent LA2250 (toughening agent C1), and mixing at a high speed of 1000rpm/min for 2min to obtain an epoxy resin composition;
step two: weighing 60g of spherical silicon dioxide (component D2, prepared by a melting method, with the particle size of 15 μm), adding into the epoxy resin composition, firstly mixing for 2min by a high-speed mixer at 1000rpm/min, and then mixing for 2min at 2500rpm/min to obtain uniform slurry;
step three: and (3) adding 9g (component B1) of aromatic amine curing agent DETDA into the slurry obtained in the step three, mixing for 2min at a high speed of 2500rpm/min, and defoaming in vacuum with the vacuum degree controlled at-0.08 MPa to obtain the bottom filling adhesive.
Comparative example 2:
the method comprises the following steps: weighing 27.38g of bisphenol F type epoxy resin (component A2), 2g of LA2230 (toughening agent C2), and mixing at a high speed of 1500rpm/min for 1min to obtain an epoxy resin composition;
step two: weighing 60g of spherical silicon dioxide (component D4, prepared by a combustion explosion method, with the particle size of 2 μm), adding into the epoxy resin composition, firstly mixing for 1min at 1500rpm/min by a high-speed mixer, and then mixing for 1min at 2000rpm/min to obtain uniform slurry;
step three: and (3) adding 11.62g (component B1) of aromatic amine curing agent DETDA into the slurry obtained in the step three, mixing for 1min at a high speed of 2000rpm/min, and defoaming in vacuum with the vacuum degree controlled at-0.09 MPa to obtain the bottom filling adhesive.
Comparative example 3:
the method comprises the following steps: weighing 18.28g of naphthalene ring epoxy resin (component A3) and 1g of X22-343 (toughening agent C3), and mixing at a high speed of 1500rpm/min for 1min to obtain an epoxy resin composition;
step two: weighing 60g of spherical silicon dioxide (component D6, prepared by a combustion explosion method and having a particle size of 0.5 mu m), adding into the epoxy resin composition, firstly mixing for 1min at 1500rpm/min of a high-speed mixer, and then mixing for 1min at 2000rpm/min to obtain uniform slurry;
step three: and (3) adding 20.72g (component B2) of anhydride curing agent methyl tetrahydrophthalic anhydride into the slurry obtained in the step three, mixing for 2min at a high speed of 2000rpm/min, and defoaming in vacuum with the vacuum degree controlled at-0.05 MPa to obtain the bottom filling adhesive.
Comparative example 4:
the method comprises the following steps: weighing 18.28g of bisphenol A epoxy resin (component A1), 1g of X22-163 (toughening agent C4) (component C4), and mixing at a high speed of 2000rpm/min for 1min to obtain an epoxy resin composition;
step two: weighing 60g of spherical silica filler (component D8, prepared by a liquid phase method, with the particle size of 100nm), adding into the epoxy resin composition, firstly mixing for 3min by a high-speed mixer at 1000rpm/min, and then mixing for 3min at 2000rpm/min to obtain uniform slurry;
step three: and (3) adding 20.72g (component B3) of anhydride curing agent methyl hexahydrophthalic anhydride into the slurry obtained in the step three, mixing for 5min at a high speed of 2000rpm/min, and performing vacuum defoamation, wherein the vacuum degree is controlled to be-0.05 MPa, thus obtaining the bottom filling adhesive.
Table 1 shows the mass parts of the components of the underfill in examples 1-4 and comparative examples 1-4 and the relevant performance test data.
[ TABLE 1 ]
The evaluation method comprises the following steps:
fluidity (see fig. 3): a test piece of a double-layer slide glass having a gap of 50 μm was formed by sticking two tapes having a thickness of 50 μm to each other on two glass slides, wherein the distance between the tapes was 10mm, placing the test piece on a heating plate set at 110 ℃, injecting underfill from one end of the gap between the two glass slides, measuring the time until the injection distance reached 30mm, and testing 2 times, and the average value of the measured values was used as the flow time to evaluate the fluidity.
TgPoint and modulus: heating the liquid underfill at 165 deg.C for 120min to cure it to form a cured product, and testing T by using DMA double-cantilever modegPoint and modulus, taking the temperature corresponding to the peak value of Tan delta as TgAnd (4) point.
K1C: a liquid underfill was poured into a mold to prepare a sample having a length of 35mm, a width of 7mm and a thickness of 3mm, and the sample was measured by an electronic universal tester (Shimadzu AGX-10kNVD) to introduce a crack with a blade in the middle.
FIG. 1 is a schematic diagram of the structure of the underfill of examples 1-4 and the underfill of comparative examples 1-4 after filling the flip chip, as can be seen: in comparative examples 1-4, the toughening agent is directly added to the epoxy resin composition in a blending manner, the poor compatibility between the toughening agent and silicon dioxide leads to the toughening agent being easily precipitated from the epoxy resin matrix and phase separation, and the poor toughening effect is caused, while in examples 1-4, the uniform dispersion of toughening agent molecules in the epoxy resin matrix is realized by taking the spherical inorganic filler as a carrier, the toughening agent molecules are chemically grafted to the spherical inorganic particles, the inorganic particles are taken as the carrier, the toughening agent molecules are introduced into the underfill, the resin compatibility with the underfill is improved, meanwhile, the spherical inorganic filler is taken as a stress-bearing framework, stress is induced and transferred, and then the surface-grafted toughening agent uniformly disperses the stress in the resin matrix, so that the high-efficiency dissipation of fracture energy is realized while the local stress concentration is inhibited, the fracture toughness is remarkably improved on the premise of not losing strength, meanwhile, the toughening agent is inhibited from separating out and splitting phase in the underfill, and the problem of the traditional toughening fluidity reduction is inhibited.
FIG. 4 is a graph showing the comparison of the performance of the underfill according to examples 1-4 of the present invention with that of the underfill according to comparative examples 1-4 in terms of increasing the dispersion of the toughening agent and suppressing the precipitation of the toughening agent, wherein (a) is a measure of the fineness of the squeegee before the underfill material of example 1 is cured, and (b) is a measure of the fineness of the squeegee before the underfill material of comparative example 1 is cured. Fig. (c) is an appearance of the underfill in example 2, and fig. (d) is an appearance of the underfill in comparative example 2. It can be seen from the figure that there is a distinct phase separation in the figure (d), i.e. the separated toughening agent, while the toughening agent is not separated out significantly in the figure (c), and the toughening agent and the resin matrix are dispersed uniformly, which shows that the separation of the toughening agent in the resin matrix can be inhibited significantly and the dispersion of the toughening agent in the resin matrix can be improved by grafting the toughening agent on the surface of the filler.
FIG. 5 is a graph of the results of comparing the performance of an underfill of example 4 of the present invention with a flip chip filled underfill of comparative example 4 in inhibiting cracking after 1000 cycles at 45 ℃ minus to 125 ℃. In fig. 5, (a) is a surface electron micrograph of a flip chip of example 4, and (b) is a partial enlarged view of the surface electron micrograph of the flip chip of example 4; FIG. (c) is a surface electron micrograph of the flip chip of comparative example 4, and FIG. (d) is a partial enlarged view of the surface electron micrograph of the flip chip of comparative example 4; as can be seen from the figures, the underfill for flip chip has obvious cracks compared to the figures (c) and (d), and the underfill for flip chip in figures (a) and (b) has obviously inhibited the generation of cracks, which shows that the underfill containing the toughening agent grafted filler can more effectively improve the fracture toughness of the underfill and thus improve the reliability of the packaged device.
As can be seen from fig. 1, 4 and table 1:
compared with the underfill which is added in a blending manner in the conventional toughening agent comparative examples 1 to 4, the underfill which is provided by the embodiments 1 to 4 of the present invention and connects the epoxy resin and the toughening agent by using the inorganic particles as a carrier has the following advantages in terms of performance:
1. in the aspect of dispersibility: in the conventional blending toughening agent in the underfill, the toughening agent and the resin matrix are difficult to uniformly disperse due to the polarity difference; the underfill containing the toughening agent filler provided by the invention can realize uniform dispersion of toughening agent molecules in the underfill material by taking the spherical filler as a carrier;
2. and (3) precipitation inhibition: the traditional blending toughening agent is easy to separate out phase separation after the resin matrix of the underfill is cured; according to the underfill containing the toughening agent filler, the content and the grafting thickness of the toughening agent chemically grafted on the surface of the filler can be controlled, so that the molecules of the toughening agent can be inhibited from being separated out from a cured underfill, and the low stress and the toughness of the cured underfill are improved;
3. and (3) fluidity: the underfill that was blended and added through the conventional toughener in comparative examples 1-4 generally had the problem of long fluidity time, while the underfill in examples 1-4 had significantly improved fluidity; the improvement of the flow property is beneficial to improving the filling effect of the underfill in the chip and avoiding the generation of hole defects in the filling process;
4. at TgAnd modulus, the toughener of comparative examples 1-4 was added to the underfill by blending, its TgPoint, modulus, fracture toughness K1CAre all lower, and the T of the underfill provided in examples 1-4gPoint, modulus, fracture toughness K1CThere is a corresponding increase.
The above description is only for the preferred embodiment of the present invention and is not intended to limit the scope of the present invention, and all equivalent modifications made by the contents of the present specification and the drawings, or applied directly or indirectly to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A chip-scale underfill comprising, in mass percent:
(A) 10-30 parts of epoxy resin;
(B) 5-25 parts of a curing agent;
(C) 45-75 parts of toughening filler;
the toughening filler is composite particles which take spherical inorganic particles as cores, are subjected to surface modification by a silane coupling agent and are grafted with a toughening agent;
preferably, the silane coupling agent is selected from one or more compounds represented by formula (1);
in the formula (1), m is an integer of 1-3; n is an integer of 0 to 3; r2、R3Each independently selected from methyl or ethyl, and at R2OR OR3When a plurality of the compounds exist, they may be the same as or different from each other; r1Is selected from
Wherein, (X)jSelected from alkyl with 1-6 hydrogen atoms and/or carbon atoms.
2. The chip scale underfill according to claim 1, wherein the spherical inorganic particles are selected from spherical SiO2Spherical Al2O3Any one or more of spherical BN, spherical SiN and spherical SiC;
preferably, the spherical inorganic particles have a particle size of 0.1 to 50 μm.
3. The chip scale underfill according to claim 1, wherein the silane coupling agent represented by formula (1) is selected from one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (β aminoethyl) - γ -aminopropylmethyl-dimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and 3- (triethoxysilyl) propyl succinic anhydride.
4. The chip scale underfill according to claim 1, wherein said toughening agent is selected from one or more of silicone oils and a-B-a type acrylic block copolymers containing reactive groups;
preferably, the molecular weight of the A-B-A type acrylic block copolymer containing the active group is 30000-300000;
preferably, in the A-B-A type acrylic block copolymer, the mass proportion of the block B is 30-80%;
preferably, the block a is selected from polymethyl methacrylate or polyethyl methacrylate;
preferably, the block B is polybutylmethacrylate;
preferably, the reactive group is an amino group or a carboxyl group; the active group is bonded to block a and/or block B;
preferably, the silicone oil is epoxy modified silicone oil or amino modified silicone oil.
5. The chip scale underfill according to claim 1, wherein the preparation method of the toughening filler comprises the following steps:
step 1, reacting spherical inorganic particles with a silane coupling agent in a solvent I to modify the surfaces of the spherical inorganic particles;
and 2, reacting the surface-modified spherical inorganic particles with a toughening agent in a solvent II to obtain the filler.
6. The chip scale underfill according to claim 5, wherein in step 1, the molar ratio of the silane coupling agent to the spherical inorganic particles is 1: 300 to 1800;
preferably, the solvent I is a mixed solution of ethanol and water; the volume ratio of the ethanol to the water is 1-9: 1;
preferably, the mass concentration of the silane coupling agent in the solvent I is 0.05-0.4%; the mass concentration of the spherical inorganic particles in the solvent I is 15-60 percent;
preferably, in step 1, the reaction is a heating reaction; the heating temperature is 50-100 ℃;
preferably, step 1 further comprises post-processing, which comprises centrifugation, washing and drying.
7. The chip-scale underfill according to claim 5, wherein in the step 2, the mass ratio of the surface-modified spherical inorganic particles to the toughening agent is 20-100: 1;
preferably, the solvent II is selected from any one or mixture of acetone and butanone;
preferably, the mass concentration of the surface-modified spherical inorganic particles in the solvent II is 5-40%; the mass concentration of the toughening agent in the solvent II is 0.1-0.7%.
Preferably, the reaction is a heating reaction; the heating temperature of the heating reaction is 50-100 ℃;
preferably, step 2 further comprises post-processing, including centrifugation, washing and drying.
8. The method for preparing chip scale underfill according to any one of claims 1 to 7, comprising the steps of:
step S1, mixing the epoxy resin and the toughening filler according to the proportion to obtain uniform slurry;
and step S2, adding a curing agent, and mixing to obtain the chip-level underfill adhesive.
9. The production method according to claim 8, wherein in step S1, the mixing is stepwise mixing; the step-by-step mixing comprises primary mixing and secondary mixing, wherein the primary mixing is 500-1000 rpm/min for 30 s-2 min; the secondary mixing is carried out at 2000-2500 rpm/min for 1-2 min.
10. The preparation method according to claim 7, wherein in the step S2, the mixed material is mixed for 1-5 min at 2000-2500 rpm/min;
preferably, the step S2 further includes a defoaming operation after mixing; the defoaming is vacuum defoaming, and the vacuum degree is preferably-0.05 MPa to-0.09 MPa.
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| CN115353846A (en) * | 2022-09-23 | 2022-11-18 | 深圳市浩力新材料技术有限公司 | Low-stress mini LED screen packaging adhesive and preparation method thereof |
| CN116496738A (en) * | 2023-05-04 | 2023-07-28 | 深圳市安伯斯科技有限公司 | Low-viscosity underfill capable of being quickly cured at low temperature and preparation method thereof |
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| CN104910845A (en) * | 2015-06-12 | 2015-09-16 | 深圳先进技术研究院 | Underfill adhesive and preparation method thereof |
| CN104962224A (en) * | 2015-07-06 | 2015-10-07 | 深圳先进技术研究院 | Underfill adhesive and preparation method thereof |
| WO2021196510A1 (en) * | 2020-03-31 | 2021-10-07 | 苏州巨峰电气绝缘***股份有限公司 | High thermal conductivity electrical insulation packaging material and preparation method therefor |
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| CN104910845A (en) * | 2015-06-12 | 2015-09-16 | 深圳先进技术研究院 | Underfill adhesive and preparation method thereof |
| CN104962224A (en) * | 2015-07-06 | 2015-10-07 | 深圳先进技术研究院 | Underfill adhesive and preparation method thereof |
| WO2021196510A1 (en) * | 2020-03-31 | 2021-10-07 | 苏州巨峰电气绝缘***股份有限公司 | High thermal conductivity electrical insulation packaging material and preparation method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115353846A (en) * | 2022-09-23 | 2022-11-18 | 深圳市浩力新材料技术有限公司 | Low-stress mini LED screen packaging adhesive and preparation method thereof |
| CN115353846B (en) * | 2022-09-23 | 2023-11-24 | 深圳市浩力新材料技术有限公司 | Low-stress packaging adhesive for mini LED screen and preparation method thereof |
| CN116496738A (en) * | 2023-05-04 | 2023-07-28 | 深圳市安伯斯科技有限公司 | Low-viscosity underfill capable of being quickly cured at low temperature and preparation method thereof |
| CN116496738B (en) * | 2023-05-04 | 2024-01-30 | 深圳市安伯斯科技有限公司 | Low-viscosity underfill capable of being quickly cured at low temperature and preparation method thereof |
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