A resin composition for electronic device sealing

Abstract

The present application relates to the technical field of semiconductor packaging materials, and in particular to a resin composition for electronic device sealing. Existing epoxy resin compositions include solid / powder nanoscale fillers to reduce CTE and inhibit the occurrence of bleeding problems. However, it is very difficult to add solid / powder nanoscale fillers to the epoxy resin composition, which will cause the overall viscosity to increase sharply and even cannot be mixed uniformly. The present application adds colloidal fillers to prepare a resin composition with lower viscosity, which means that the filler load in the resin composition (underfill) can be further increased, and the overall excellent moisture resistance and better temperature resistance of the composition can be improved. In addition, due to the increase in the filler load, the CTE of the cured resin composition is reduced, thereby improving the reliability of the cured resin mixture.

Description

Technical Field

[0001] This invention relates to the field of semiconductor packaging materials technology, and in particular to a resin composition for sealing electronic devices. Background Technology

[0002] As electronic devices become smaller, thinner, lighter, and more high-performance, semiconductor packaging is shifting from wire bonding to flip-chip packaging.

[0003] Flip-chip technology is a method of interconnecting semiconductor devices, IC chips, integrated passive devices, and microelectromechanical systems (MEMS) dies to external circuits via solder bumps deposited on chip pads. Flip-chip semiconductor devices have a structure where electrodes on a substrate and semiconductor elements are connected via solder bumps or copper pillars. When external temperature changes, such as temperature cycling, are applied to the semiconductor device, stress is generated on the bump electrodes due to the difference in thermal expansion coefficients between the substrate (organic materials such as epoxy resin or polyimide resin) and the semiconductor element (Si material). Therefore, cracks may appear in the bump electrodes. Furthermore, external physical shocks or impacts can also apply stress to the bump electrodes, leading to bump crack defects. To suppress bump crack defects, resin compositions (so-called underfill) are currently widely used to fill the gap between the semiconductor element and the substrate.

[0004] In recent years, high-density packaging has been developed to achieve lower costs, more functionality, and higher performance due to finer wiring, multilayers, high pin counts, miniaturization, and thinning of packages. As a result, chip-scale packages (CSPs), which have nearly the same size as components such as integrated circuits, have been widely used. In particular, wafer-level chip-scale packaging has received increasing attention. In this type of wafer-level chip-scale packaging, a large number of components are packaged using compression molding or transfer molding of epoxy resin compositions. However, the sealed silicon wafer can warp, affecting subsequent transportation, polishing, inspection, and monolithization. Silicon wafer warping can lead to a deterioration in package reliability. The causes of silicon wafer warping include stress generated by the curing shrinkage of the epoxy resin composition and CTE (coefficient of thermal expansion) mismatch between the silicon wafer and the epoxy resin composition.

[0005] In the field of component sealing / encapsulation for electronic devices, epoxy resin compositions remain the mainstream choice as underfillers due to considerations of cost and productivity. Currently, an effective method for reducing stress in epoxy resin compositions is to use highly filled inorganic fillers to lower CTE (Cellular Strength Emitting Factor).

[0006] Patent JP2020070347A describes an underfill comprising (A) an epoxy resin; (B) a curing agent; (C) an inorganic filler with an average particle size of 7 nm to 100 nm; and (D) a liquid silicone compound having carboxyl groups. This patent discloses a liquid epoxy resin composition comprising at least a liquid epoxy resin, a liquid curing agent, and an inorganic filler, as a liquid resin composition for liquid underfill to reduce and redistribute stress problems between semiconductor elements and a substrate.

[0007] In the patent JP2020070347A, which uses nanoscale silica (7nm~100nm) and liquid silicone compounds with carboxyl groups, exudation, creep, and voids can be suppressed, and the CTE of epoxy resin cured products can be reduced. However, the technology in the aforementioned patent has the problem of difficulty in adding solid / powder nanoscale fillers to epoxy resin compositions, which leads to a sharp increase in the viscosity of the overall composition and even makes it impossible to mix uniformly. These unevenly mixed fillers will reduce the performance of the underfiller and even lead to poor flowability, creep, and reliability problems such as voids and delamination. Usually, in order to achieve a certain balance between viscosity / flowability and the performance of the underfiller, the amount of filler is usually reduced to reduce the overall viscosity, but this will increase the CTE of epoxy resin cured products, thus leading to a risk of partially sacrificing reliability. In addition, while maintaining the same filler load, another approach is to use fillers with larger particle sizes to reduce the viscosity of the composition. However, with the current trend of semiconductor devices becoming smaller and smaller, the gap between the chip and the substrate is becoming smaller and smaller. Therefore, it will be difficult for fillers with larger particle sizes to completely fill the small gap between semiconductor devices and substrates. Summary of the Invention

[0008] The purpose of this invention is to provide a new resin composition that, without sacrificing the reliability of some resin compositions, exhibits good viscosity and flow properties, and allows for further increases in filler loading.

[0009] To achieve the objective of this invention, the technical solution is as follows:

[0010] A resin composition for sealing electronic devices comprises, by weight percentage: 10-30% thermosetting resin, 15-35% curing agent, 0.1-3% catalyst, 0.8-5% additives, 5-20% colloidal filler, and 45-68% solid filler. The thermosetting resin is selected from epoxy resins, and the thermosetting resin is liquid at 25°C. Furthermore, "the thermosetting resin is liquid at 25°C" means that when the thermosetting resin is selected from two or more mixtures, it is liquid at 25°C. This can be understood as the combined use of a solid epoxy resin and a liquid epoxy resin at room temperature, where the solid epoxy resin is dissolved or dispersed in the liquid epoxy resin, as long as the mixture is liquid at room temperature (25°C).

[0011] Further, the colloidal filler is selected from silica sol, alumina sol, or a mixture of both, with a particle size ≤100nm. More further, the solid filler is selected from clay, kaolin, talc, mica, silica, calcium carbonate, sodium sulfate, magnesium sulfate, barium sulfate, alumina, boron nitride, and aluminum nitride. Preferably, the solid filler is selected from silica, alumina, boron nitride, aluminum nitride, or a mixture of any combination of silica, alumina, boron nitride, and aluminum nitride. The shape of the solid filler can be spherical and / or plate-like and / or random, more preferably spherical solid filler. The particle size of the solid filler is: 0.010 μm ≤ particle size ≤ 10 μm, preferably: 0.015 μm ≤ particle size ≤ 5 μm, more preferably 0.015 μm ≤ particle size < 5 μm. Particularly preferred solid filler is spherical silica particles. Most commercially available spherical silica particles have been surface modified with silane coupling agents. Surface modification ensures the compatibility of the filler with epoxy resin and the flowability of the entire composition, making them a preferred choice.

[0012] The colloidal filler is a suspension of silica or aluminum in a liquid phase, wherein the silica or aluminum particles are fine, amorphous, non-porous, and typically spherical. The liquid phase can be selected from organic liquid resins, organic solvents, or aqueous solutions as the matrix. As a specific embodiment, the organic liquid resin can be selected from liquid epoxy resins, liquid acrylic resins, liquid silicone resins, liquid polyether resins, and liquid polyester resins. Liquid epoxy resins, liquid acrylic resins, and liquid silicone resins are preferred. Liquid epoxy resins and liquid silicone resins are particularly preferred.

[0013] More specifically, the colloidal fillers include Nanobox A410, Nanobox A510, Nanobox A611, Nanobox E430, Nanobox E470, Nanobox E500, Nanobox E601, Nanobox E770, Nanobox F400, Nanobox F440, Nanobox F520, Nanobox F631, Nanobox F700, EVONP-470, LUDOX® HS-30, MAS colloidal silica, 406 colloidal silica, AEROSIL® Colloidal Silica, AEROPERL® Collidal Silica, and AMSol. TM 8 SM, AMSol TM 8SMX, AMSol TM 15. AMSol TM 15SM, AMSol TM 20 SM, AMSol TM 30. AMSol TM 30 SM, AMSol TM 4012, AMSol TM 4015, AMSol TM 50. AMSol TM HT, etc., but not limited to these.

[0014] The packing material can be composed of organic packing material or inorganic packing material.

[0015] The above-mentioned resin composition may further include an organic filler, which is selected from carbon black, graphite, graphene, carbon nanotubes, and acrylate beads. The organic filler may be spherical, flake-shaped, or randomly shaped. The organic filler can be added as needed; for example, if the resin composition is required to have a color recognition function, an organic filler may be added. When adding an organic filler, its addition amount is 0.01% to 5% of the total weight of the resin composition, preferably 0.05% to 2%, without affecting the various properties of the resin composition.

[0016] Furthermore, the thermosetting resin is selected from one or more of the following: epoxy resin, epoxy phenolic varnish resin, phenolic resin, unsaturated polyester, polyurethane, diallyl phthalate resin, bismaleimide resin, melamine resin, benzoxazine, polyimide, cyanate ester, furan resin, and silicone resin.

[0017] Preferably, epoxy resins are selected from the perspective of the curability and adhesion of the resin composition (bottom filler), as well as the heat resistance, mechanical resistance, moisture resistance, durability and electrical insulation of the cured epoxy resin composition.

[0018] Epoxy resins are selected from aliphatic epoxy resins, aromatic epoxy resins, saturated epoxy resins, or unsaturated epoxy resins. These epoxy resins can be further divided into two types: glycidyl-based epoxy resins and non-glycidyl-based resins. Glycidyl-based epoxy resins are further divided into glycidyl ether epoxy resins, glycidyl ester epoxy resins, and glycidylamine epoxy resins. Non-glycidyl-based epoxy resins are divided into aliphatic epoxy resins or alicyclic epoxy resins.

[0019] Preferably, the epoxy resin is selected from phenolic varnish-type epoxy resins, such as phenolic varnish-type and cresol varnish-type; bisphenol-type epoxy resins, such as bisphenol a-type and bisphenol F-type; bisphenol AD-type epoxy resins; aromatic glycidylamine-type epoxy resins, such as N,N-diglycidylaniline, N,N-diglycidyltoluidine, diaminodiphenylmethane-type glycidylamine and aminophenol-type glycidylamine epoxy resins; hydroquinone-type epoxy resins and stilbene-type epoxy resins; propane-type epoxy resins; triazine-core epoxy resins; dicyclopentadiene-modified phenolic-type epoxy resins; naphthol-type epoxy resins; and / or biphenyl skeletons; aliphatic series epoxy resins, such as alicyclic epoxy resins, such as vinylcyclohexene dioxide-type epoxy resins.

[0020] Bisphenol A epoxy resins can be selected from the following models: NPEL-127, NPEL-127E, NPEL-127H, NPEL-128, NPEL-128E, NPEL-128G, NPEL-128R, NPEL-128S, NPEL-134, NPEL-136, NPEL-231, EPICLON 840, EPICLON 840S, EXA-850CRP, EPICLON 850, EPICLON 850-LC, Araldite® GY 2600, Araldite® GY 6010, Araldite® GY 6020, Araldite® MY 790-1, Araldite® LY 1556, Tactix® 123, Araldite® GY 502, Araldite® GY 506, Araldite® GY 507, Araldite®GY508, Araldite®GY 509, Araldite®GY 512, Araldite®GY 6004, Araldite®GY 6005, Araldite®GY 9413, Araldite®GY 9513, Araldite®GY 9580, Araldite®GY 9613, Araldite®GY 9615, Araldite®GY 9667, Araldite®LY 1564, BE124A.

[0021] Bisphenol F epoxy resins can be selected from the following models: NPEF-164X, NPEF-170, NPEF-175, NPEF-176, NPEF-185, NPEF-187, NPEF-198, NPEF-500, EPICLON 830, EPICLON 830-S, EPICLON 835, EXA-830CRP, EXA-830LVP, EXA-835LV, Araldite®GY 281, Araldite®GY 282, Araldite®GY 285, Araldite®PY 306, Araldite®PY 302-2, and Araldite®PY 313.

[0022] From the perspective of the flowability and adhesion of the resin composition, as well as the heat resistance, moisture resistance, mechanical resistance, durability and electrical insulation of the cured resin composition, epoxy resin is preferred.

[0023] The epoxy resin component can be used alone or in combination of two or more. Further, the epoxy resin is selected from solid, liquid, or combinations of two of the above epoxy resins. Solid epoxy resins at room temperature can also be used in combination with liquid epoxy resins, wherein the solid epoxy resin is dissolved or dispersed in the liquid epoxy resin, provided that the mixture is preferably liquid at room temperature (25°C).

[0024] Particularly preferably, the thermosetting resin is liquid at 25°C, and each molecule has at least two epoxy groups, and more particularly preferably is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD ​​epoxy resin and naphthalene epoxy resin.

[0025] Furthermore, the curing agent can be selected from acid anhydrides, amine forms, phenolic forms, blends of acid anhydrides and phenol, blends of amines and phenol, polysulfide resins, and organic hydrazides. The acid anhydride and phenol blends are mixed in a weight ratio of 99:1 to 60:40, preferably 97:3 to 75:25. The amine and phenol blends are mixed in a weight ratio of 10:90 to 90:10, preferably 25:75 to 75:25.

[0026] The phenolic curing agent is selected from aliphatic polyamines, alicyclic amines, aromatic amines, and dicyandiamide. Aliphatic polyamines include chain-like aliphatic polyamines, alicyclic polyamines, and aliphatic aromatic amines. As specific examples, chain-like aliphatic polyamines include diethylenetriamine (DETA), triethylenetetramine (TFTA), tetraethylenepentamine (TEPA), dipropylenediamine (DPDA), diethylaminopropylamine (DEAPA), and 1,3-bis(aminomethyl)benzene (MXDA), etc. Alicyclic polyamines include N-aminoethylpiperazine (N-AEP), methanediamine (MDA), isophoronediamine (IPDA), Lamiron C-260, and Wandamin HM, etc. Aliphatic aromatic amines include m-xylenediamine (m-XDA), tertiary amine X, tertiary amine N, and tertiary amine 1001, etc. Aromatic amines include m-phenylenediamine (MPDA), diaminodiphenylmethane (DDM), diamine diphenyl sulfone (DDS), 4,4'-methylenediphenylamine, etc.

[0027] Alicyclic amines can be selected from VERSACURE® RAC 3387, VERSACURE® RAC 3391, VERSACURE® RAC 9961, VERSACURE® RAC 9963, VERSACURE® RAC 9964, VERSACURE® RAC 9965, VERSACURE® RAC 9974, VERSACURE® RAC 9978, VERSACURE® RAC 9982, VERSACURE® RAC 9983, VERSACURE® RAC 9990, VERSACURE® RAC 9991, VERSACURE® RAC 9997, AP 5618, AP5205, AP 5956, AP 5768, AP 5904, AP 5905…

[0028] Acid anhydrides include phthalic anhydride (PA), hexahydrophthalic anhydride (HHPA), and naphthalic anhydride.

[0029] Polysulfide resins include POLYTHIOL™ QE-340M, Three Bond 2104, etc.

[0030] Organic hydrazides include dihydrazide adipic acid, dihydrazide m-phenylenediamine, dihydrazide sebacate, argikul LDH, and argikul VDH.

[0031] Organic anhydride curing agents are preferred for their ability to regulate the activity and viscosity of the resin composition (meeting the requirements of the underfill / encapsulant process). Specific examples of key anhydride varieties are provided, but are not limited to: methylated hydrogenated anhydrides: methyltetrahydrophthalic anhydride (MTHPA), hexahydro-4-methylphthalic anhydride. Bridged cyclic anhydrides: intracyclic bicyclic [2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, methylintramethylenetetrahydrophthalic anhydride. Polycyclic anhydrides: bicyclic [2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic anhydride. Fluorinated anhydrides: 4,4'-(hexafluoroisopropylidene)diphthalic anhydride. Aromatic polyhydrides: benzophenone-3,3',4,4'-tetracarboxylic anhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride. Ether chain anhydrides: 4,4'-oxydiphthalic anhydride, 4,4'-(4,4'-isopropylidene diphenoxy)bis(phthalic anhydride). Special structural anhydrides: dodecenyl succinic anhydride, chlorogenic anhydride, polyazelic anhydride. Hexahydro-4-methylphthalic anhydride (HHPA) is particularly preferred, considering a comprehensive balance of curing speed, viscosity, and heat resistance.

[0032] Furthermore, the catalyst is selected from any one of Lewis acids, imidazole compounds, metal complexes, and amine complexes.

[0033] As a specific embodiment, the imidazole compound may be selected from 2-ethyl-4-methylimidazolium (2E4MZ), 4-methyl-2-phenyl-1H-imidazolium (2P4MZ), 2-phenyl-4,5-dihydroimidazolium (2PZ-L), 1-(2-cyanoethyl)-2-ethyl-4-methylmidazolium (2E4MZ-CN), 4,5-bis(hydroxymethyl)-2-phenylimidazolium (2PHZ), and 4-hydroxymethyl-5-methyl-2-phenylimidazolium. The Lewis acid is composed of boron trifluoride (BF3), zinc chloride (ZnCl2), tin chloride (IV) (SnCl4), ferric chloride (FeCl3), aluminum chloride (AlCl3), etc. The amine complex is selected from triple bond 2285B, triple bond 2287, triple bond 2287B, etc. The metal complexes are selected from platinum(II), cobalt(II), cobalt(III), nickel(II), copper(II), iron(II), iron(III), chromium(II), chromium(III), manganese(II), manganese(III), magnesium(II)...

[0034] Furthermore, the additives can be added differently depending on the desired properties of the resin composition. The additives can be selected from functional silicone resins, functional acrylate resins, coupling agents, or blends thereof. When the additive is a blend of functional silicone resins, functional acrylate resins, and coupling agents, it represents a mixture of two or more additives, without any limitation on the proportions. As long as the addition of these additives achieves the expected effect without affecting the properties of the existing resin composition, it is acceptable.

[0035] As a specific example, the coupling agent includes alkoxysilanes, silazanes, etc. Alkoxysilane coupling agents include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 7-octenyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, glycidoxypropyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, and p-styrenetrimethoxysilane. 3-Methacryloxypropylmethyldimethoxysilane, methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, methacryloxypropyltriethoxysilane, 8-methacryloxyoctyltrimethoxysilane, acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-8-aminooctyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-glycidyl etheroxypropyltrimethoxysilane, etc.

[0036] Functional silicone resins include VQM XP1773, VQM 803, VQM 806, VQM807, VQM 809, VQM881, VQM-885, EP0408, EP0409, MA0735, MA0736, AL0125, AM0265, AM0281, MS0802, MS0805, SO1455, SO1458, SQ106, SQ107, SQ109, SQ506, SQ511, SQ508, SQ510, KF-868, KF-865, KF-864, KF-859, K... F-393, KF-860, KF-880, KF-8002, KF-8004, KF-8005, KF-867, KF-8021, KF-869, KF-861, KF-877, KF-8 89. X-22-3939A, X-22-343, X-22-2000, KF-101, KF-1001, F-1005, X-22-4039, B. KF-8012, KF-8008, KF-105, X-22-163, X-22-163A, X-22-163B, X-22-163C, X-22-169AS, X-22-169B , KF-6000, KF-6001, KF-6002, KF-6003, X-22-164, X-22-164AS, X-22-164A, X-22-164B, X-22-164C, -22-164E, X-22-4952, X-22-4272, KF-6123,

[0037] The advantage of the above combinations is that they do not exhibit phase separation.

[0038] Furthermore, the resin composition provided by the present invention, wherein all components are mixed together using a three-roll mill, a bead mill, or a planetary mixer, can yield a homogeneous liquid epoxy resin composition.

[0039] Furthermore, the resin composition provided by the present invention first dissolves colloidal filler in a portion of thermosetting resin to form mixture A, then dissolves solid filler, curing agent, catalyst, and additives in the remaining thermosetting resin to form mixture B, and then pours mixture A into mixture B and stirs to obtain the resin mixture.

[0040] The resin composition provided by this invention can be used as a sealant (underfill) for flip-chip mounting or BGA (Ball Grid Array) / CSP (Chip Scale Package) mounting of electronic components such as semiconductor devices. This resin composition can also be used as an adhesive for bonding electronic components to a substrate or package. When used as a sealant, the resulting mixture can be degassed using a planetary vacuum mixer.

[0041] In flip-chip mounting or BGA / CSP mounting, the semiconductor device is first bonded to the substrate (or package). Next, a sealant is injected between the semiconductor device and the substrate; specifically, a resin composition is applied along the outer periphery of the semiconductor device, and the resin composition diffuses into the gap via capillary action.

[0042] The principle of this invention is:

[0043] Reducing the physical size of solid particles while keeping the volume ratio of solid particles in a composition or mixture constant leads to a dramatic increase in the number of particles. This increased number causes particles to move closer together, significantly enhancing their interactions (collisions, attraction / repulsion, etc.). This effect is particularly pronounced when particle sizes are less than 1 micrometer. Furthermore, the presence of surface charge layers, water molecule layers, or adsorbed molecule layers significantly increases the actual size (effective hydrodynamic size) of these small particles as they move in the liquid, further exacerbating interparticle interactions and the complexity of the entire system (e.g., making the composition or mixture more viscous and less fluid).

[0044] When the size of particles suspended in a material increases, the overall viscosity of the material increases only slightly. This is because for large particles, the increase in "effective size" due to surface charge, water molecule layers, or adsorbed molecule layers is negligible relative to the already large physical size of the particles. However, when the material is slowly agitated or flowed (at low shear rates), strong interparticle forces (colloidal forces) can develop. These interparticle forces are the main factors that truly impede flow and increase viscosity. Therefore, although the increase in particle size itself has a small direct effect on viscosity, under these low-speed flow conditions, the minute viscosity changes caused by the increase in particle size (and possibly other accompanying factors) are amplified and become noticeable through enhanced interparticle interactions.

[0045] Particles with a wide size distribution (high polydispersity) exhibit superior packing structure compared to particles of a single size (narrow distribution). In a wide-distribution system, individual particles have greater free movement space, significantly improving sample flowability and consequently reducing system viscosity. Therefore, narrowing the particle size distribution can simultaneously improve the viscosity and stability of the suspension.

[0046] When the volume fraction is constant, a sample composed of larger particles and a small number of smaller particles will have a lower viscosity than a system with either a single particle size or a system with large or small particles. This is essentially due to a dual mechanism: on the one hand, interparticle interactions increase with decreasing particle size, leading to an increase in viscosity; on the other hand, other factors triggered by increased polydispersity reduce viscosity. In this specific system, the introduction of small particles significantly reduces viscosity, making the viscosity-reducing effect of polydispersity more pronounced.

[0047] Therefore, mixing fillers of different particle sizes (especially nano-sized fillers) can maintain their flowability and permeability without excessively increasing the viscosity of the underfill. However, as... Figure 2 As shown in Figure A, filler 2 is prone to agglomeration due to its extremely small particle size (nanoscale), making it difficult to uniformly disperse with filler 1 in thermosetting resin 1 during preparation. Besides agglomeration, it also significantly increases the overall viscosity of the system and worsens its flowability. Due to the sharp increase in viscosity and deterioration in flowability, the amount of bottom filler must be reduced, leading to a decrease in its moisture resistance and temperature resistance.

[0048] In the technical solution protected in this application, such as Figure 2 As shown in Figure B, the nano-sized filler 2 (colloidal inorganic filler) has been pre-dispersed uniformly in the liquid phase system. When larger-diameter filler 1 (micrometer-scale) is further mixed in, the nanoparticles can quickly fill the gaps between large particles and are less prone to aggregation. Therefore, compared to other methods... Figure 2 A. Underfill adhesives prepared using colloidal inorganic fillers have lower viscosity and better flowability at the same filler content.

[0049] Based on the low viscosity of this colloidal filler system, the filling amount of the bottom filler can be further increased, thereby giving the product excellent moisture resistance and temperature resistance.

[0050] The significant advantages of this invention compared to existing technologies are:

[0051] The resin composition formulated with this colloidal filler has a lower viscosity, which means that the filler loading in the resin composition (bottom filler) can be further increased, resulting in excellent moisture resistance and better temperature resistance. Furthermore, due to the increased filler loading, the CTE of the cured resin composition should be reduced, thereby improving the reliability of the cured resin mixture. Attached Figure Description

[0052] Figure 1 This is a schematic diagram of a liquid flowability evaluation method according to an embodiment of the present invention.

[0053] Figure 2 This is a schematic diagram illustrating the principle of the present invention.

[0054] The components are: 1. substrate, 2. glass plate, 3. gap filler, and 4. resin composition. Detailed Implementation

[0055] The embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0056] Example 1

[0057] A resin composition for sealing electronic devices comprises the following components in the following mass percentages: epoxy resin selected from bisphenol A type BE124A 16.5%, curing agent selected from hexahydrophthalic anhydride HHPA 19.9%, catalyst selected from 2-ethyl-4-methylimidazolium 2E4MZ 0.4%, additive 3-glycidyl etheroxypropyltrimethoxysilane GLYMO 1.6%, colloidal filler selected from colloidal silica (particle size 10~20 nm) EVONP-470 8.5%, and solid filler selected from spherical silica microparticles (average particle size 0.5 μm) ANAD-E22 53.1%. The above mixture is kneaded using a three-roll mill until homogeneous, and then degassed using a planetary vacuum mixer to obtain the final product.

[0058] Example 2

[0059] The resin composition was formulated and prepared according to Example 1, except that the solid filler was selected from spherical silica micropowder (average particle size 0.5 μm) EM-DCS-005 53.1%.

[0060] Example 3

[0061] The resin composition was formulated and prepared according to Example 1, except that the solid filler was selected from spherical silica micropowder (average particle size 2.0 μm) EM-SQB-2020 53.1%.

[0062] Example 4

[0063] The resin composition was formulated and prepared according to Example 1, except that the solid filler was selected from spherical silica micropowder (average particle size 4.0 μm) EM-SQL-1028 53.1%.

[0064] Comparative Example 1

[0065] A resin composition comprising the following components in the following mass percentages: epoxy resin selected from bisphenol A type BE124A2 0.1%, curing agent selected from hexahydrophthalic anhydride HHPA 21.1%, catalyst selected from 2-ethyl-4-methylimidazolium 2E4MZ 0.4%, additive 3-glycidyl etheroxypropyltrimethoxysilane GLYMO 1.7%, and solid filler selected from spherical silica powder (average particle size 0.5 μm) ANAD-E22 53.2% and spherical silica powder (average particle size 8.0 nm) EM-BCF-007 3.5%. The above mixture is kneaded using a three-roll mill, and after homogenization, the resulting mixture is degassed using a planetary vacuum mixer to obtain the final product.

[0066] Comparative Example 2

[0067] The resin composition was formulated and prepared according to Comparative Example 1, except that the solid filler was selected from 53.2% of spherical silica powder (average particle size 0.5 μm) EM-DCS-005 and 3.5% of spherical silica powder (average particle size 8.0 nm) EM-BCF-007.

[0068] Comparative Example 3

[0069] The resin composition was formulated and prepared according to Comparative Example 1, except that the solid filler was selected from 53.2% of spherical silica powder (average particle size 2.0 μm) EM-SQB-2020 and 3.5% of spherical silica powder (average particle size 8.0 nm) EM-BCF-007.

[0070] Comparative Example 4

[0071] The resin composition was formulated and prepared according to Comparative Example 1, except that the solid filler was selected from 53.2% of spherical silica powder (average particle size 4.0 μm) EM-SQL-1028 and 3.5% of spherical silica powder (average particle size 8.0 nm) EM-BCF-007.

[0072] The ingredients used above were purchased from the following suppliers:

[0073] 1: Bisphenol A type epoxy resin BE124A (Manufacturer: Changchun Artificial Resin Factory Co., Ltd.)

[0074] 2: Hexahydrophthalic anhydride (HHPA) (Manufacturer: Merck)

[0075] 3: 2-Ethyl-4-methylimidazolium 2E4MZ (Manufacturer: Merck, Germany)

[0076] 4: 3-Glycidyl etheroxypropyltrimethoxysilane GLYMO (Manufacturer: Merck, Germany)

[0077] 5: Colloidal filler (particle size 10~20 nm) EVONP-470 (Supplier: Yu Rong Trading Co., Ltd.)

[0078] 6: Spherical silica micropowder ANAD-E22 (average particle size: 0.5 μm) (Supplier: Yuanhong Technology Co., Ltd.)

[0079] 7: Spherical silica micropowder EM-SQB-2020 (average particle size 2.0 μm) (Supplier: WellionTrade Company)

[0080] 8: Spherical silica micropowder EM-SQL-1028 (average particle size 4.0 μm) (Supplier: WellionTrade Company)

[0081] 9: Spherical silica micropowder EM-DCS-005 (average particle size 0.5 μm) (Supplier: WellionTrade Company)

[0082] 10: Spherical silica micropowder EM-BCF-007 (average particle size 8.0 nm) (Supplier: WellionTrade Company)

[0083] The group allocation ratios are shown in Table 1:

[0084] Table 1

[0085]

[0086] The resin composition prepared above was subjected to viscosity and flow property tests, as detailed below:

[0087] 1. Viscosity Measurement: Viscosity was measured using a BROOKFIELD DV-1 viscometer equipped with an ASTM standard, at 25°C.

[0088] 2. Liquidity testing: such as Figure 1 As shown, the liquid flowability evaluation method includes the following steps: First, as... Figure 1 As shown in Figure A, a test carrier is fabricated: a gap of 30 μm or 60 μm is formed on a substrate 1, and a glass plate 2 is fixed to it instead of a semiconductor element. However, as the substrate 1, a glass substrate is used instead of a flexible substrate; as shown in Figure A. Figure 1 As shown in Figure B, the test carrier is placed on a heating plate at a temperature of 70°C, and the prepared resin compositions of Examples 1-4 and Comparative Examples 1-4 are applied to one end of glass plate 2. Figure 1 As shown in C, the distance and time of the resin composition 4 filling the gap 3 were measured, and the results are shown in Table 2.

[0089] Table 2

[0090]

[0091] Note: In Table 2, 30 μm Gap / 2cm / 9min: means that at a 30 μm Gap, it takes 9 minutes of flow time to complete a 2cm flow distance. 30 μm Gap / 0.4cm / >30min: means that at a 30 μm Gap, even if the flow time exceeds 30 minutes, the flow distance is only 0.4cm. 60 μm Gap: 0.5cm / Time: >30min: means that at a 60 μm Gap, even after 30 minutes of flow, it only fills a 0.5cm distance. 30 μm Gap: 0cm / Time: >30min: means that at a 30 μm Gap, despite 30 minutes of flow, it cannot flow at all (0cm). 60 μm Gap: 0cm / Time: >30min: means that at a 60 μm Gap, despite 30 minutes of flow, it cannot flow at all (0cm).

[0092] As can be seen from the experimental results in Table 2 (Comparative Examples 1-4), if nanoparticles (EM-BCF-007, particle size: 8.0 nm) are directly added to the powder / solid formulation, the viscosity of the formulation increases significantly due to severe agglomeration, making it impossible to produce a uniformly dispersed resin composition. In contrast, by adding colloidal particles (EVONP-470, particle size: 10-20 nm), a uniformly dispersed resin composition can be formed. The epoxy resin composition formed by this method does not show a significant increase in viscosity and exhibits excellent flowability in narrow gaps (30 μm).

[0093] It should be noted that the silica filler in Examples 1 and 2 both have a particle size of 0.5 μm (generally, the particle size of the filler is determined by D50). However, due to differences in particle size distribution and surface treatment, different filler products may result in significant differences in the viscosity of the bottom filler. In Comparative Examples 1-4, solid SiO2 was used as the filler. Without the addition of colloidal filler, it could not be uniformly dispersed in the epoxy resin BE124A, causing the entire mixture to form viscous lumps, making it impossible to measure the viscosity.

Claims

1. A resin composition for sealing electronic devices, characterized in that: The resin composition comprises, by weight percentage: 10-30% thermosetting resin, 15-35% curing agent, 0.1-3% catalyst, 0.8-5% additives, 5-20% colloidal filler and 45-68% solid filler; The thermosetting resin is selected from epoxy resin, and the thermosetting resin is liquid at 25°C; The solid filler is selected from silicon dioxide, aluminum oxide, boron nitride, aluminum nitride, or any combination of silicon dioxide, aluminum oxide, boron nitride, and aluminum nitride; the particle size of the solid filler is 0.010 μm ≤ 10 μm; The colloidal filler is selected from Nanobox A410, Nanobox A510, Nanobox A611, Nanobox E430, Nanobox E470, Nanobox E500, Nanobox E601, Nanobox F400, Nanobox F440, Nanobox F520, Nanobox F631, EVONP-470, LUDOX® HS-30, 406 colloidal silica, AEROSIL® Colloidal Silica, AEROPERL® Collidal Silica, AMSol™ 8 SM, AMSol™ 8 SMX, AMSol™ 15, AMSol™ 15 SM, AMSol™ 20 SM, AMSol™ 30, AMSol™ 30 SM, AMSol™ 4012, AMSol™ 4015, AMSol™ 50, and AMSol™ HT.

2. The resin composition according to claim 1, characterized in that: The curing agent can be selected from acid anhydrides, amine types, phenol types, blends of acid anhydrides and phenol, blends of amines and phenol, polysulfide resins, and organic hydrazides.

3. The resin composition according to claim 1, characterized in that: The catalyst is selected from any one of Lewis acids, imidazole compounds, metal complexes, and amine complexes; the additive is selected from functional organosilicon resins, functional acrylate resins, coupling agents, or blends thereof.

4. A semiconductor sealant, characterized in that: The semiconductor sealant uses the resin composition according to any one of claims 1 to 3.

5. A semiconductor device, characterized in that: The semiconductor device uses the semiconductor sealant as described in claim 4.

Images