A kind of low-melting-point metal micro-nano powder conducting resinl and preparation method thereofTechnical field
The invention belongs to technical field of integrated circuits, and in particular to a kind of chip encapsulation material and preparation method thereof.
Background technique
Currently, the material of substitution Sn-Pb solder has two classes, lead-free brazing and conducting resinl both at home and abroad.Most have in lead-free brazingThe brazing temperature ratio Sn-Pb solder of Sn-Ag, Sn-Ag-Cu brazing filler metal of application prospect is higher by 40 DEG C or so, most of welding memberThe all unbearable such temperature of device, the use of lead-free brazing greatly reduce the reliability of electronic component.In addition, Sn-The solders such as Bi, Sn-In are then since the factors such as ingredient is rare, selling at exorbitant prices limit application.
Conducting resinl is a kind of adhesive solidified or have certain electric conductivity after dry, it usually with matrix resin and leadsElectric filler, that is, conducting particles is main constituents, and conducting particles is combined together to form by the bonding effect of matrix resinConductive path realizes the conductive connection for being glued material.
The most popular conducting resinl of tradition mainly uses silver powder and copper powder as conductive filler.Silver powder has good conductionProperty, it is widely used since its oxide also has certain electric conductivity, silver powder or silver coating material as conductive filler,Some fields for requiring conducting resinl to have excellent conductive performance generally use sliver-powder conducting glue, but sliver-powder conducting glue is in wet environmentIn be easy to happen ELECTROMIGRATION PHENOMENON, reduce the reliability of conducting resinl.And the higher cost of sliver-powder conducting glue, sedimentation stability compared withDifference；Copper powder has preferable electric conductivity, and cost is significantly less than silver powder, but copper system conducting resinl is easy to oxidize, and electric conductivity is big after oxidationIt is big to reduce, or even conductive path cannot be formed, copper system conducting resinl after decades of development, has achieved significant progress, butThe problem of unstability is still long-term existence.Such as limited impact resistance, long-term mechanicalness and conductive stable etc. makeConducting resinl is not received widely still instead of welding in electronics industry.
To solve the problems, such as to exist in this respect, the present invention proposes a kind of low-melting-point metal micro-nano powder conducting resinl, utilizesLow melting point, high conductivity metal powder with low melting point mixed with silver powder as conductive filler, have the advantage that (1) low melting pointCharacteristic can guarantee preferably to be combined with silver powder in the curing process and contact with each other to form line or face access, reduce metalThe formation in gap between grain；(2) in the dosage of the reduction noble metal silver powder of the electric conductivity guaranteed, it can be greatly reduced and be produced intoThis；(3) mechanical performance that low-melting-point metal has had improves conducting resinl tensile shear strength, adaptability enhancing after solidification.
Summary of the invention
The first purpose of this invention is to solve traditional Sn-Pb solder, lead-free solder welding temperature height, thermal stressGreatly, the disadvantages of energy consumption is high, harmful to environment, while overcoming currently on the market that conductive silver glue is thermally conductive, adhesive property is poor, volume is electricThe disadvantages of resistance rate is big, complex process, at high cost, therefore propose a kind of low-melting-point metal micro-nano powder conducting resinl.
Second object of the present invention is to propose the preparation method of the low-melting-point metal micro-nano powder conducting resinl.
Third object of the present invention is to propose the application of the low-melting-point metal micro-nano powder conducting resinl.
The purpose of the present invention is achieved through the following technical solutions:
A kind of low-melting-point metal micro-nano powder conducting resinl includes conductive filler 50%-90% and matrix tree in mass ratioRouge 10%-50%；Wherein, the conductive filler includes following component in mass ratio: low-melting-point metal micro-nano powder 50%-90%, silver powder 10-50%.
Wherein, described matrix resin includes following component by mass parts: 100 parts of resin, 10-20 parts of curing agent, and promotor0.5-1.5 parts, 0.5-3 parts of coupling agent, 8-18 parts of diluent, 0.5-1 parts of defoaming agent, 0.1-0.8 parts of antioxidant.
Wherein, the resin is polybutadiene, polyvinyl alcohol resin, polyvinylpyrrolidone, bisphenol type epoxyResin, polybutadiene, Kynoar, polystyrene, polytetrafluoroethylene (PTFE), epoxy resin, gathers bisphenol f type epoxy resinAcrylic resin, polyester resin, alkyd resin, polyurethane, silicone resin, organosilicon acrylic resin, vinyl chloride-vinyl acetate resin, phenolic resin, polyamideOne of resin, aldehyde ketone resin, celluosic resin, fluorocarbon resin, vinylite, Arabic gum are a variety of.
Wherein, the curing agent is polysulfide alcohol type, isocyanate-based, triethanolamine, 2-ethyl-4-methylimidazole, firstBase hexahydrophthalic anhydride, methyl T-31 modified amine, YH-82 modified amine, aliphatic polyamine, alicyclic polyamine, polyamide, 2- undecylOne of imidazoles, aromatic polyamine, acid anhydrides, phenolic resin, amino resins, dicyandiamide, hydrazides are a variety of；
The promotor be triethylamine, imidazoles, DMP-30, EP-184, BDMA, CT-152X, DBU, EP-184,399,One of K-61B, CT-152X, 2E4MZ or a variety of.
Wherein, the coupling agent is vinyltriethoxysilane, vinyltrimethoxysilane, (the β alkene of vinyl threeMethoxy ethoxy) silane, titanate esters, Aluminate, tri- mercaptopropyltriethoxysilane of γ, in 3- aminopropyl triethoxysilaneIt is one or more；
The diluent be alkylidene glycidol ether, butyl glycidyl ether, 1,4- butanediol diglycidyl ether,Ethylene glycol diglycidylether, phenyl glycidyl ether, polypropylene glycol diglycidyl ether, C12-14 fatty glycidyl ether,One or more of benzyl glycidyl ether, 1,6- hexanediol diglycidyl ether.
Wherein, the defoaming agent is silicone emulsion, the fatty acid ester compounded object of higher alcohols, polyoxyethylene polyoxypropylene season pentaFour alcohol ethers, polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether and polyoxyethylene polyoxypropylene glycerin ether, poly dimethyl siliconOne of oxygen alkane, phosphate defoaming agent are a variety of；
The antioxidant is IRGANOX1010, IRGANOX245, IRGANOX1726, UV1130, the tertiary fourth of 3,5- bis-Base -4- hydroxy propionate, HHY-534 amine type antioxidant, phosphorous acid three (2.4- di-tert-butyl-phenyl) ester, 2.6- di-tert-butylOne of phenol is a variety of.
Wherein, it is elemental metals, bianry alloy, three that the low-melting-point metal micro-nano powder, which is selected from the low-melting-point metal,One of first alloy, quaternary alloy, multicomponent alloy are a variety of, and the elemental metals are selected from one of tin, indium, zinc, bismuth, aluminiumOr two kinds；The bianry alloy is selected from tin bismuth, tin indium, tin zinc, tin aluminium, indium bismuth, indium zinc, indium aluminium, zinc bismuth, zinc-aluminium, bismuth aluminium, tinOne of silver, tin copper binary alloy；The ternary alloy three-partalloy be selected from bismuth indium tin, bismuth indium zinc, bismuth indium aluminium, bismuth tin zinc, bismuth tin aluminium,One of bismuth zinc-aluminium, indium tin zinc, indium tin aluminium, indium zinc-aluminium, Tin-zinc-aluminium, tin bismuth silver, tin bismuth copper, tin silver copper ternary alloy three-partalloy are moreKind；The quaternary alloy is selected from bismuth indium tin zinc, bismuth indium tin aluminium, bismuth indium zinc-aluminium, bismuth Tin-zinc-aluminium, indium Tin-zinc-aluminium, tin bismuth copper silver fourOne of first alloy；The multicomponent alloy be by one of tin, indium, zinc, bismuth, aluminium, silver, copper, nickel or it is a variety of with it is describedOne of the middle low temperature multicomponent alloy that one of bianry alloy, ternary alloy three-partalloy, quaternary alloy are formulated.
The particle size of the low-melting-point metal micro-nano powder is 1 nanometer -25 microns.
Preferably, the conductive filler is by tin, indium, silver, tin indium, bismuth indium tin, tin silver copper, Tin-zinc-aluminium, tin bismuth copper silverMicro-nano powder 60:(1-2 in mass ratio): (10-20): (8-12): (3-6): (8-12): (1-3): (1-2) be sufficiently mixed andAt.
The preparation method of the low-melting-point metal micro-nano powder conducting resinl, comprising steps of
1) resin, curing agent, promotor, coupling agent, diluent, defoaming agent, antioxidant are weighed according to the proportion,What is be thoroughly mixed obtains matrix resin；The agitating mode is hand operated mixing and/or magnetic agitation；
2) low-melting-point metal micro-nano powder, silver powder, other conductive fillers are weighed, the powder hand operated mixing is sufficiently mixedIt closes, as conductive filler；
3) conductive filler in step 2) is added in the uniform matrix resin in step 1), is sufficiently mixed using rolling equipmentRolling is until form paste, as low-melting-point metal micro-nano powder conducting resinl.
Preferably, the equipment of the rolling is three-roll grinder or planetary ball mill.
Application of the low-melting-point metal micro-nano powder conducting resinl in chip package.
The beneficial effects of the present invention are:
(1) compared with Pd-Sn alloy, lead-free solder, this conducting resinl has environmental-friendly, low-temperature bonding, adhesive force good, thinLine printing capability is strong, can be used for flexible circuit connection；(2) with currently on the market conductive silver glue, compared with copper glue, this conducting resinl toolHave the advantages that good heat conductivity, volume resistivity are small, adhesive strength is high, simple process, while preparation method is simple, is easy to graspMake, cost is far below conductive silver glue.
Detailed description of the invention
Fig. 1: the preparation method flow chart of low-melting-point metal micro-nano powder conducting resinl of the present invention.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiments of the present invention will be described in further detail.Implement belowExample is not intended to limit the scope of the invention for illustrating the present invention.
In embodiment, tin, indium, silver, tin indium powder are sheet or dendroid, and partial size is 1 nanometer -8 microns；Bismuth indium tin, tinSilver-bearing copper, Tin-zinc-aluminium, tin bismuth copper silver powder be it is spherical, particle size be 5 microns -25 microns.The conductive filler is by tin, indium, silver, tinIndium, bismuth indium tin, tin silver copper, Tin-zinc-aluminium, tin bismuth copper silver micro-nano powder 60:1:15:10:5:10:2:2 in mass ratio are abundant manuallyIt is stirred, mixing time 10-20min.
Conductive filler mixing has the advantage that the conductive path for increasing metal powder in conducting resinl, significant dropLow conducting resinl volume resistivity；By the way that the alloy powder of ternary is added, the antioxygenic property of conducting resinl is significantly improved, is extended conductiveThe service life of glue.
Embodiment 1
The present invention provides a kind of low-melting-point metal micro-nano powder conducting resinl, in mass ratio by 30% matrix resin and70% conductive filler composition.Wherein matrix resin is by bisphenol f type epoxy resin, tertiary amines triethanolamine, 2- ethyl -4- methyl miaowAzoles, 3- aminopropyl triethoxysilane, carbon 12-14 alkyl glycidyl ether, phosphate defoaming agent, IRGANOX1726 press qualityIt is mixed than 100:16:1.2:2:10:0.8:0.5；Conductive filler is tin, indium, silver, tin indium, bismuth indium tin, tin silver copper, tin zincAluminium, tin bismuth copper silver micro-nano powder 60:1:15:10:5:10:2:2 in mass ratio are prepared by fully mixing.
A kind of low-melting-point metal micro-nano powder conducting resinl preparation method, preparation method flow chart such as Fig. 1.It is madeIt is standby that steps are as follows:
1) epoxy resin, curing agent, promotor, coupling agent, diluent, defoaming agent, antioxygen are weighed according to the proportionAgent, what is be thoroughly mixed obtains matrix resin；
2) low-melting-point metal micro-nano powder, silver powder, other conductive fillers are weighed, the powder hand operated mixing is sufficiently mixedIt closes, as conductive filler；
3) conductive filler in step 2) is added in the uniform matrix resin in step 1), is sufficiently mixed using rolling equipmentRolling is until form paste, as low-melting-point metal micro-nano powder conducting resinl.
Embodiment 2:
The present invention provides a kind of low-melting-point metal micro-nano powder conducting resinl, in mass ratio by 25% matrix resin and75% conductive filler composition.Wherein matrix resin is by bisphenol f type epoxy resin, tertiary amines triethanolamine, 2- ethyl -4- methyl miaowAzoles, 3- aminopropyl triethoxysilane, carbon 12-14 alkyl glycidyl ether, phosphate defoaming agent, IRGANOX1726 press qualityIt is mixed than 100:16:1.2:2:10:0.8:0.5；Conductive filler is tin, indium, silver, tin indium, bismuth indium tin, tin silver copper, tin zincAluminium, tin bismuth copper silver micro-nano powder 60:1:15:10:5:10:2:2 in mass ratio are prepared by fully mixing.
A kind of low-melting-point metal micro-nano powder conducting resinl preparation method, preparation method flow chart such as Fig. 1.It is madeIt is standby that steps are as follows:
1) resin, curing agent, promotor, coupling agent, diluent, defoaming agent, antioxidant are weighed according to the proportion,What is be thoroughly mixed obtains matrix resin；
2) low-melting-point metal micro-nano powder, silver powder, other conductive fillers are weighed, the powder hand operated mixing is sufficiently mixedIt closes, as conductive filler；
3) conductive filler in step 2) is added in the uniform matrix resin in step 1), is sufficiently mixed using rolling equipmentRolling is until form paste, as low-melting-point metal micro-nano powder conducting resinl.
Embodiment 3:
The present invention provides a kind of low-melting-point metal micro-nano powder conducting resinl, in mass ratio by 20% matrix resin and80% conductive filler composition.Wherein matrix resin is by bisphenol f type epoxy resin, tertiary amines triethanolamine, 2- ethyl -4- methyl miaowAzoles, 3- aminopropyl triethoxysilane, carbon 12-14 alkyl glycidyl ether, phosphate defoaming agent, IRGANOX1726 press qualityIt is mixed than 100:16:1.2:2:10:0.8:0.5；Conductive filler is tin, indium, silver, tin indium, bismuth indium tin, tin silver copper, tin zincAluminium, tin bismuth copper silver micro-nano powder 60:1:15:10:5:10:2:2 in mass ratio are prepared by fully mixing.
A kind of low-melting-point metal micro-nano powder conducting resinl preparation method, preparation method flow chart such as Fig. 1.It is madeIt is standby that steps are as follows:
1) resin, curing agent, promotor, coupling agent, diluent, defoaming agent, antioxidant are weighed according to the proportion,What is be thoroughly mixed obtains matrix resin；
2) low-melting-point metal micro-nano powder, silver powder, other conductive fillers are weighed, the powder hand operated mixing is sufficiently mixedIt closes, as conductive filler；
3) conductive filler in step 2) is added in the uniform matrix resin in step 1), is sufficiently mixed using rolling equipmentRolling is until form paste, as low-melting-point metal micro-nano powder conducting resinl.
Embodiment 4:
The present invention provides a kind of low-melting-point metal micro-nano powder conducting resinl, in mass ratio by 15% matrix resin and85% conductive filler composition.Wherein matrix resin is by bisphenol f type epoxy resin, tertiary amines triethanolamine, 2- ethyl -4- methyl miaowAzoles, 3- aminopropyl triethoxysilane, carbon 12-14 alkyl glycidyl ether, phosphate defoaming agent, IRGANOX1726 press qualityIt is mixed than 100:16:1.2:2:10:0.8:0.5；Conductive filler is tin, indium, silver, tin indium, bismuth indium tin, tin silver copper, tin zincAluminium, tin bismuth copper silver micro-nano powder 60:1:15:10:5:10:2:2 in mass ratio are prepared by fully mixing.
A kind of low-melting-point metal micro-nano powder conducting resinl preparation method, preparation method flow chart such as Fig. 1.It is madeIt is standby that steps are as follows:
1) resin, curing agent, promotor, coupling agent, diluent, defoaming agent, antioxidant are weighed according to the proportion,What is be thoroughly mixed obtains matrix resin；
2) low-melting-point metal micro-nano powder, silver powder, other conductive fillers are weighed, the powder hand operated mixing is sufficiently mixedIt closes, as conductive filler；
3) conductive filler in step 2) is added in the uniform matrix resin in step 1), is sufficiently mixed using rolling equipmentRolling is until form paste, as low-melting-point metal micro-nano powder conducting resinl.
Embodiment 5:
The present invention provides a kind of low-melting-point metal micro-nano powder conducting resinl, in mass ratio by 10% matrix resin and90% conductive filler composition.Wherein matrix resin is by bisphenol f type epoxy resin, tertiary amines triethanolamine, 2- ethyl -4- methyl miaowAzoles, 3- aminopropyl triethoxysilane, carbon 12-14 alkyl glycidyl ether, phosphate defoaming agent, IRGANOX1726 press qualityIt is mixed than 100:16:1.2:2:10:0.8:0.5；Conductive filler is tin, indium, silver, tin indium, bismuth indium tin, tin silver copper, tin zincAluminium, tin bismuth copper silver micro-nano powder 60:1:15:10:5:10:2:2 in mass ratio are prepared by fully mixing.
A kind of low-melting-point metal micro-nano powder conducting resinl preparation method, preparation method flow chart such as Fig. 1.It is madeIt is standby that steps are as follows:
1) resin, curing agent, promotor, coupling agent, diluent, defoaming agent, antioxidant are weighed according to the proportion,What is be thoroughly mixed obtains matrix resin；
2) low-melting-point metal micro-nano powder, silver powder, other conductive fillers are weighed, the powder hand operated mixing is sufficiently mixedIt closes, as conductive filler；
3) conductive filler in step 2) is added in the uniform matrix resin in step 1), is sufficiently mixed using rolling equipmentRolling is until form paste, as low-melting-point metal micro-nano powder conducting resinl.
In above-described embodiment, from example 1 to example 5, conductive filler content rises to 90% from 70%, conducting resinl electric conductivityIt is promoted.It can also be adjusted between 50% to 90% according to actual needs.The conducting resinl of embodiment 1-5 preparation is tested.ItsThe results are shown in Table 1.
Table 1: conducting resinl test performance parameter
Finally it should be noted that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referencePreferred embodiment describes the invention in detail, it will be appreciated by those skilled in the art that can be to technical side of the inventionCase is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be covered in this hairIn bright scope of the claims.