CN115011294B - Sintered nano silver conductive adhesive for chip packaging and preparation method thereof - Google Patents
Sintered nano silver conductive adhesive for chip packaging and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a sintered nano silver conductive adhesive for chip packaging and a preparation method thereof; in order to enhance the conductivity of the conductive adhesive, the conductive filler compounded by the nano silver wires and the nano silver particles is prepared, and a conductive network is formed by lapping the nano silver wires in the conductive adhesive by utilizing the one-dimensional structure of the nano silver wires, so that the transmission of electrons is facilitated; meanwhile, in order to enhance the fluidity of the epoxy resin and improve the distribution of the nano silver, the hyperbranched epoxy resin is synthesized to be used as a resin matrix, the dispersion of the nano silver is assisted by virtue of the spherical structure and numerous branches of the hyperbranched compound, and meanwhile, because the hyperbranched epoxy resin has high fluidity, the addition of a diluent can be avoided, and the influence on the function of the conductive agent caused by the cavity of the conductive adhesive due to the volatilization and decomposition of the diluent in the curing process is prevented. The conductive adhesive prepared by the invention has excellent performance, good thermal conductivity and lower volume resistivity, can be applied to a plurality of precise lines, has good flexibility and low void ratio, and has a wide market.
Description
Technical Field
The invention relates to the technical field of chip packaging, in particular to a sintered nano silver conductive adhesive for chip packaging and a preparation method thereof.
Background
The conductive adhesive is a conductive adhesive, can replace tin-lead solder to be used as one of electronic assembly solders after being cured or dried, and is used for mechanically and electrically communicating a circuit. The existing conductive adhesive generally comprises conductive filler and a resin matrix, wherein the resin matrix wraps the conductive filler dispersed in the resin matrix to form a whole, and the conductive filler achieves the purpose of transmitting electrons by mutual contact or seepage. However, in order to uniformly disperse the conductive filler into the resin matrix during the preparation of the conventional conductive adhesive, a diluent is often added into the resin to adjust the viscosity of the resin system. When the resin matrix is cured, the diluents are decomposed and volatilized along with the rise of the temperature, and finally more micro cavities are generated in the conductive adhesive, and at the moment, the resin matrix is cured and cannot fill the gaps, so that the contact distance of the conductive filler is increased, and the conductive capacity of the conductive filler is greatly reduced.
Disclosure of Invention
The invention aims to provide a sintered nano silver conductive adhesive for chip packaging and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the sintered nano silver conductive adhesive for chip packaging has the following characteristics: the sintered nano silver conductive adhesive comprises the following components in parts by weight: 45-55 parts of nano silver particles, 15-20 parts of nano silver wires, 15-45 parts of hyperbranched epoxy resin matrix, 12-40 parts of curing agent and 0.3-0.5 part of curing accelerator;
the hyperbranched epoxy resin matrix is mixed resin of epoxy resin E51 and hyperbranched epoxy resin, wherein the weight ratio of the epoxy resin E51 to the hyperbranched epoxy resin is (2-3): (4-8).
Further, the curing agent is phthalic anhydride; the curing accelerator is 2-ethyl-4-methylimidazole.
A preparation method of sintered nano silver conductive adhesive for chip packaging comprises the following steps:
s1, preparing a nano silver wire;
s2, preparing nano silver particles;
s3, preparing hyperbranched epoxy resin;
s31, mixing 4-hydroxybenzoic acid and 1-1.5 parts of polyethylene glycol glycidyl ether in parts by mole and mixing with N, N-dimethylformamide, uniformly stirring, adding 0.05-0.1 part of catalyst, introducing nitrogen, and raising the temperature to 80-90 ℃ in an oil bath to react for 8-12 hours;
s32, after the reaction is finished, performing rotary evaporation to remove the redundant solvent, washing the reaction product for 3-5 times by using a saturated NaCl solution and saturated NaHCO3, and then performing rotary evaporation to remove the redundant water solvent until the quality of the product is not changed any more;
s33, dissolving trimethylolpropane triglycidyl ether and a catalyst in N, N-dimethylformamide, stirring and mixing, adding the rotary evaporation product prepared in the step S32, introducing nitrogen, heating in an oil bath to 90-120 ℃, and reacting for 8-12h;
s34, after the reaction is finished, performing rotary evaporation for 3-4 hours to remove unreacted solvent, adding tetrahydrofuran with the volume 2-3 times that of the residual product, stirring and mixing, washing for 2-3 times by using pure water and diethyl ether, performing suction filtration, and drying the suction filtration product to obtain hyperbranched epoxy resin;
s4, placing the nano silver wires and the nano silver particles prepared in the steps S1 and S2 in a silane coupling agent, performing dispersion treatment for 2-3h by using 15-20KHz ultrasonic waves, and performing centrifugal separation to obtain modified nano silver wires and modified nano silver particles;
s5, mixing the modified nano silver wires, the nano silver particles and the hyperbranched epoxy resin, stirring and dispersing at the speed of 200-300rpm for 0.5-1h, adding the epoxy resin and the curing agent, continuously stirring for 0.5h, adding the curing accelerator, and continuously stirring until the materials are uniformly mixed.
The invention firstly limits the composition of the conductive filler, and uses the silver nanoparticles and the silver nanowires to carry out compounding, so that the unique one-dimensional structure of the silver nanowires in the resin matrix can achieve the purpose of conductivity in a longer distance. The method comprises the steps of synthesizing a nano silver wire by using a polyol method, using the polyol as a reducing agent, reducing silver ions under a heating condition, using polyvinylpyrrolidone as a polymer dispersing agent in a reaction process, wherein in the process of generating the nano silver wire, carbonyl in polyvinylpyrrolidone molecules can be preferentially combined with certain crystal faces of silver due to lone pair electrons, and electric balance is maintained, so that the growth of the silver in the crystal face direction is prevented, and the silver grows into a nano wire with a one-dimensional linear structure. In the resin matrix, the nano silver wires are mutually lapped to form a conductive network, and a plurality of nano silver particles which cannot conduct electricity are lapped, so that the conductivity of the conductive adhesive is enhanced, and the resistivity is reduced.
During curing, the epoxy resin is usually cured and shrunk, so that the conductive filler is pressed and is enabled to be contacted more tightly, but due to the addition of the diluent component, the volatilization and decomposition of the diluent component can occur together with the curing and shrinkage in the curing process, and in the process, the cavity in the conductive adhesive caused by the volatilization of the diluent is far larger than the influence caused by the shrinkage and curing of the epoxy resin, so that the cavity rate in the conductive adhesive is increased, and the resistance is increased. The hyperbranched epoxy resin prepared by the method is nearly spherical, has small intermolecular entanglement and good fluidity, can effectively improve the distribution performance of conductive particles in a resin matrix, has numerous branched groups, and can be crosslinked with nano silver particles after surface treatment to prevent the nano silver particles from settling.
In addition, when the hyperbranched epoxy resin is prepared, polyethylene glycol glycidyl ether with ether bonds is used as a raw material, the raw material is mixed with 4-hydroxybenzoic acid with hydroxyl groups, a polyether substance with a long-chain structure is generated under the catalysis of a catalyst, and then the polyether substance is mixed with epoxy diluent trimethylolpropane triglycidyl ether, so that the hyperbranched epoxy resin with the end group of an epoxy group is finally prepared; meanwhile, compared with ester bonds, the ether bonds have stronger hydrolysis resistance and chemical corrosion resistance, the service life of the conductive adhesive can be effectively prolonged, and the product quality is enhanced.
Further, in step S1, preparing a silver nanowire specifically includes the following steps:
s11, dissolving polyvinylpyrrolidone and NaCl in ethylene glycol, stirring and mixing, carrying out oil bath heating to 150-180 ℃, dropwise adding a silver nitrate ethylene glycol solution, and stirring and reacting for 1-2 hours after dropwise adding is finished;
s12, adding absolute ethyl alcohol, fully mixing, performing centrifugal separation to obtain a gray precipitate, alternately cleaning for 3-4 times by using pure water and absolute ethyl alcohol, and drying to obtain the nano silver wire;
in step S1, the mass ratio of polyvinylpyrrolidone, naCl, silver nitrate and absolute ethyl alcohol is (2-2.5): (0.1-0.3): (5-8): (150-200).
Further, in step S2, preparing a silver nanowire specifically includes the following steps:
s21, dissolving polyvinylpyrrolidone in absolute ethyl alcohol, adding silver nitrate and pure water after uniformly stirring, and continuously stirring for later use after uniformly stirring;
s22, dissolving potassium borohydride and sodium citrate in absolute ethyl alcohol, mixing with a polyvinylpyrrolidone ethanol solution, stirring and reacting for 1.5-2h at the speed of 450-600rpm, performing suction filtration, washing for 3-4 times by using absolute ethyl alcohol, and then drying to obtain nano silver particles;
in step S2, the mass ratio of polyvinylpyrrolidone, silver nitrate, potassium borohydride and sodium citrate is (2-4): (3-5): (0.5-1.5): (1.5-2).
Furthermore, in step S31, the molar ratio of the 4-hydroxybenzoic acid, the polyethylene glycol glycidyl ether, the N, N-dimethylformamide, and the catalyst is (2-4): (1-1.5): (40-50): (0.05-0.1).
Furthermore, in step S33, the molar ratio of trimethylolpropane triglycidyl ether, catalyst and N, N-dimethylformamide is (4-6): (0.1-0.2): (50-80).
Further, in step S3, the catalyst is any one or more of tetraethylammonium bromide, tetrabutylammonium bromide and triethylbenzylammonium chloride.
A method for using sintering type nano silver conductive adhesive for chip packaging comprises the following steps: and directly coating the conductive adhesive on the surface of the printed circuit board, and reacting at 150-200 ℃ for 0.5-1h to finish the curing of the conductive adhesive.
Compared with the prior art, the invention has the following beneficial effects: in order to enhance the conductivity of the conductive adhesive, the conductive filler compounded by the nano silver wires and the nano silver particles is prepared, and a conductive network is formed by lapping the nano silver wires in the conductive adhesive by utilizing the one-dimensional structure of the nano silver wires, so that the transmission of electrons is facilitated; meanwhile, in order to enhance the fluidity of the epoxy resin and improve the distribution of the nano silver, the hyperbranched epoxy resin is synthesized to be used as a resin matrix, the dispersion of the nano silver is assisted by virtue of the spherical structure and numerous branches of the hyperbranched compound, and meanwhile, because the hyperbranched epoxy resin has high fluidity, the addition of a diluent can be avoided, and the influence on the function of the conductive agent caused by the conductive adhesive hole due to the volatilization and decomposition of the diluent in the curing process is prevented. The conductive adhesive prepared by the invention has excellent performance, good thermal conductivity and lower volume resistivity, can be applied to a plurality of precise lines, has good flexibility and low void ratio, and has a wide market.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1.
A preparation method of sintered nano silver conductive adhesive for chip packaging comprises the following steps:
s1, preparing a nano silver wire;
s11, adding 2 parts of polyvinylpyrrolidone and 0.1 part of NaCl in 80 parts of ethylene glycol in a reaction container according to parts by weight, stirring and mixing, heating to 180 ℃ in an oil bath, dissolving 5 parts of silver nitrate in 40 parts of ethylene glycol, slowly adding the mixture into the reaction container in a dropwise manner, and continuously stirring and reacting for 2 hours at the speed of 150rpm after dropwise addition is completed;
s12, adding 150 parts of absolute ethyl alcohol, fully mixing, centrifuging by using a centrifuge to obtain a gray precipitate, alternately cleaning for 4 times by using pure water and absolute ethyl alcohol, and drying for 4 hours by using a vacuum evaporator to obtain the nano silver wire;
s2, preparing nano silver particles;
s21, adding 2 parts of polyvinylpyrrolidone and 80 parts of absolute ethyl alcohol into a reaction container, uniformly stirring, adding 3 parts of silver nitrate and 80 parts of pure water, uniformly stirring, and continuously stirring for later use;
s22, weighing 0.5 part of potassium borohydride and 1.5 parts of sodium citrate, dissolving in 60 parts of absolute ethyl alcohol, adding into a reaction container, stirring and reacting at the speed of 600rpm for 1.5 hours, performing suction filtration, washing a filtered product with the absolute ethyl alcohol for 4 times, and drying with a vacuum drying oven to obtain nano-silver particles;
s3, preparing hyperbranched epoxy resin;
s31, mixing 4 parts of 4-hydroxybenzoic acid and 1.5 parts of polyethylene glycol glycidyl ether with 50 parts of N, N-dimethylformamide in parts by mole, uniformly stirring, adding 0.1 part of tetraethylammonium bromide catalyst, introducing nitrogen, carrying out oil bath, heating to 90 ℃, and reacting for 12 hours;
s32, after the reaction is finished, removing the redundant solvent by rotary evaporation, and using a saturated NaCl solution and saturated NaHCO 3 Washing for 5 times, and then performing rotary evaporation to remove the excessive water solvent until the quality of the product is not changed any more;
s33, dissolving 6 parts of trimethylolpropane triglycidyl ether and 0.2 part of catalyst in 80 parts of N, N-dimethylformamide, stirring and mixing, adding the rotary evaporation product prepared in the step S32, introducing nitrogen, and heating in an oil bath to 120 ℃ for reaction for 12 hours;
s34, after the reaction is finished, performing rotary evaporation for 4 hours to remove the unreacted solvent, adding tetrahydrofuran in an amount which is 3 times the volume of the residual product, stirring and mixing, washing for 3 times by using pure water and diethyl ether, performing suction filtration, and drying the suction filtration product to obtain hyperbranched epoxy resin;
s4, placing the nano silver wires and the nano silver particles prepared in the steps S1 and S2 in a silane coupling agent, performing dispersion treatment for 3 hours by using 20KHz ultrasonic waves, and performing centrifugal separation to obtain modified nano silver wires and modified nano silver particles;
s5, mixing 15 parts of modified nano silver wires, 45 parts of nano silver particles and 10 parts of hyperbranched epoxy resin, stirring and dispersing for 1 hour at the speed of 300rpm, adding 5 parts of E51 epoxy resin and 14 parts of phthalic anhydride curing agent, continuously stirring for 0.5 hour, adding 0.3 part of 2-ethyl-4-methylimidazole curing accelerator, and continuously stirring until the materials are uniformly mixed to obtain the conductive adhesive.
Example 2.
Compared with example 1, the present example increases the amount of the hyperbranched epoxy resin added in step S5;
a preparation method of sintered nano silver conductive adhesive for chip packaging comprises the following steps:
s1, preparing a nano silver wire;
s11, adding 2 parts of polyvinylpyrrolidone and 0.1 part of NaCl in 80 parts of ethylene glycol in a reaction container according to parts by weight, stirring and mixing, heating to 180 ℃ in an oil bath, dissolving 5 parts of silver nitrate in 40 parts of ethylene glycol, slowly adding the mixture into the reaction container in a dropwise manner, and continuously stirring and reacting for 2 hours at the speed of 150rpm after dropwise addition is completed;
s12, adding 150 parts of absolute ethyl alcohol, fully mixing, centrifuging by using a centrifuge to obtain a gray precipitate, alternately cleaning for 4 times by using pure water and absolute ethyl alcohol, and drying for 4 hours by using a vacuum evaporator to obtain the nano silver wire;
s2, preparing nano silver particles;
s21, adding 2 parts of polyvinylpyrrolidone and 80 parts of absolute ethyl alcohol into a reaction container, uniformly stirring, adding 3 parts of silver nitrate and 80 parts of pure water, uniformly stirring, and continuously stirring for later use;
s22, weighing 0.5 part of potassium borohydride and 1.5 parts of sodium citrate, dissolving in 60 parts of absolute ethyl alcohol, adding into a reaction container, stirring and reacting at the speed of 600rpm for 1.5h, performing suction filtration, washing a filtered product with the absolute ethyl alcohol for 4 times, and drying with a vacuum drying oven to obtain nano-silver particles;
s3, preparing hyperbranched epoxy resin;
s31, mixing 4 parts of 4-hydroxybenzoic acid and 1.5 parts of polyethylene glycol glycidyl ether in parts by mole with 50 parts of N, N-dimethylformamide, uniformly stirring, adding 0.1 part of tetraethylammonium bromide catalyst, filling nitrogen, carrying out oil bath, heating to 90 ℃, and reacting for 12 hours;
s32. After the reaction is finished, removing the redundant solvent by rotary evaporation, and using saturated NaCl solution and saturated NaHCO 3 Washing for 5 times, and then performing rotary evaporation to remove the excessive water solvent until the quality of the product is not changed any more;
s33, dissolving 6 parts of trimethylolpropane triglycidyl ether and 0.2 part of catalyst in 80 parts of N, N-dimethylformamide, stirring and mixing, adding the rotary evaporation product prepared in the step S32, introducing nitrogen, and heating in an oil bath to 120 ℃ for reaction for 12 hours;
s34, after the reaction is finished, performing rotary evaporation for 4 hours to remove unreacted solvent, adding tetrahydrofuran of which the volume is 3 times that of the residual product, stirring and mixing, washing for 3 times by using pure water and diethyl ether, performing suction filtration, and drying the suction filtration product to obtain hyperbranched epoxy resin;
s4, placing the nano silver wires and the nano silver particles prepared in the steps S1 and S2 in a silane coupling agent, performing dispersion treatment for 3 hours by using 20KHz ultrasonic waves, and performing centrifugal separation to obtain modified nano silver wires and modified nano silver particles;
s5, mixing 15 parts of modified nano-silver wires, 45 parts of nano-silver particles and 12 parts of hyperbranched epoxy resin, stirring and dispersing at the speed of 300rpm for 1 hour, adding 5 parts of E51 epoxy resin and 14 parts of phthalic anhydride curing agent, continuously stirring for 0.5 hour, adding 0.3 part of 2-ethyl-4-methylimidazole curing accelerator, and continuously stirring until the materials are uniformly mixed to obtain the conductive adhesive.
Example 3.
Compared with the embodiment 1, the embodiment increases the adding amount of the nano silver wire in the step S5;
a preparation method of sintered nano silver conductive adhesive for chip packaging comprises the following steps:
s1, preparing a nano silver wire;
s11, adding 2 parts of polyvinylpyrrolidone and 0.1 part of NaCl in 80 parts of ethylene glycol into a reaction container according to parts by weight, stirring and mixing, heating to 180 ℃ in an oil bath, dissolving 5 parts of silver nitrate in 40 parts of ethylene glycol, slowly adding the silver nitrate into the reaction container in a dropwise manner, and continuously stirring and reacting for 2 hours at the speed of 150rpm after the dropwise addition is finished;
s12, adding 150 parts of absolute ethyl alcohol, fully mixing, using a centrifugal machine, carrying out centrifugal separation to obtain a gray precipitate, alternately cleaning the gray precipitate for 4 times by using pure water and absolute ethyl alcohol, and drying the gray precipitate for 4 hours by using a vacuum evaporator to obtain the nano silver wire;
s2, preparing nano silver particles;
s21, adding 2 parts of polyvinylpyrrolidone and 80 parts of absolute ethyl alcohol into a reaction container, uniformly stirring, adding 3 parts of silver nitrate and 80 parts of pure water, uniformly stirring, and continuously stirring for later use;
s22, weighing 0.5 part of potassium borohydride and 1.5 parts of sodium citrate, dissolving in 60 parts of absolute ethyl alcohol, adding into a reaction container, stirring and reacting at the speed of 600rpm for 1.5h, performing suction filtration, washing a filtered product with the absolute ethyl alcohol for 4 times, and drying with a vacuum drying oven to obtain nano-silver particles;
s3, preparing hyperbranched epoxy resin;
s31, mixing 4 parts of 4-hydroxybenzoic acid and 1.5 parts of polyethylene glycol glycidyl ether with 50 parts of N, N-dimethylformamide in parts by mole, uniformly stirring, adding 0.1 part of tetraethylammonium bromide catalyst, introducing nitrogen, carrying out oil bath, heating to 90 ℃, and reacting for 12 hours;
s32, after the reaction is finished, removing the redundant solvent by rotary evaporation, and using a saturated NaCl solution and saturated NaHCO 3 Washing for 5 times, and then performing rotary evaporation to remove the excessive water solvent until the quality of the product is not changed any more;
s33, dissolving 6 parts of trimethylolpropane triglycidyl ether and 0.2 part of catalyst in 80 parts of N, N-dimethylformamide, stirring and mixing, adding the rotary evaporation product prepared in the step S32, introducing nitrogen, and heating in an oil bath to 120 ℃ for reaction for 12 hours;
s34, after the reaction is finished, performing rotary evaporation for 4 hours to remove unreacted solvent, adding tetrahydrofuran of which the volume is 3 times that of the residual product, stirring and mixing, washing for 3 times by using pure water and diethyl ether, performing suction filtration, and drying the suction filtration product to obtain hyperbranched epoxy resin;
s4, placing the nano silver wires and the nano silver particles prepared in the steps S1 and S2 in a silane coupling agent, performing dispersion treatment for 2-3h by using 20KHz ultrasonic waves, and performing centrifugal separation to obtain modified nano silver wires and modified nano silver particles;
s5, mixing 20 parts of modified nano-silver wires, 45 parts of nano-silver particles and 10 parts of hyperbranched epoxy resin, stirring and dispersing at the speed of 300rpm for 1 hour, adding 5 parts of E51 epoxy resin and 14 parts of phthalic anhydride curing agent, continuously stirring for 0.5 hour, adding 0.3 part of 2-ethyl-4-methylimidazole curing accelerator, and continuously stirring until the materials are uniformly mixed to obtain the conductive adhesive.
Comparative example 1.
Compared with the example 1, the hyperbranched epoxy resin is replaced by the epoxy resin E51 with the same amount, and 3 parts of acetone is added as a diluent in the comparative example;
a preparation method of sintered nano silver conductive adhesive for chip packaging comprises the following steps:
s1, preparing a nano silver wire;
s11, adding 2 parts of polyvinylpyrrolidone and 0.1 part of NaCl in 80 parts of ethylene glycol in a reaction container according to parts by weight, stirring and mixing, heating to 180 ℃ in an oil bath, dissolving 5 parts of silver nitrate in 40 parts of ethylene glycol, slowly adding the mixture into the reaction container in a dropwise manner, and continuously stirring and reacting for 2 hours at the speed of 150rpm after dropwise addition is completed;
s12, adding 150 parts of absolute ethyl alcohol, fully mixing, using a centrifugal machine, carrying out centrifugal separation to obtain a gray precipitate, alternately cleaning the gray precipitate for 4 times by using pure water and absolute ethyl alcohol, and drying the gray precipitate for 4 hours by using a vacuum evaporator to obtain the nano silver wire;
s2, preparing nano silver particles;
s21, adding 2 parts of polyvinylpyrrolidone and 80 parts of absolute ethyl alcohol into a reaction container, uniformly stirring, adding 3 parts of silver nitrate and 80 parts of pure water, uniformly stirring, and continuously stirring for later use;
s22, weighing 0.5 part of potassium borohydride and 1.5 parts of sodium citrate, dissolving in 60 parts of absolute ethyl alcohol, adding into a reaction container, stirring and reacting at the speed of 600rpm for 1.5 hours, performing suction filtration, washing a filtered product with the absolute ethyl alcohol for 4 times, and drying with a vacuum drying oven to obtain nano-silver particles;
s3, placing the nano silver wires and the nano silver particles prepared in the steps S1 and S2 in a silane coupling agent, performing dispersion treatment for 3 hours by using 20KHz ultrasonic waves, and performing centrifugal separation to obtain modified nano silver wires and modified nano silver particles;
s4, mixing 15 parts of modified nano silver wires, 45 parts of nano silver particles, 10 parts of epoxy resin E51 and 3 parts of acetone diluent, stirring and dispersing at the speed of 300rpm for 1 hour, adding 5 parts of E51 epoxy resin and 14 parts of phthalic anhydride curing agent, continuously stirring for 0.5 hour, adding 0.3 part of 2-ethyl-4-methylimidazole curing accelerator, and continuously stirring until the materials are uniformly mixed to obtain the conductive adhesive.
Comparative example 2.
Compared with the embodiment 1, the embodiment increases the amount of the nano silver wires and reduces the amount of the nano silver particles in an equivalent way;
a preparation method of sintered nano silver conductive adhesive for chip packaging comprises the following steps:
s1, preparing a nano silver wire;
s11, adding 2 parts of polyvinylpyrrolidone and 0.1 part of NaCl in 80 parts of ethylene glycol in a reaction container according to parts by weight, stirring and mixing, heating to 180 ℃ in an oil bath, dissolving 5 parts of silver nitrate in 40 parts of ethylene glycol, slowly adding the mixture into the reaction container in a dropwise manner, and continuously stirring and reacting for 2 hours at the speed of 150rpm after dropwise addition is completed;
s12, adding 150 parts of absolute ethyl alcohol, fully mixing, centrifuging by using a centrifuge to obtain a gray precipitate, alternately cleaning for 4 times by using pure water and absolute ethyl alcohol, and drying for 4 hours by using a vacuum evaporator to obtain the nano silver wire;
s2, preparing nano silver particles;
s21, adding 2 parts of polyvinylpyrrolidone and 80 parts of absolute ethyl alcohol into a reaction container, uniformly stirring, adding 3 parts of silver nitrate and 80 parts of pure water, uniformly stirring, and continuously stirring for later use;
s22, weighing 0.5 part of potassium borohydride and 1.5 parts of sodium citrate, dissolving in 60 parts of absolute ethyl alcohol, adding into a reaction container, stirring and reacting at the speed of 600rpm for 1.5h, performing suction filtration, washing a filtered product with the absolute ethyl alcohol for 4 times, and drying with a vacuum drying oven to obtain nano-silver particles;
s3, preparing hyperbranched epoxy resin;
s31, mixing 4 parts of 4-hydroxybenzoic acid and 1.5 parts of polyethylene glycol glycidyl ether with 50 parts of N, N-dimethylformamide in parts by mole, uniformly stirring, adding 0.1 part of tetraethylammonium bromide catalyst, introducing nitrogen, carrying out oil bath, heating to 90 ℃, and reacting for 12 hours;
s32, after the reaction is finished, removing the redundant solvent by rotary evaporation, and using a saturated NaCl solution and saturated NaHCO 3 Washing for 5 times, and then performing rotary evaporation to remove the excessive water solvent until the quality of the product is not changed any more;
s33, dissolving 6 parts of trimethylolpropane triglycidyl ether and 0.2 part of catalyst in 80 parts of N, N-dimethylformamide, stirring and mixing, adding the rotary evaporation product prepared in the step S32, introducing nitrogen, and raising the temperature to 120 ℃ in an oil bath to react for 12 hours;
s34, after the reaction is finished, performing rotary evaporation for 4 hours to remove unreacted solvent, adding tetrahydrofuran of which the volume is 3 times that of the residual product, stirring and mixing, washing for 3 times by using pure water and diethyl ether, performing suction filtration, and drying the suction filtration product to obtain hyperbranched epoxy resin;
s4, placing the nano silver wires and the nano silver particles prepared in the steps S1 and S2 in a silane coupling agent, performing dispersion treatment for 3 hours by using 20KHz ultrasonic waves, and performing centrifugal separation to obtain modified nano silver wires and modified nano silver particles;
s5, mixing 25 parts of modified nano-silver wires, 35 parts of nano-silver particles and 10 parts of hyperbranched epoxy resin, stirring and dispersing at the speed of 300rpm for 1 hour, adding 5 parts of E51 epoxy resin and 14 parts of phthalic anhydride curing agent, continuously stirring for 0.5 hour, adding 0.3 part of 2-ethyl-4-methylimidazole curing accelerator, and continuously stirring until the materials are uniformly mixed to obtain the conductive adhesive.
Example 3.
Compared with the embodiment 1, the modified nano silver wire is equivalently replaced by the nano silver particle;
a preparation method of sintered nano silver conductive adhesive for chip packaging comprises the following steps:
s1, preparing nano silver particles;
s11, adding 2 parts of polyvinylpyrrolidone and 80 parts of absolute ethyl alcohol into a reaction container, uniformly stirring, adding 3 parts of silver nitrate and 80 parts of pure water, uniformly stirring, and continuously stirring for later use;
s12, weighing 0.5 part of potassium borohydride and 1.5 parts of sodium citrate, dissolving in 60 parts of absolute ethyl alcohol, adding into a reaction container, stirring and reacting at the speed of 600rpm for 1.5h, performing suction filtration, washing a filtered product with the absolute ethyl alcohol for 4 times, and drying with a vacuum drying oven to obtain nano-silver particles;
s2, preparing hyperbranched epoxy resin;
s21, mixing 4 parts of 4-hydroxybenzoic acid and 1.5 parts of polyethylene glycol glycidyl ether in parts by mole with 50 parts of N, N-dimethylformamide, uniformly stirring, adding 0.1 part of tetraethylammonium bromide catalyst, filling nitrogen, carrying out oil bath, heating to 90 ℃, and reacting for 12 hours;
s22, after the reaction is finished, removing the redundant solvent by rotary evaporation, and using a saturated NaCl solution and saturated NaHCO 3 Washing for 5 times, and then performing rotary evaporation to remove the excessive water solvent until the quality of the product is not changed any more;
s23, dissolving 6 parts of trimethylolpropane triglycidyl ether and 0.2 part of catalyst in 80 parts of N, N-dimethylformamide, stirring and mixing, adding the rotary evaporation product prepared in the step S32, introducing nitrogen, and raising the temperature to 120 ℃ in an oil bath to react for 12 hours;
s24, after the reaction is finished, performing rotary evaporation for 4 hours to remove unreacted solvent, adding tetrahydrofuran of which the volume is 3 times that of the residual product, stirring and mixing, washing for 3 times by using pure water and diethyl ether, performing suction filtration, and drying the suction filtration product to obtain hyperbranched epoxy resin;
s3, placing the nano silver particles in a silane coupling agent, dispersing for 3 hours by using 20KHz ultrasonic waves, and performing centrifugal separation to obtain modified nano silver wires and modified nano silver particles;
s4, mixing 60 parts of nano silver particles and 10 parts of hyperbranched epoxy resin in parts by weight, stirring and dispersing for 1 hour at the speed of 300rpm, adding 5 parts of E51 epoxy resin and 14 parts of phthalic anhydride curing agent, continuously stirring for 0.5 hour, adding 0.3 part of 2-ethyl-4-methylimidazole curing accelerator, and continuously stirring until the materials are uniformly mixed to obtain the conductive adhesive.
Comparative example 4.
Compared with the example 1, the comparative example uses the hyperbranched epoxy resin disclosed in the patent CN109232862B to replace the hyperbranched epoxy resin prepared by the invention with equal amount;
a preparation method of sintered nano silver conductive adhesive for chip packaging comprises the following steps:
s1, preparing a nano silver wire;
s11, adding 2 parts of polyvinylpyrrolidone and 0.1 part of NaCl in 80 parts of ethylene glycol in a reaction container according to parts by weight, stirring and mixing, heating to 180 ℃ in an oil bath, dissolving 5 parts of silver nitrate in 40 parts of ethylene glycol, slowly adding the mixture into the reaction container in a dropwise manner, and continuously stirring and reacting for 2 hours at the speed of 150rpm after dropwise addition is completed;
s12, adding 150 parts of absolute ethyl alcohol, fully mixing, centrifuging by using a centrifuge to obtain a gray precipitate, alternately cleaning for 4 times by using pure water and absolute ethyl alcohol, and drying for 4 hours by using a vacuum evaporator to obtain the nano silver wire;
s2, preparing nano silver particles;
s21, adding 2 parts of polyvinylpyrrolidone and 80 parts of absolute ethyl alcohol into a reaction container, uniformly stirring, adding 3 parts of silver nitrate and 80 parts of pure water, uniformly stirring, and continuously stirring for later use;
s22, weighing 0.5 part of potassium borohydride and 1.5 parts of sodium citrate, dissolving in 60 parts of absolute ethyl alcohol, adding into a reaction container, stirring and reacting at the speed of 600rpm for 1.5 hours, performing suction filtration, washing a filtered product with the absolute ethyl alcohol for 4 times, and drying with a vacuum drying oven to obtain nano-silver particles;
s3, preparing hyperbranched epoxy resin according to a mode disclosed by a comparison document;
s4, placing the nano silver wires and the nano silver particles prepared in the steps S1 and S2 in a silane coupling agent, performing dispersion treatment for 3 hours by using 20KHz ultrasonic waves, and performing centrifugal separation to obtain modified nano silver wires and modified nano silver particles;
s5, mixing 15 parts of modified nano-silver wires, 45 parts of nano-silver particles and 10 parts of hyperbranched epoxy resin, stirring and dispersing at the speed of 300rpm for 1 hour, adding 5 parts of E51 epoxy resin and 14 parts of phthalic anhydride curing agent, continuously stirring for 0.5 hour, adding 0.3 part of 2-ethyl-4-methylimidazole curing accelerator, and continuously stirring until the materials are uniformly mixed to obtain the conductive adhesive.
And (3) detection: the volume resistivity of the conductive adhesives of examples 1-3 and comparative examples 1-2 was measured according to GB/T15662; the thermal conductivity of the conductive adhesives of examples 1-3 and comparative examples 1-2 was measured according to astm d 5470, and the results are shown in the following table:
according to the comparison between examples 1-2 and comparative example 1, it can be found that, after the hyperbranched epoxy resin is added, the volume resistivity of the conductive adhesive is far smaller than that of the conductive adhesive using the diluent, and the thermal conductivity of the conductive adhesive is also larger than that of the conductive adhesive using the diluent, that is, the conductive adhesive prepared by using the hyperbranched epoxy resin to replace the epoxy resin doped with the diluent has more excellent = electrical properties; the comparison of examples 1 and 3 with comparative examples 2 and 3 shows that the performance of the conductive adhesive doped with the nano silver wires is superior to that of the conductive adhesive not doped with the nano silver wires, and the nano silver wires can be lapped in the 1-dimensional direction in the resin to form a conductive network, so that the transmission of electrons can be enhanced, but the performance is reduced when the doping amount of the nano silver wires exceeds a certain proportion, and the entanglement in the one-dimensional direction is formed in the resin, so that the dispersibility of the nano silver wires in the resin matrix is hindered, and the performance is reduced; through comparison between the example 1 and the comparative example 4, the hyperbranched epoxy resin prepared by the invention has better combination performance with E51, and can realize better performance improvement when being used in a compounding way;
finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A preparation method of sintered nano silver conductive adhesive for chip packaging is characterized by comprising the following steps:
s1, preparing a nano silver wire;
s11, dissolving polyvinylpyrrolidone and NaCl in ethylene glycol, stirring and mixing, carrying out oil bath, heating to 150-180 ℃, dropwise adding a silver nitrate ethylene glycol solution, and stirring and reacting for 1-2 hours after dropwise adding;
s12, adding absolute ethyl alcohol, fully mixing, performing centrifugal separation to obtain a gray precipitate, alternately cleaning for 3-4 times by using pure water and the absolute ethyl alcohol, and drying to obtain the nano silver wire;
s2, preparing nano silver particles;
s21, dissolving polyvinylpyrrolidone in absolute ethyl alcohol, adding silver nitrate and pure water after uniformly stirring, and continuously stirring for later use after uniformly stirring;
s22, dissolving potassium borohydride and sodium citrate in absolute ethyl alcohol, mixing with a polyvinylpyrrolidone ethanol solution, stirring and reacting for 1.5-2h at the speed of 450-600rpm, performing suction filtration, washing for 3-4 times by using absolute ethyl alcohol, and then drying to obtain nano silver particles;
s3, preparing hyperbranched epoxy resin;
s31, mixing 4-hydroxybenzoic acid and 1-1.5 parts of polyethylene glycol glycidyl ether in parts by mole and mixing with N, N-dimethylformamide, stirring uniformly, adding 0.05-0.1 part of catalyst, charging nitrogen and raising the temperature to 80-90 ℃ in an oil bath to react for 8-12 hours;
s32, after the reaction is finished, removing the redundant solvent by rotary evaporation, washing the reaction product for 3 to 5 times by using a saturated NaCl solution and saturated NaHCO3, and then removing the redundant water solvent by rotary evaporation until the quality of the product is not changed any more;
s33, dissolving trimethylolpropane triglycidyl ether and a catalyst in N, N-dimethylformamide, stirring and mixing, adding the rotary evaporation product prepared in the step S32, introducing nitrogen, and heating in an oil bath to 90-120 ℃ for reacting for 8-12h;
s34, after the reaction is finished, performing rotary evaporation for 3-4 hours to remove the unreacted solvent, adding tetrahydrofuran with the volume 2-3 times that of the residual product, stirring and mixing, washing for 2-3 times by using pure water and diethyl ether, performing suction filtration, and drying the suction filtration product to obtain the hyperbranched epoxy resin;
s4, placing the nano silver wires and the nano silver particles prepared in the steps S1 and S2 in a silane coupling agent, dispersing for 2-3h by using 15-20KHz ultrasonic waves, and performing centrifugal separation to obtain modified nano silver wires and modified nano silver particles;
s5, mixing the modified nano silver wires, the nano silver particles and the hyperbranched epoxy resin, stirring and dispersing at the speed of 200-300rpm for 0.5-1h, adding the epoxy resin and the curing agent, continuously stirring for 0.5h, adding the curing accelerator, and continuously stirring until the materials are uniformly mixed;
in the step S1, the mass ratio of polyvinylpyrrolidone, naCl, silver nitrate and absolute ethyl alcohol is (2-2.5): (0.1-0.3): (5-8): (150-200);
in the step S2, the mass ratio of the polyvinylpyrrolidone, the silver nitrate, the potassium borohydride and the sodium citrate is (2-4): (3-5): (0.5-1.5): (1.5-2);
the sintered nano silver conductive adhesive prepared by the method comprises the following components in parts by weight: 45-55 parts of modified nano silver particles, 15-20 parts of modified nano silver wires, 15-45 parts of hyperbranched epoxy resin matrix, 12-40 parts of curing agent and 0.3-0.5 part of curing accelerator;
the hyperbranched epoxy resin matrix is mixed resin of epoxy resin E51 and hyperbranched epoxy resin, wherein the weight ratio of the epoxy resin E51 to the hyperbranched epoxy resin is (2-3): (4-8).
2. The method for preparing the sintered nano silver conductive adhesive for chip packaging according to claim 1, wherein the method comprises the following steps: the curing agent is phthalic anhydride; the curing accelerator is 2-ethyl-4-methylimidazole.
3. The method for preparing the sintered nano silver conductive adhesive for chip packaging according to claim 1, wherein the method comprises the following steps: in step S31, the molar ratio of the 4-hydroxybenzoic acid, the polyethylene glycol glycidyl ether, the N, N-dimethylformamide and the catalyst is (2-4): (1-1.5): (40-50): (0.05-0.1).
4. The method for preparing the sintered nano silver conductive adhesive for chip packaging according to claim 1, wherein the method comprises the following steps: in step S33, the molar ratio of trimethylolpropane triglycidyl ether, catalyst and N, N-dimethylformamide is (4-6): (0.1-0.2): (50-80).
5. The method for preparing the sintered nano silver conductive adhesive for chip packaging according to claim 1, wherein the method comprises the following steps: in step S3, the catalyst is any one or more of tetraethylammonium bromide, tetrabutylammonium bromide and triethylbenzylammonium chloride.
6. The use method of the sintering type nano silver conductive adhesive prepared by the preparation method of the sintering type nano silver conductive adhesive for chip packaging according to any one of claims 1 to 5, characterized by comprising the following steps: and directly coating the conductive adhesive on the surface of the printed circuit board, and reacting at 150-200 ℃ for 0.5-1h to finish the curing of the conductive adhesive.
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