CN118325505A - Anisotropic conductive tin adhesive and preparation method thereof - Google Patents
Anisotropic conductive tin adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN118325505A CN118325505A CN202410482286.5A CN202410482286A CN118325505A CN 118325505 A CN118325505 A CN 118325505A CN 202410482286 A CN202410482286 A CN 202410482286A CN 118325505 A CN118325505 A CN 118325505A
- Authority
- CN
- China
- Prior art keywords
- tin
- bismuth alloy
- conductive
- conductive filler
- alloy powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 32
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 32
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title description 18
- 239000000843 powder Substances 0.000 claims abstract description 60
- 239000011231 conductive filler Substances 0.000 claims abstract description 51
- 229910001152 Bi alloy Inorganic materials 0.000 claims abstract description 42
- JWVAUCBYEDDGAD-UHFFFAOYSA-N bismuth tin Chemical compound [Sn].[Bi] JWVAUCBYEDDGAD-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000011159 matrix material Substances 0.000 claims abstract description 42
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 239000013207 UiO-66 Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000003822 epoxy resin Substances 0.000 claims abstract description 19
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 19
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- 239000003085 diluting agent Substances 0.000 claims abstract description 11
- 150000007524 organic acids Chemical class 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000012190 activator Substances 0.000 claims abstract description 8
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 8
- 239000000956 alloy Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000001723 curing Methods 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003292 glue Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000003094 microcapsule Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- 229920013809 TRITON DF-20 Polymers 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000013543 active substance Substances 0.000 claims description 5
- 238000007872 degassing Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 238000009689 gas atomisation Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 239000011812 mixed powder Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 claims description 4
- 238000000707 layer-by-layer assembly Methods 0.000 claims description 4
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000679 solder Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 3
- 239000007864 aqueous solution Substances 0.000 claims 2
- 238000004806 packaging method and process Methods 0.000 abstract description 16
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000004020 conductor Substances 0.000 abstract 1
- 239000004005 microsphere Substances 0.000 description 16
- 239000002313 adhesive film Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000011295 pitch Substances 0.000 description 8
- 238000013007 heat curing Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012356 Product development Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses an anisotropic conductive tin adhesive, which comprises 20-25% of conductive filler and 75-80% of polymer matrix by mass percent. The conductive filler is composed of tin-bismuth alloy powder and MOF material according to the mass percentage of 1:1, wherein the tin-bismuth alloy powder is selected from one of Sn99.3Bi0.7, sn58Bi42 and Sn42Bi57.6-Ag0.4, the grain diameter of the alloy powder is of the grade T10, and the grain diameter is 1.0-2.0 mu m. The MOF material is UiO-66. Polymer matrix component: 60.0 to 80.0 percent of epoxy resin, 5.0 to 20.0 percent of curing agent, 1.0 to 3.0 percent of surfactant, 5.0 to 7.0 percent of organic acid activator, 1.0 to 5.0 percent of antioxidant and 3.0 to 5.0 percent of diluent. Based on tin bismuth alloy powder uniformly distributed in MOF material holes, conductive filler can be uniformly distributed in a polymer matrix, so that the problem of random distribution state of conductive particles in mechanical mixing is solved, the anisotropic conductive material has stable anisotropy and high reliability of a packaging interface, and no short circuit risk exists between adjacent electrodes with micro-spacing.
Description
Technical Field
The invention relates to conductive tin glue, in particular to anisotropic conductive tin glue suitable for packaging micro-spacing electronic components and a preparation method thereof.
Background
With the continuous progress of the electronic information industry, electronic components are gradually miniaturized, thinned and flexible, and the requirements for packaging and interconnection of micro-pitch electronic components are also higher and higher. Taking Mini-LEDs and Micro-LEDs which are rapidly developed in recent years as examples, the chip size of the LED is reduced from larger than 200 mu m of a high-power LED to Mini-LEDs with the size of 100-200 mu m and Micro-LEDs with the size of 1-100 mu m (or smaller than 50 mu m). The miniaturization and matrixing technology of LEDs make the density of micro-sized LED arrays integrated on the same chip higher and higher, which requires that the packaging of the chip is not just to achieve reliable connection, but also to achieve electrical conduction on the vertical path of the narrow-pitch interconnection interface, and meanwhile, electrical insulation is provided between parallel I/O ports, so that short-circuit risks are not generated between adjacent terminals with narrow pitches. Traditional electronic packaging materials (such as solder paste, conductive adhesive, etc.) cannot completely meet the technical requirements of the current electronic components, but anisotropic conductive adhesive can meet the packaging requirements of micro-pitch electronic components, and is widely used in the manufacturing fields of liquid crystal display modules, camera modules, flexible circuit boards, touch screen connecting wires, high-precision flat cables, integrated circuits, etc. with high-density and micro-pitch packaging requirements in recent years.
The anisotropic conductive adhesive is different from the conventional conductive adhesive, integrates conductivity and conductivity, and has multiple characteristics of sealing, water resistance, insulation and the like. The unique conductivity and insulation performance of the semiconductor device show differences in different directions, so that incomparable advantages are shown in the fields of high-difficulty packaging, such as high welding density, small bonding pad size, small packaging interval and the like. In short, anisotropic conductive adhesives have become an indispensable key material in the field of modern electronic manufacturing by virtue of their unique physical and chemical properties, and a wide range of application fields. However, despite its wide application, the current major manufacturers worldwide are still on the vergence of being limited by technological thresholds. Current research and product development focus mainly on how to further optimize and improve the conductivity, thermal performance and reliability of anisotropic conductive adhesives.
The invention patent of Chinese patent publication No. CN115386318A discloses a preparation method of an anisotropic conductive adhesive film for packaging an ultrafine pitch electrode, which is characterized in that insulating nickel-plated polystyrene microspheres with controllable thickness are prepared by combining a bottom-up microsphere synthesis method with a top-down photoetching technology, and the microspheres are self-assembled into a conductive adhesive matrix with a periodical hole topological structure under the action of capillary force to form regular arrangement. The prepared anisotropic conductive adhesive film has good anisotropic conductive performance, ensures the capturing rate of a single electrode to conductive particles, can realize the encapsulation of an ultrafine-pitch electrode, and prevents the occurrence of the short circuit condition of adjacent electrodes in the encapsulation of electronic components with continuously increased integration level.
The invention patent application with the Chinese patent publication number of CN116004144A discloses a preparation method and application of a composite conductive microsphere for anisotropic conductive adhesive, wherein the inner core of the composite conductive microsphere is a Sn sphere with the diameter of 25-35 mu m, and the outer shell is an Au nano particle. The composite microsphere can be distributed in a single layer on the x-y plane by fully mixing and hot-pressing the conductive microsphere and the resin adhesive. Since Sn has strong ductility, the contact area in the z-axis direction can be increased in the hot pressing process, conductivity can be improved, and anisotropy can be achieved by controlling the filler ratio of conductive particles in the resin. The contact resistance of the prepared anisotropic conductive adhesive can be as low as 0.7 omega.
The invention patent application with the Chinese patent publication number of CN116640529A discloses a preparation method of an anisotropic conductive adhesive film and the anisotropic conductive adhesive film, wherein array-distributed conductive microspheres are obtained through a preparation route of a micropore template, the obtained array-distributed conductive microspheres are transferred to a first layer of photo-thermal dual-cured resin adhesive film, a second layer of resin adhesive film is coated on the first layer of resin adhesive film, ultraviolet light pre-curing treatment is carried out on the first layer of resin adhesive film, and the pre-curing ensures that the array form of the conductive microspheres is preliminarily fixed in the resin adhesive film, so that the particle array type anisotropic conductive adhesive film is obtained.
The invention patent application with the Chinese patent publication number of CN117292889A discloses an anisotropic conductive film and a preparation method thereof, wherein the preparation of the conductive film is that firstly, conductive microspheres distributed in an array are preset, then the conductive microspheres distributed in the array are transferred to a first resin adhesive film, finally, second resin dispersion liquid is spin-coated on the conductive microspheres distributed in the array, and after drying, the anisotropic conductive film internally containing the uniformly dispersed conductive microspheres distributed in the array can be obtained, and the connection of an ultra-high precision circuit can be realized. The preparation method provided can effectively solve the problems that the conductive particles in the anisotropic conductive film prepared by the existing method are unevenly distributed, but high-precision circuit connection cannot be realized.
The composition of the existing anisotropic conductive adhesive mainly comprises conductive filler and polymer matrix, and the mixing method of the conductive filler and the polymer matrix comprises mechanical mixing, a self-assembly method and a multilayer adhesive film superposition process for presetting array microspheres. Research and development directions are also focused on the respective performance improvement of the conductive filler and the polymer matrix, and research on the improvement of the overall performance of the interconnection interface and the interface between the conductive filler and the polymer matrix is relatively less. At present, a bonding interface of physical connection is mostly adopted between the conductive filler and the polymer matrix, and the performance of the interface also directly determines the overall performance of the conductive adhesive. Therefore, there is a need to comprehensively consider the overall performance improvement of the conductive filler, the polymer matrix and the connection interface between the conductive filler and the polymer matrix, and propose an anisotropic conductive tin adhesive based on a Metal Organic Framework (MOF) and a low Wen Xibi alloy as the conductive filler, and meanwhile, the conductive filler and the polymer matrix are chemically bonded, and a preparation method thereof.
Disclosure of Invention
The invention aims to provide anisotropic conductive tin glue and a preparation method thereof, which solve the problems that the conventional anisotropic conductive tin glue conductive filler and a polymer matrix are distributed randomly and have short circuit risks during micro-space encapsulation. Meanwhile, a physical connection interface is formed between the packaged conductive filler and the polymer matrix, and the problem of interface failure is likely to occur in the long-time service process.
The invention provides a high-stability conductive tin adhesive for forming chemical bonding between a conductive filler and a polymer matrix, wherein the conductive filler of the tin adhesive is a metal organic framework Material (MOF) and a low Wen Xibi alloy, and functional groups based on the MOF material can also participate in the crosslinking reaction of a thermosetting polymer matrix, so that the conductive filler and the polymer matrix directly form chemical bonding, and the stability of an interface in a long-time service process is improved. The specific technical scheme is as follows:
the anisotropic conductive tin adhesive consists of 20-25% of conductive filler and 75-80% of polymer matrix. The conductive filler consists of tin-bismuth alloy powder and MOF material, wherein the tin-bismuth alloy powder comprises one of the following alloys Sn99.3Bi0.7, sn58Bi42 and Sn42Bi57.6Ag0.4, the grain size of the alloy powder is of the T10 grade, and the grain size range is 1.0-2.0 mu m. The MOF material is UiO-66, and the mass percentage of the tin-bismuth alloy powder to the MOF material is 1:1.
The polymer matrix consists of the following components in percentage by mass:
The epoxy resin comprises any one or more of bisphenol A type resin E51, bisphenol A type resin E44 and bisphenol F type epoxy resin DER 351.
The curing agent is microcapsule coated curing agent, and comprises one or more of SC10208A Latent curing agent, henkel's Latent curing agent and Dow Chemical's Microencapsulated curing agent. The curing agent can not produce curing effect on the conductive tin glue in the normal temperature storage process, and can be rapidly released and initiate the curing reaction of the epoxy resin only under the heat curing condition.
The surfactant is TRITON DF-20 surfactant, is nonionic surfactant, has good low-foam surface wettability, can be dissolved in an epoxy resin matrix, and can promote tin-bismuth alloy to rapidly wet the packaging matrix at a heat curing temperature.
The organic acid activator is mixed dibasic acid (Sokalan DCS), the melting range of the activator is 100-130 ℃, the activator can be melted in the heat curing process, oxide films capable of removing the surfaces of the packaging matrix and the tin-bismuth alloy powder are rapidly released, the wetting of the conductive filler and the packaging matrix is promoted, and meanwhile, no residual corrosion exists after heat curing.
The antioxidant comprises any one or more of antioxidants Irganox1076, IRGANOX 245 and IRGANOX 1330, has the characteristics of low melting point and good compatibility with a matrix, and can effectively prevent discoloration and oxidization caused by light and heat.
The diluent is any one or more of anhydrous acetone and ethanol.
According to the invention, firstly, tin-bismuth alloy micro powder is self-assembled into MOF holes through an electrostatic self-assembly process to form the conductive filler with stable chemical bonding. Adding conductive filler into the polymer matrix to prepare the anisotropic conductive adhesive, wherein the method comprises the following steps:
(1) Preparing a metal organic framework Material (MOF) and low Wen Xibi alloy conductive filler based on electrostatic self-assembly;
(2) And (3) preparing a polymer matrix, and mixing the conductive filler and the polymer matrix to prepare the anisotropic conductive adhesive.
Specifically, the step (1) includes: firstly, tin-bismuth alloy powder with the T10 particle size prepared by gas atomization is added into ethanol solution, and the addition amount is according to the proportion of 1g of powder to 1000ml of solution. And (3) stirring the powder-added solution for 30min under the ultrasonic condition of 1KW by using a magnetic stirrer, adding 3-aminopropyl triethoxysilane, continuing ultrasonic stirring for 6h, and carrying out vacuum suction filtration after full reaction to prepare the tin-bismuth alloy powder with positive charges on the surface. The tin-bismuth alloy powder with positive charges and UiO-66 are added into the water solution, wherein the mass ratio of the tin-bismuth alloy powder to the UiO-66 is 1:1, and the ratio of the composite powder to the water solution is 1g of powder to 30 ml. And (3) in a hydrothermal reaction kettle, carrying out vacuum suction filtration after reacting for 12 hours at 80 ℃, and then freeze-drying the mixed powder to obtain the UiO-66 composite powder conductive filler containing the tin-bismuth alloy.
The step (2) comprises: firstly, adding epoxy resin, a diluent and an antioxidant into a beaker according to the adding proportion, magnetically stirring for 30min at 40 ℃, then sequentially adding a curing agent coated by microcapsules, an organic acid active agent and a surfactant, and magnetically stirring for 30min at room temperature. And (3) adding the conductive filler prepared in the step (1) under the magnetic stirring condition assisted by 1KW ultrasonic, magnetically stirring for 30min, adding the conductive tin glue into a vacuum drying oven, and carrying out degassing treatment at the temperature of 40 ℃ for 1h to obtain the anisotropic conductive tin glue.
The anisotropic conductive tin adhesive for packaging the micro-pitch electronic components has the following advantages: 1) Based on the added microcapsule coated curing agent and antioxidant, the epoxy resin has good light and heat stability under long-time storage conditions, releases activity only under a heat curing packaging process, realizes the crosslinking curing reaction of the epoxy resin, and ensures high-reliability packaging; 2) The surface of the tin-bismuth alloy powder prepared by adopting the electrostatic self-assembly process has positive charges, and electrostatic attraction with UiO-66 metal organic framework materials with carboxyl negative charges, and the conductive filler is uniformly distributed in the pore channels of the UiO-66, as shown in figure 1. The problem of the random distribution state of the conductive particles of the traditional mechanical mixed conductive filler is solved, and the conductive filler has the advantages of stable anisotropism and no short circuit risk between adjacent electrodes with micro-spacing; 3) The MOF material UiO-66 has a large number of carboxyl functional groups on the surface, can form hydrogen bond combination with the polymer matrix epoxy resin and the curing agent in the crosslinking curing process, effectively improves the connection interface strength of the conductive filler and the polymer matrix, ensures that the interface can be kept stable in the long-time service process, and reduces the fatigue failure risk.
Drawings
FIG. 1 is a schematic diagram of the process for preparing the anisotropic conductive adhesive of the present invention.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific embodiments and the accompanying drawings.
Example 1 preparation of Anisotropic conductive adhesive
The conductive tin adhesive comprises the following components in percentage by mass: the mass percentage of the conductive filler is 20 percent, and the mass percentage of the polymer matrix is 80 percent. Wherein Sn99.3Bi0.7, MOF materials with the grain diameter of 1.0-2.0 mu m of tin-bismuth alloy powder in the conductive filler are UiO-66, and the mass percentage of the two materials is 1:1; wherein the polymer matrix comprises the following components in percentage by mass: the epoxy resin is bisphenol A resin E51 with the content of 60.0 percent; the curing agent is SC10208A latent curing agent with the content of 5.0 percent; the surfactant is TRITON DF-20 with the content of 1.0 percent; the organic acid activator is mixed dibasic acid (Sokalan DCS) with the content of 5.0 percent; the antioxidant is Irganox1076, and the content is 1.0%; the diluent is acetone, and the content is 3.0%. The preparation process mainly comprises the following steps:
The step (1) comprises: firstly, tin-bismuth alloy powder with the T10 particle size prepared by gas atomization is added into ethanol solution, and the addition amount is according to the proportion of 1g of powder to 1000ml of solution. And (3) stirring the powder-added solution for 30min under the ultrasonic condition of 1KW by using a magnetic stirrer, adding 3-aminopropyl triethoxysilane, continuing ultrasonic stirring for 6h, and carrying out vacuum suction filtration after full reaction to prepare the tin-bismuth alloy powder with positive charges on the surface. The tin-bismuth alloy powder with positive charges and UiO-66 are added into the water solution, wherein the mass ratio of the tin-bismuth alloy powder to the UiO-66 is 1:1, and the ratio of the composite powder to the water solution is 1g of powder to 30 ml. And (3) in a hydrothermal reaction kettle, carrying out vacuum suction filtration after reacting for 12 hours at 80 ℃, and then freeze-drying the mixed powder to obtain the UiO-66 composite powder conductive filler containing the tin-bismuth alloy.
The step (2) comprises: firstly, adding epoxy resin, a diluent and an antioxidant into a beaker according to the adding proportion, magnetically stirring for 30min at 40 ℃, then sequentially adding a curing agent coated by microcapsules, an organic acid active agent and a surfactant, and magnetically stirring for 30min at room temperature. And (3) adding the conductive filler prepared in the step (1) under the magnetic stirring condition assisted by 1KW ultrasonic, magnetically stirring for 30min, adding the conductive tin glue into a vacuum drying oven, and performing degassing treatment at the temperature of 40 ℃ for 1h to obtain the anisotropic conductive tin glue.
Example 2 preparation of Anisotropic conductive adhesive
The conductive tin adhesive comprises the following components in percentage by mass: the mass percentage of the conductive filler is 25 percent, and the mass percentage of the polymer matrix is 75 percent. Wherein the tin-bismuth alloy powder in the conductive filler is Sn58Bi42 with the grain diameter of 1.0-2.0 mu m, the MOF material is UiO-66, and the mass percentage of the two is 1:1; wherein the polymer matrix comprises the following components in percentage by mass: the epoxy resin is bisphenol A resin E44 with the content of 80.0 percent; the curing agent is a Henkel Latent curing agent, and the content is 20.0%; the surfactant is TRITON DF-20 with the content of 3.0 percent; the organic acid activator is mixed dibasic acid (Sokalan DCS) with the content of 7.0 percent; the antioxidant is IRGANOX 245, and the content is 5.0%; the diluent is acetone, and the content is 5.0%. The preparation process mainly comprises the following steps:
The step (1) comprises: firstly, tin-bismuth alloy powder with the T10 particle size prepared by gas atomization is added into ethanol solution, and the addition amount is according to the proportion of 1g of powder to 1000ml of solution. And (3) stirring the powder-added solution for 30min under the ultrasonic condition of 1KW by using a magnetic stirrer, adding 3-aminopropyl triethoxysilane, continuing ultrasonic stirring for 6h, and carrying out vacuum suction filtration after full reaction to prepare the tin-bismuth alloy powder with positive charges on the surface. The tin-bismuth alloy powder with positive charges and UiO-66 are added into the water solution, wherein the mass ratio of the tin-bismuth alloy powder to the UiO-66 is 1:1, and the ratio of the composite powder to the water solution is 1g of powder to 30 ml. And (3) in a hydrothermal reaction kettle, carrying out vacuum suction filtration after reacting for 12 hours at 80 ℃, and then freeze-drying the mixed powder to obtain the UiO-66 composite powder conductive filler containing the tin-bismuth alloy.
The step (2) comprises: firstly, adding epoxy resin, a diluent and an antioxidant into a beaker according to the adding proportion, magnetically stirring for 30min at 40 ℃, then sequentially adding a curing agent coated by microcapsules, an organic acid active agent and a surfactant, and magnetically stirring for 30min at room temperature. And (3) adding the conductive filler prepared in the step (1) under the magnetic stirring condition assisted by 1KW ultrasonic, magnetically stirring for 30min, adding the conductive tin glue into a vacuum drying oven, and performing degassing treatment at the temperature of 40 ℃ for 1h to obtain the anisotropic conductive tin glue.
Example 3 preparation of Anisotropic conductive adhesive
The conductive tin adhesive comprises the following components in percentage by mass: the mass percentage of the conductive filler is 23 percent, and the mass percentage of the polymer matrix is 77 percent. Wherein the tin-bismuth alloy powder in the conductive filler is Sn42Bi57.6Ag0.4 with the grain diameter of 1.0-2.0 mu m, the MOF material is UiO-66, and the mass percentage of the tin-bismuth alloy powder and the MOF material is 1:1; wherein the polymer matrix comprises the following components in percentage by mass: the epoxy resin is bisphenol F type epoxy resin DER351 with the content of 70.0 percent; the curing agent is Microencapsulated of Dow Chemical, and the content is 12.0%; the surfactant is TRITON DF-20 with the content of 2.0 percent; the organic acid activator is mixed dibasic acid (Sokalan DCS) with the content of 6.0 percent; the antioxidant is IRGANOX 245, and the content is 3.0%; the diluent is ethanol with the content of 4.5 percent. The preparation process mainly comprises the following steps:
The step (1) comprises: firstly, tin-bismuth alloy powder with the T10 particle size prepared by gas atomization is added into ethanol solution, and the addition amount is according to the proportion of 1g of powder to 1000ml of solution. And (3) stirring the powder-added solution for 30min under the ultrasonic condition of 1KW by using a magnetic stirrer, adding 3-aminopropyl triethoxysilane, continuing ultrasonic stirring for 6h, and carrying out vacuum suction filtration after full reaction to prepare the tin-bismuth alloy powder with positive charges on the surface. The tin-bismuth alloy powder with positive charges and UIO-66 are added into the water solution, wherein the mass ratio of the tin-bismuth alloy powder to the UiO-66 is 1:1, and the ratio of the composite powder to the water solution is 1g of powder to 30 ml. And (3) in a hydrothermal reaction kettle, carrying out vacuum suction filtration after reacting for 12 hours at 80 ℃, and then freeze-drying the mixed powder to obtain the UiO-66 composite powder conductive filler containing the tin-bismuth alloy.
The step (2) comprises: firstly, adding epoxy resin, a diluent and an antioxidant into a beaker according to the adding proportion, magnetically stirring for 30min at 40 ℃, then sequentially adding a curing agent coated by microcapsules, an organic acid active agent and a surfactant, and magnetically stirring for 30min at room temperature. And (3) adding the conductive filler prepared in the step (1) under the magnetic stirring condition assisted by 1KW ultrasonic, magnetically stirring for 30min, adding the conductive tin glue into a vacuum drying oven, and performing degassing treatment at the temperature of 40 ℃ for 1h to obtain the anisotropic conductive tin glue.
Detection examples
The conventional conductive adhesive prepared by using the conventional conductive filler and the polymer matrix is used as a comparative example (the conductive filler is conductive microspheres with the diameter of 5 mu m, the core material is polystyrene, the shell material is silver, the addition amount is 25 wt%, the polymer matrix is polyurethane, the addition amount is 75 wt%) for hot-pressing, curing and packaging, and the resistance and the peeling strength after packaging are tested, and the results are shown in the following table:
| Sample name | Curing temperature | Curing pressure | Resistor | Peel strength of |
| Common conductive adhesive | 150℃ | 2MPa | 1.17Ω | 4.0N/cm |
| Example 1 | 150℃ | 2MPa | 0.32Ω | 8.9N/cm |
| Example 2 | 150℃ | 2MPa | 0.16Ω | 11.3N/cm |
Claims (4)
1. An anisotropic conductive tin glue is composed of conductive filler and polymer matrix; 20-25% of conductive filler and 75-80% of polymer matrix by mass percent;
The conductive filler consists of tin-bismuth alloy powder and MOF material with the mass percentage of 1:1; the tin-bismuth alloy powder comprises but is not limited to one of the following alloys Sn99.3Bi0.7, sn58Bi42 and Sn42Bi57.6Ag0.4, wherein the grain size of the tin-bismuth alloy powder is of the grade T10, and the grain size range is 1.0-2.0 mu m; the MOF material is UiO-66;
the polymer matrix consists of the following components in percentage by mass:
2. The anisotropic conductive solder paste according to claim 1, wherein: the epoxy resin is selected from any one or more of bisphenol A type resin E51, bisphenol A type resin E44 and bisphenol F type epoxy resin DER 351;
The curing agent is a microcapsule coated curing agent and is selected from any one or more of SC10208A Latent curing agent, henkel's Latent curing agent and Dow Chemical's Microencapsulated curing agent;
the surfactant is TRITON DF-20 surfactant;
the organic acid activator is mixed dibasic acid (Sokalan DCS);
The antioxidant is selected from any one or more of antioxidant Irganox1076, IRGANOX 245 and IRGANOX 1330;
The diluent is any one or more of anhydrous acetone and ethanol.
3. The method for preparing the anisotropic conductive tin paste according to claim 1 or 2, comprising the following steps:
(1) Preparing a metal organic framework Material (MOF) and low Wen Xibi alloy conductive filler based on electrostatic self-assembly;
(2) And (3) preparing a polymer matrix, and mixing the conductive filler with the polymer matrix to prepare the anisotropic conductive adhesive.
4. The method for preparing anisotropic conductive tin paste according to claim 3, wherein the step (1): firstly, adding tin-bismuth alloy powder with the particle size of T10 prepared by gas atomization into ethanol solution, wherein the adding amount is according to the proportion of 1g of powder to 1000ml of solution; stirring the solution added with the powder for 30min under the ultrasonic condition of 1KW by using a magnetic stirrer, adding 3-aminopropyl triethoxysilane, continuing ultrasonic stirring for 6h, and carrying out vacuum suction filtration after full reaction to prepare tin-bismuth alloy powder with positive charges on the surface; adding the tin-bismuth alloy powder with positive charges and UiO-66 into an aqueous solution, wherein the mass ratio of the tin-bismuth alloy powder to the UiO-66 is 1:1, and the ratio of the composite powder to the aqueous solution is 1g of powder to 30 ml; in a hydrothermal reaction kettle, carrying out vacuum suction filtration after reacting for 12 hours at 80 ℃, and then freeze-drying the mixed powder to obtain the UiO-66 composite powder conductive filler containing the tin-bismuth alloy;
The step (2) is as follows: firstly, adding epoxy resin, a diluent and an antioxidant into a beaker according to an adding proportion, magnetically stirring for 30min at 40 ℃, then sequentially adding a curing agent, an organic acid active agent and a surfactant coated by microcapsules, and magnetically stirring for 30min at room temperature; and (3) adding the composite powder conductive filler prepared in the step (1) under the magnetic stirring condition assisted by 1KW ultrasonic, magnetically stirring for 30min, adding the conductive tin glue into a vacuum drying oven, and carrying out degassing treatment at the temperature of 40 ℃ for 1h to obtain the anisotropic conductive tin glue.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410482286.5A CN118325505A (en) | 2024-04-22 | 2024-04-22 | Anisotropic conductive tin adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410482286.5A CN118325505A (en) | 2024-04-22 | 2024-04-22 | Anisotropic conductive tin adhesive and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118325505A true CN118325505A (en) | 2024-07-12 |
Family
ID=91775627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410482286.5A Pending CN118325505A (en) | 2024-04-22 | 2024-04-22 | Anisotropic conductive tin adhesive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118325505A (en) |
-
2024
- 2024-04-22 CN CN202410482286.5A patent/CN118325505A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100290993B1 (en) | Semiconductor device, wiring board for mounting semiconductor and method of production of semiconductor device | |
| JP3678547B2 (en) | Multilayer anisotropic conductive adhesive and method for producing the same | |
| JP4848674B2 (en) | Resin metal composite conductive material and method for producing the same | |
| JP2895872B2 (en) | Anisotropic conductive material, anisotropic conductive adhesive, method for electrically connecting electrodes using the anisotropic conductive adhesive, and electric circuit board formed by the method | |
| KR101234597B1 (en) | method for bonding flip chip and structure at the same | |
| US20020005247A1 (en) | Electrically conductive paste materials and applications | |
| TWI323901B (en) | Anisotropic conductive material | |
| JP2011192651A (en) | Anisotropic conductive film, connection method, and connection structure | |
| JP2004507089A (en) | Highly reliable non-conductive adhesive for non-solder flip chip bonding and flip chip bonding method using the same | |
| EP2592127B1 (en) | Anisotropic conductive adhesive, process for producing same, connection structure, and process for producing same | |
| JPH0346774A (en) | Anisotropic conductive adhesive, method of electrical connection between electrodes using such adhesive, and electric circuit base formed in such method | |
| CN105567112A (en) | Anisotropic conductive adhesive and preparation method thereof | |
| JPH0570750A (en) | Conductive adhesive | |
| JP2006339160A (en) | Thermosetting circuit connection member, connection structure of electrode using it and connection method of electrode | |
| Lu et al. | Electrically conductive adhesives (ECAs) | |
| CN118325505A (en) | Anisotropic conductive tin adhesive and preparation method thereof | |
| JP4387653B2 (en) | Metal fine particles and adhesive, film and electric circuit board using the fine particles | |
| JP4175347B2 (en) | Method for producing anisotropic conductive adhesive film | |
| JP2001052780A (en) | Electric connector and its manufacture | |
| JP5210236B2 (en) | Conductive fine particles, anisotropic conductive material, and connection structure | |
| JP5143329B2 (en) | Manufacturing method of circuit connection body | |
| JPH09153516A (en) | Semiconductor device and ic chip inspecting method | |
| JPH087658A (en) | Anisotropic conductive adhesive film | |
| JP5438450B2 (en) | Conductive fine particles, anisotropic conductive material, and connection structure | |
| JP2004164910A (en) | Anisotropic conductive adhesive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |